WO2019021542A1 - Tychite particles, method for producing tychite particles, and use of tychite particles - Google Patents

Abstract

The present invention provides Thaichaite particles capable of achieving high functionalization of products by micronization of particles, a method for producing the same, and a resin composition containing the Thaichaite particles and a molded article thereof. The present invention relates, in one embodiment, to tie chait particles having a BET specific surface area of 0.5 m ² / g or more. It is preferable that the 50% cumulative diameter (d ₅₀ ) on a volume basis in the particle size distribution obtained by the laser diffraction type particle size distribution analyzer of the tie particles is 15 μm or less. The cumulative 90% diameter (d ₉₀ ) on a volume basis in the particle size distribution obtained by the laser diffraction type particle size distribution analyzer of the tie particles is preferably 30 μm or less.

Description

Thaichaite particle, method of producing Thaichaite particle and use of Thaichaite particle

The present invention relates to Thaichaite particles, a process for producing Thaichaite particles and the use of Thaichaite particles.

Thailand, which is a natural and rare mineral, has properties such as high thermal conductivity, low refractive index, high dispersion, low Mohs hardness, water resistance, etc., and is expected to be used in various applications. For example, a technology has also been proposed in which tie chaiting is applied to a heat conductive filler (Patent Document 1).

JP, 2017-7904, A

In recent years, in order to achieve high added value of products, high functionality, miniaturization, thinning and the like of products have been promoted. In order to enhance the functionality of products incorporating a tie chait, it is desirable to reduce the particle size in order to fully exhibit the properties possessed by the tie chait.

However, in the case of natural Thailand, the average particle size is several hundred μm to several mm, and even with the above-mentioned heat conductive filler technology, the average particle size is several tens μm to several hundreds μm, leaving room for further reduction in particle size. ing.

An object of the present invention is to provide a tie chait particles capable of enhancing the function of the product by micronization of the particles, a method for producing the same, and a resin composition containing the tie chait particles and a molded article thereof.

As a result of intensive investigations, the inventor of the present invention has found that the problems described above can be solved by adopting the following configuration, and the present invention has been accomplished.

The present invention relates, in one embodiment, to tie chait particles having a BET specific surface area of 0.5 m ² / g or more.

Since the tie chait particles have a BET specific surface area in a predetermined range due to the miniaturization of the particles, it is possible to highly functionalize the product incorporating the small size caustic tie particles.

It is preferable that a 50% cumulative diameter (d ₅₀ ) on a volume basis in the particle size distribution obtained by the laser diffraction type particle size distribution analyzer of the tie-chaet particles is 15 μm or less. By miniaturizing the particles of the tie to the above-described particle size, it is possible to further enhance the functionality of the product.

It is preferable that a 90% cumulative diameter (d ₉₀ ) on a volume basis in the particle size distribution obtained by the laser diffraction type particle size distribution analyzer of the tie-chaet particles is 30 μm or less. As a result, it is possible to miniaturize the particles even when viewed as a whole of the particles.

In the case of the particles, it is preferable that the particles have an octahedral shape. Thereby, high dispersibility can be exhibited. In addition, it is also possible to pulverize the particles of the large-sized titanite particles to make the particles finer. However, when the particle size is reduced by pulverization, the particle shape includes an indeterminate form, and there is a possibility that a predetermined BET specific surface area can not be obtained or the dispersibility is lowered.

The present invention relates, in one embodiment, to a method for producing Thaichaite particles, comprising a mixing step of mixing a magnesium raw material and a sodium raw material,
The magnesium source comprises basic magnesium carbonate,
The present invention relates to a method for producing taichaite particles, wherein the ratio of the number of moles of sulfate ions to the number of moles of magnesium ions in the mixture is 1 or more.

According to the said manufacturing method, since basic magnesium carbonate is used as a magnesium raw material, micronization of a particle of a tie can be promoted. In addition, by setting the sulfate ion to a stoichiometric amount or more with respect to the magnesium ion, it is suppressed that the basic magnesium carbonate which is the raw material is left unreacted and that byproducts such as aiterite are generated. Thus, most of the particles can be efficiently formed as a single phase of a tie-chait. In addition, although the mechanism of micronization of Thaichaite particles by use of basic magnesium carbonate is not certain, it is guessed as follows. In the process of forming a conventional tie, it is believed that the magnesium source once passes through the basic magnesium carbonate phase as a precursor of the tie. In the said manufacturing method, by using basic magnesium carbonate as a magnesium raw material, since the speed of the phase change to a tie can be raised, many small crystals can be generated and it can be refined.

In the said manufacturing method, it is preferable to perform the said mixing process under heating. The titanium particles can be produced only by mixing and reacting the above-mentioned specific magnesium source and sodium source. However, depending on the conditions, a magnesium carbonate phase may be formed on the particle surface. By conducting the mixing step under heating, the magnesium carbonate phase formed on the particle surface can be efficiently converted to the tie-chaite phase.

In the mixing step, the heating temperature is preferably 70 ° C. or more. This can further accelerate the conversion of the magnesium carbonate phase to the tie phase of the particle surface.

It is preferable that the sodium source contains sodium sulfate. Thereby, solid solution of sodium ion and sulfate ion in basic magnesium carbonate is promoted, and conversion of magnesium carbonate phase to tie chait phase can be efficiently promoted.

The ratio of the number of moles of sodium ions to the number of moles of magnesium ions in the mixture is preferably 5 or more and 20 or less. This makes it possible to more efficiently promote the conversion of the magnesium carbonate phase to the tie phase.

The present invention relates to, in another embodiment, a resin composition in which 0.1 to 600 parts by mass of the particles of the present invention are added to 100 parts by mass of a resin.

The resin is preferably at least one of an acrylic resin, an ABS resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polycarbonate resin, a polyphenylene resin, a polyester resin, and a polyamide resin. .

The present invention relates, in a further embodiment, to a molded article comprising the resin composition.

It is a SEM photograph of Thaichaite particles of Example 1 of the present invention. The IR spectrum of Example 1 of the present invention, Comparative Example 1 and EVA resin alone is shown.

<Thaichaite particle>
The particles of the tie chait are particles mainly composed of the tie chait. Tychite is typically represented by Na ₆ Mg ₂ (SO ₄ ) (CO ₃ ) ₄ , and the molar ratio in the composition formula of Na / Mg is Na / Mg = 3. The tie cell unit cell has a cubic crystal structure.

In the tie particle, the particle is preferably octahedral in shape. Thereby, high dispersibility at the primary particle level can be exhibited. Moreover, since high dispersibility can be exhibited, mixing of the air layer can be excluded even when the resin and the particles of the tie are mixed, and the transparency of the resin mixture can be improved. In addition, particles of an irregular shape, a spherical shape, a tetrahedron, a hexahedron, or the like may be included in part of the tie particles. The amount of octahedral particles is preferably at least 50% by weight of the total particles of the tie.

The BET specific surface area of the tie particles may be 0.5 m ² / g or more. The BET specific surface area is preferably 1 m ² / g or more, and more preferably 1.5 m ² / g or more. The fine particles of the particles have a BET specific surface area in the above range due to the reduction of the particles, so that it is possible to enhance the functionality of products incorporating the particles of the fine particles. Note that the BET specific surface area, from the viewpoint of dispersibility and properties exhibited, preferably ^{20 m} 2 / g or less, ^{10 m} 2 / g or less is more preferable.

The cumulative 50% diameter (d ₅₀ ) on a volume basis in the particle size distribution obtained by the laser diffraction type particle size distribution analyzer of the tie-chaite particles is preferably 15 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, 8 μm The following are particularly preferred. In light of securing the dispersibility, the cumulative 50% diameter (d ₅₀ ) is preferably 0.5 μm or more, and more preferably 1 μm or more. By miniaturizing the particles of the tie to the above-described particle size, it is possible to further enhance the functionality of the product.

The cumulative 90% diameter (d ₉₀ ) on a volume basis in the particle size distribution obtained by the laser diffraction type particle size distribution analyzer of the tie-chaite particles is preferably 30 μm or less, more preferably 25 μm or less, and still more preferably 20 μm or less. The cumulative 90% diameter (d ₉₀ ) is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of securing the dispersibility. As a result, it is possible to miniaturize the particles even when viewed as a whole of the particles.

The particles of the tie are transparent to translucent and optical applications are also possible. The refractive index of the tie particles is preferably 1.50 or more and 1.52 or less. A common resin also has the same refractive index, so that the transparency can be maintained by mixing with such a resin, and the functionalization of the product can be promoted.

True density of Taichaito particles is not particularly limited, it is preferably 3.5 g / cm ³ or less, more preferably 3 g / cm ³ or less, further not less 2.8 g / cm ³ or less preferable. The true density is preferably 2 g / cm ³ or more, more preferably 2.5 g / cm ³ or more. As a result, even if the particles of the present invention are compounded with resins or the like at a high filling rate, the final product can be reduced in weight because the true density is relatively small.

The tie particles may contain impurities depending on the production method and the like. For example, compounds of metals such as iron, copper, manganese, chromium, cobalt, nickel and vanadium. The content of these impurities is preferably 0.5% by mass or less in terms of metal.

The tie-chite particles of this embodiment have properties such as high thermal conductivity, transparency, low refractive index, high dispersibility, ease of processing, heat resistance, water resistance, etc. It can apply suitably. The application is not particularly limited, and suitable examples include fillers for artificial marble, antiblocking agents, infrared absorbers, abrasives, resin hardness imparting agents (reinforcement materials), light diffusing agents, alkali catalysts and the like.

<Production method of Thaichaite particle>
The method for producing tie-chite particles according to the present embodiment includes a mixing step of mixing a magnesium raw material and a sodium raw material, wherein the magnesium raw material contains basic magnesium carbonate, and the molar number of magnesium ions in the mixture is the number of moles of sulfate ion. The ratio to the number is 1 or more.

In the mixing step, the magnesium source and the sodium source are mixed. The sodium source is not particularly limited as long as it is a water-soluble sodium compound, and examples thereof include sodium chloride, sodium sulfate, sodium carbonate, sodium hydrogencarbonate, sodium bicarbonate, sodium hydroxide, sodium nitrate, sodium acetate, sodium phosphate and the like. . The said sodium raw material can be used combining 1 type, or 2 or more types. Sodium chloride, sodium sulfate, sodium carbonate and sodium hydrogen carbonate are preferable from the viewpoint of easy availability and easy progress of the reaction.

The sodium source preferably contains sodium sulfate. Thereby, solid solution of sodium ion and sulfate ion in basic magnesium carbonate is promoted, and conversion of magnesium carbonate phase to tie chait phase can be efficiently promoted.

In the manufacturing method of this embodiment, basic magnesium carbonate is used as a magnesium raw material. This makes it possible to promote miniaturization of the particles of the tie. Other magnesium compounds can also be used in combination, and examples thereof include magnesium chloride, magnesium sulfate, neutral magnesium carbonate, anhydrous magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium nitrate, magnesium acetate, magnesium phosphate and the like. You may use seawater, irrigation etc. as a magnesium raw material.

Although the above-mentioned compounds can be used without limitation as sodium source and magnesium source, they contain carbonate compounds and sulfate compounds as carbonate ion (CO ₃ ^2- ) sources and sulfate ion (SO ₄ ^2- ) sources, respectively. It is preferred that the

In this embodiment, the ratio of the number of moles of sulfate ions to the number of moles of magnesium ions (SO ₄ ²⁻ / Mg ²⁺ ratio) in the mixture obtained by mixing the magnesium source and the sodium source is 1 or more. The SO ₄ ²⁻ / Mg ²⁺ ratio is preferably 1.2 or more, more preferably 1.5 or more. By setting the sulfate ion to a stoichiometric amount or more with respect to the magnesium ion, it is suppressed that the basic magnesium carbonate which is the raw material is left unreacted, or generation of byproducts such as aiterite is caused. , Most of the particles can be efficiently formed as a single phase of a tie-chait. If the SO ₄ ²⁻ / Mg ²⁺ ratio is too high, unreacted sulfate ion (SO ₄ ²⁻ ) will remain in excess, and it will tend to remain as an impurity even after washing with water, so SO ₄ ²⁻ / Mg ²⁺ The ratio is preferably 10 or less, more preferably 5 or less.

The ratio (Na ⁺ / Mg ²⁺ ratio) of the number of moles of sodium ions to the number of moles of magnesium ions in the mixture is preferably 5 or more and 20 or less, and more preferably 6 or more and 10 or less. This makes it possible to more efficiently promote the conversion of the magnesium carbonate phase to the tie phase. When the Na ⁺ / Mg ²⁺ ratio is too small, crystal growth is difficult to progress, and when the Na ⁺ / Mg ²⁺ ratio is too large, the particle size tends to be large.

The mass ratio of the solid to the solvent at the time of charging in the mixing step is not particularly limited as long as the reaction can be carried out, but from the viewpoint of reaction promotion, the solid is preferably 50 to 500 parts by mass with respect to 100 parts by mass of the solvent. 100 to 300 parts by mass is more preferable. Within the above range, crystal growth can be efficiently promoted. When each raw material is excessively charged, the reaction may be nonuniform and the particle size may vary.

As a solvent, water is preferable from the viewpoint of the solubility of the raw material. Other than water, organic solvents such as alcohol and acetone can be used as long as the reaction proceeds. As the solvent, either water alone or a mixture of water and an organic solvent can be suitably used.

When adding each raw material, the sodium raw material and the magnesium raw material are mixed while being stirred in order to ensure uniformity. The stirring speed may be set from the viewpoint of the target particle diameter and production efficiency, preferably 200 to 800 rpm, and more preferably 300 to 700 rpm. Furthermore, in order to miniaturize the particles, grinding media such as glass beads may be added together at the time of stirring and mixing. The input amount and size of the grinding media can be appropriately set in consideration of the target particle size and production efficiency of the particles.

The temperature for mixing may be either room temperature or under heating. Crystal growth can be promoted even by stirring and mixing at room temperature. When the reaction is performed at room temperature, the mixing time is preferably 0.01 to 24 hours, more preferably 0.02 to 12 hours, and still more preferably 0.03 to 6 hours.

In the present embodiment, the mixing step is preferably performed under heating. The tie particles can be produced simply by mixing and reacting a specific magnesium source and a sodium source as described above. However, depending on the conditions, a magnesium carbonate phase may be formed on the particle surface. By conducting the mixing step under heating, the magnesium carbonate phase formed on the particle surface can be efficiently converted to the tie-chaite phase.

In the mixing step, the heating temperature is preferably 70 ° C. or more, more preferably 80 or more, still more preferably 90 ° C. or more, and particularly preferably 100 ° C. or more. This can further accelerate the conversion of the magnesium carbonate phase to the tie phase of the particle surface. The temperature of the heating is preferably 200 ° C. or less, more preferably 120 ° C. or less, from the viewpoint of energy saving.

When performing a mixing process under heating, the timing in particular of heating is not limited. The raw materials may be mixed and then heated, or the raw materials may be introduced into the heated solvent. When mixing and heating the raw materials, it is preferable to stir at room temperature for about 1 to 10 minutes to dissolve the raw materials and then to heat. When the mixing step is performed under heating, the mixing time (the time from the start of heating or the addition of the raw material to the end of the reaction) is preferably 0.01 to 24 hours, more preferably 0.02 to 12 hours, and 0.03 to 6 Time is even more preferred.

When the mixing step is carried out under heating, it may be carried out under normal pressure or under pressure. From the viewpoint of efficiently forming a single phase of tie chait, it is preferable to carry out a hydrothermal treatment by mixing under heating and pressing. The hydrothermal treatment method is not particularly limited, but it is usually carried out in a heat resistant container such as an autoclave. The pressure in the container at the time of the hydrothermal treatment is not particularly limited, but is preferably 0.1 to 10 MPa, and more preferably 0.1 to 5 MPa. When the hydrothermal treatment pressure is in this range, the crystal growth and the average particle size can be controlled in an appropriate range.

The slurry obtained after the mixing step is preferably vacuum-filtered to be separated into a solid (cake) containing particulate particles and a filtrate, and thoroughly washed with water at least 20 times the solid content. There is no particular limitation on the number of times of washing. Thereby, water-soluble impurities contained in the slurry can be removed. The solid after washing with water is dried in an oven or the like at 100 to 150 ° C. for 1 to 24 hours, and if necessary, the dried solid content is dry-crushed to obtain desired tiechaite particles.

The method for producing tiechatite particles of the present embodiment may include steps other than the steps described above. For example, after the mixing step, it may include a step of surface-treating the surface-treating agent by a known method, if necessary.

As the surface treatment agent, known compounds used for the application can be used. The surface treatment includes higher fatty acids, higher fatty acid alkaline earth metal salts, silane coupling agents, higher fatty acid esters consisting of fatty acids and polyhydric alcohols, higher fatty acid amides, and alcohol phosphoric acids consisting of phosphoric acid and higher alcohols. It is preferably carried out using at least one selected from the group consisting of esters. Inorganic materials generally have low hydrophilicity to the compounding resin and the like because the surface is hydrophilic, but according to this configuration, the tie particles are treated with a predetermined surface treatment agent, so the resin or the like is treated. It is possible to improve the dispersibility, to improve the adhesion with the resin component, and to maintain or improve the physical properties of the resin composition and the molded article by this. In addition, surfactants can also be used as surface treatment agents.

Examples of higher fatty acids include stearic acid, oleic acid, palmitic acid, linoleic acid, lauric acid, caprylic acid, behenic acid, montanic acid and the like. Examples of higher fatty acid metal salts include, for example, stearates, oleates, palmitates, linoleates, laurates, laurates, caprylates, behenates, montanates, etc. Na, K, Al, Ca, Mg, Zn, Ba etc. are mentioned.

As the silane coupling agent, for example, methacryloxy type such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, etc. Vinyl compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltritrixsilane Epoxy systems such as ethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyl Amino systems such as dimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Can be mentioned.

As higher fatty acid esters, for example, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erbate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, isopropyl palmitate, There are monoesters such as octyl palmitate, coconut fatty acid octyl ester, octyl stearate, special beef tallow fatty acid octyl ester, lauryl laurate, long stearyl stearate, long chain fatty acid higher alcohol ester, behenyl acid benylate, cetyl myristate Also, for example, neopentyl polyol long chain fatty acid ester, partial esterified product of neopentyl polyol long chain fatty acid ester, neopentyl polyol fatty acid ester, neopentyl poly Lumpur medium chain fatty acid esters, neopentyl polyol C9 chain fatty acid esters, dipentaerythritol long chain fatty acid esters, heat-resistant special higher fatty acid esters such as complex medium chain fatty acid esters.

As alcohol phosphates, phosphates of mono- and di-saturated alcohols such as mono-stearyl acid phosphate, di-stearyl acid phosphate, mono-lauryl acid phosphate, di-lauryl acid phosphate, mono- Myristyl acid phosphate, di-myristyl acid phosphate, mono-palmityl acid phosphate, di-palmityl acid phosphate, mono-alkyl acid phosphate, di-alkyl acid phosphate, mono-gel acid phosphate Fate, di-velchel acid phosphate, mono-lignoceryl acid phosphate, di-lignoceryl acid phosphate, etc., and mono- and di-saturated alcohol phosphate esters It may also be used mixtures thereof.

Examples of higher fatty acid amides include stearic acid amides, oleic acid amides, palmitic acid amides, linoleic acid amides, lauric acid amides, caprylic acid amides, behenic acid amides, montanic acid amides and the like. Examples of higher alcohols include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and the like. As a hardened oil, a beef tallow hardened oil, a castor hardened oil etc. are mentioned, for example.

As the surfactant, nonionic surfactants can be suitably used. As nonionic surfactants, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, etc., polyoxyethylene Polyoxyethylene alkyl aryl ethers such as nonylphenyl ether; polyoxyethylene derivatives; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate Sorbitan fatty acid esters such as sorbitan distearate; polyoxyethylene sorbitan monolaurate, polyoxy acids Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, etc. polyoxyethylene sorbitan Fatty acid ester; polyoxyethylene sorbitol fatty acid ester such as tetraoleate polyoxyethylene sorbit; glycerol fatty acid ester such as glycerol monostearate, glycerol monooleate, self-emulsifying glycerol monostearate; polyethylene glycol monolaurate, polyethylene glycol Monostearate, polyethylene glycol distearate, polyethylene glycol Polyoxyethylene fatty acid esters, such as oleate polyoxyethylene alkylamine, polyoxyethylene hardened castor oil, alkyl alkanol amide.

In order to perform surface treatment of the particles of the tie using such a surface treatment agent, a known dry method or wet method can be applied. As a dry method, it is sufficient to add powder of lynchite particles in a liquid, emulsion or solid state with stirring using a mixer such as a Henschel mixer, and sufficiently mix it under heating or non-heating. As a wet method, a powder of Thailandite particles is added to a non-aqueous solvent slurry in a solution state or an emulsion state, and mechanically mixed at, for example, a temperature of about 1 to 100 ° C. Should be removed. Examples of non-aqueous solvents include isopropyl alcohol and methyl ethyl ketone. The amount of addition of the surface treatment agent can be selected appropriately, but when the dry method is adopted, the surface treatment level tends to be uneven compared to the wet method, so a slightly larger addition amount is preferable to the wet method. Good. Specifically, the range of 0.1 to 10 parts by mass is preferable, and the range of 0.5 to 5 parts by mass is more preferable with respect to 100 parts by mass of the particles of the tie. When a wet method is employed, a range of 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass of the particles from the viewpoint of sufficient surface treatment and aggregation prevention of the surface treatment agent, and 0.5 to 5 parts by mass The range is more preferred.

The surface-treated Thaichaite particles can be provided, as required, with water washing, dehydration, granulation, drying, grinding, classification and the like.

<Resin composition>
The resin composition in the present embodiment is a resin composition in which tie particles are mixed with a resin. As resin, a well-known thing can be suitably set according to a use etc. For example, acrylic resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, polyethylene resin (linear polyethylene, low density polyethylene, high density polyethylene), polypropylene resin (homopolypropylene, propylene-ethylene random copolymer) Polymer, propylene-ethylene block copolymer, copolymer of propylene and other small amount of α-olefin), ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, polystyrene resin, polybutadiene resin Isoprene resin, ethylene-propylene rubber, polyolefin such as ethylene-propylene rubber, polyester resin (polybutylene terephthalate, polyethylene terephthalate), polyamide resin, polyacetal resin, syndiotactic resin Black polystyrene, polyphenylene resin (polyphenylene sulfide, polyphenylene ether, polyphenylene oxide), liquid crystal polymer, polyether ketone resin, polyether nitrile resin, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyarylate There are system resins, polyamideimide resins, polyetherimide resins, and thermoplastic polyimide resins. From the viewpoint of affinity with the inorganic material, polyolefin is preferred. In addition, it is also possible to use these resin individually or in multiple. Among them, the resin is at least one of acrylic resin, ABS resin, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, polyphenylene resin, polyester resin and polyamide resin. preferable.

In the above-mentioned resin composition, 0.1 to 600 parts by mass of Thailand particles are blended with 100 parts by mass of resin, preferably 0.2 to 500 parts by mass, more preferably 0.2 parts by mass. More than 0.5 parts by weight and less than 300 parts by weight are preferably blended. The tie particles of this embodiment are controlled to make the average particle size relatively small, and thus the functionality of the resin can be improved.

In the resin composition, other additives may be blended in addition to the above components as long as the effects of the present invention are not impaired. As such additives, for example, antioxidants, antistatic agents, pigments, foaming agents, plasticizers, fillers, reinforcing agents, flame retardants, crosslinking agents, light stabilizers, ultraviolet light absorbers, lubricants, lubricants, Antiaging agents, weathering agents, coloring agents, curing accelerators and the like can be mentioned. One or more of these additives may be blended. The compounding amount of the other additive is not particularly limited from the viewpoint of not impairing the effect of the present invention, but it is preferable to be compounded in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin.

The mixing and filling of the particles and the resin can be obtained by a known mixing method or filling method, for example, a roll kneader, a Banbury mixer, a kneader, a single-screw kneader, a twin-screw kneader, a centrifugal kneader, It mixes uniformly by a revolution rotation type kneader etc. It can also knead | mix while removing the bubble in a resin composition using the apparatus which added the degassing effect. The obtained resin composition may be subjected to a crosslinking reaction by various methods such as heat treatment or electron beam, ultraviolet treatment and the like. Examples of the crosslinking method include a chemical crosslinking method, an electron beam crosslinking method, and a silane crosslinking method.

<Molded body>
A molded body contains the said resin composition. Such a molded body can be obtained by a known molding method after compounding a predetermined amount of tie chait particles etc. with a resin etc. to make a resin composition. As such a molding method, molding is performed by an extrusion molding machine, an injection molding machine, a blow molding machine, a press molding machine, a calendar molding machine, a lamination molding, a doctor blade method or the like. In addition, the obtained molded product may be subjected to a crosslinking reaction by various methods such as heat treatment or electron beam, ultraviolet treatment and the like. Examples of the crosslinking method include a chemical crosslinking method, an electron beam crosslinking method, and a silane crosslinking method.

The molded article of the present embodiment can be used in various forms such as a film, sheet, plate, block, special shape and the like according to various applications.

The molded body is formed of a resin composition containing the above-mentioned tie chait particles, and therefore, applications requiring high thermal conductivity, transparency, low refractive index, high dispersibility, easy processability, heat resistance, water resistance, etc. Can be suitably applied. It does not specifically limit as a use of a molded object, For example, an artificial marble, an optical film (a light-diffusion sheet, an anti-glare film, an anti blocking film etc.), a vinyl sheet, paints (for example, matting agent etc.) etc. are mentioned .

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

Example 1
The molar ratio of the raw material feed is set to be Mg ²⁺ : Na ⁺ : CO ₃ ^2- : SO ₄ ^2- = 1.0: 7.9: 3.1: 2.0 in a ² L volume SUS container (SO ₄ ^2- / Mg ²⁺ ratio = 2.0), 58.4 g of basic magnesium carbonate powder (magnesium carbonate Venus manufactured by Kamijima Chemical Industry Co., Ltd.) and 200 g of water, anhydrous sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) Add 101.6 g of sodium hydrogencarbonate (Wako Pure Chemical Industries, Ltd., reagent special grade) 40.4 g and sodium sulfate (Wako Pure Chemical Industries, reagent special grade) 179 g, and stir at 500 rpm for 3 minutes at room temperature The mixture was stirred to be uniform. 30 ml of the mixed slurry was put in a 50 ml Teflon (registered trademark) autoclave equipped with a stirring bar, and kept in a closed state at 120 ° C. for 12 hours to react under hydrothermal conditions. The temperature rising rate at this time was about 1 ° C./min. Thereafter, the container is allowed to cool to room temperature, and the semisolid slurry obtained after the reaction is taken out, vacuum filtered with a Nutche, thoroughly washed with water having a volume of at least 20 times the solid content, and washed at 120 ° C. It was dried in a drier for 10 hours to obtain tie chait particles.

Example 2
200 g of water and 300 ml of φ2 mm glass beads are placed in a 2 L volume of a SUS container, and the molar ratio of the raw materials charged is Mg ²⁺ : Na ⁺ : CO ₃ ^2- : SO ₄ ^2- = 1.0: 7.9: 3 .5: ² g of basic magnesium carbonate powder (magnesium carbonate Venus manufactured by Kamijima Chemical Industry Co., Ltd.) powder with stirring so as to be 1: 2.0 (SO ₄ ²⁻ / Mg ²⁺ ratio = 2.0), anhydrous Add 101.6 g of sodium carbonate (Wako Pure Chemical Industries, Ltd., special grade reagent), sodium hydrogen carbonate (Wako Pure Chemical Industries, Ltd.) and 179 g of sodium sulfate (special grade reagent, Wako Pure Chemical Industries, Ltd.), and room temperature The stirring process and mixing were simultaneously performed by stirring at a stirring speed of 500 rpm for 3 minutes. Thereafter, the glass beads were separated and removed using a sieve. In an autoclave, 30 ml of the slurry from which the glass beads were removed was put and kept in a closed state at 120 ° C. for 12 hours to react under hydrothermal conditions. The temperature rising rate at this time was about 1 ° C./min. Thereafter, the container is allowed to cool to room temperature, and the semisolid slurry obtained after the reaction is taken out, vacuum filtered with a Nutche, thoroughly washed with water having a volume of at least 20 times the solid content, and washed at 120 ° C. It was dried in a drier for 10 hours to obtain tie chait particles.

Example 3
In a 2 L volume SUS container, the molar ratio of the raw material feed is Mg ²⁺ : Na ⁺ : CO ₃ ^2- : SO ₄ ^2-1 = 1: 8.4: 4.0: 1.0 (SO ₄ ^{2 -} / Mg ²⁺ ratio = 1.0), 70.1 g of basic magnesium carbonate powder (magnesium carbonate Venus manufactured by Kamishima Chemical Industry Co., Ltd.) and 106.5 g of sodium sulfate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) Of a final volume 250 ml of aqueous solution dispersed (partially dissolved) and 254.4 g of anhydrous sodium carbonate (reagent special grade made by Wako Pure Chemical Industries, Ltd.) dispersed (partially dissolved) in water And stirred for 3 minutes at room temperature to mix uniformly. 30 ml of the mixed slurry was put in a 50 ml Teflon (registered trademark) autoclave equipped with a stirring bar, and kept in a closed state at 120 ° C. for 12 hours to react under hydrothermal conditions. The temperature rising rate at this time was about 1 ° C./min. Thereafter, the container is allowed to cool to room temperature, and the semisolid slurry obtained after the reaction is taken out, vacuum filtered with a Nutche, thoroughly washed with water having a volume of at least 20 times the solid content, and washed at 120 ° C. It was dried in a drier for 10 hours to obtain tie chait particles.

Comparative Example 1
In a 3-liter Ti autoclave, the molar ratio of the raw materials charged is such that Mg ²⁺ : Na ⁺ : CO ₃ ^2- : SO ₄ ^2- : 1: 8.0: 2.5: 2.5 (SO ₄ ^2- / Mg ²⁺ ratio = 2.5), magnesium sulfate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd .; reagent special grade) 131.5 g, anhydrous sodium carbonate (Wako Pure Chemical Industries, Ltd .: reagent special grade) 141.3 g and 113.6 g of sodium sulfate (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) were added, and water was used to make a final liquid volume of 1600 mL. After stirring for 1 minute at room temperature and mixing to be uniform, the mixture was placed in an autoclave and kept sealed at 120 ° C. for 12 hours while being stirred at 250 rpm for reaction under hydrothermal conditions. The temperature rising rate at this time was 1 ° C./min. Thereafter, the container is allowed to cool to room temperature, and the slurry obtained after the reaction is taken out, vacuum filtered with a Nutche, thoroughly washed with water having a volume of at least 20 times the solid content, and sufficiently washed at 120 ° C. for 10 hours. Drying in a drier gave Thaichaite particles.

Comparative Example 2
50 L of neutral magnesium carbonate (MgCO ₃ · 3 H ₂ O) suspension prepared to a concentration of 0.3 mol / L was placed in a 100 L autoclave equipped with a stirrer and subjected to hydrothermal treatment at 140 ° C for 10 hours while stirring . The temperature rising rate at this time was 1 ° C./min. The obtained suspension was dehydrated and then dried at 120 ° C. for 10 hours to obtain anhydrous magnesium carbonate particles.

Comparative Example 3
In a 300 mL glass container, the molar ratio of the raw materials charged is such that Mg ²⁺ : Na ⁺ : CO ₃ ^2- : SO ₄ ^2- : = 1: 4.9: 3.1: 0.6 (SO ₄ ^2- / Mg ²⁺ ratio = 0.6), 29.2 g of basic magnesium carbonate (magnesium carbonate Venus manufactured by Kamishima Chemical Industry Co., Ltd.), 50.8 g of anhydrous sodium carbonate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.), Sodium hydrogencarbonate (Wako Pure Chemical Industries, Ltd., reagent special grade) 20.2 g and sodium sulfate (Wako Pure Chemical Industries, Ltd., reagent special grade) 22.4 g were added, and 100 g of water was added. After stirring for 1 minute at room temperature and mixing to be uniform, the reaction was carried out at 80 ° C. for 12 hours without stirring. The slurry obtained after the reaction is vacuum-filtered with a Nutche, washed thoroughly with water at a volume of at least 20 times the solid content, and dried in a dryer at 120 ° C. for 10 hours to obtain tie chait particles and aiterite (MgCO ₃ · Na A mixture with ₂ CO ₃ ) particles was obtained.

Comparative Example 4
In a water bath set at 80 ° C., a 500 mL SUS vessel was installed, and the molar ratio of the raw materials charged was Mg ²⁺ : Na ⁺ : CO ₃ ^2- : SO ₄ ^2- = 1.0: 3.8: 3. 200 g of water, 58.4 g of basic magnesium carbonate powder (magnesium carbonate Venus manufactured by Kamijima Chemical Industry Co., Ltd.), anhydrous sodium carbonate (Wako Pure Chemical Industries, Ltd.) so as to be 1: 0 (SO ₄ ²⁻ / Mg ²⁺ ratio = 0) The reaction was performed for 12 hours while stirring at a stirring speed of 500 rpm by adding 101.6 g of industrial special grade reagent special grade reagent and 40.4 g of sodium hydrogen carbonate (reagent special grade special grade reagent made by Wako Pure Chemical Industries, Ltd.). Thereafter, the container is allowed to cool to room temperature, and the slurry obtained after the reaction is taken out, vacuum filtered with a Nutche, thoroughly washed with water having a volume of at least 20 times the solid content, and sufficiently washed at 120 ° C. for 10 hours. It was dried in a drier to obtain aitelite (MgCO ₃ .Na ₂ CO ₃ ) particles.

<Evaluation>
The following evaluation was performed about each particle | grain obtained by the Example and the comparative example. Each evaluation result is shown in Table 1.

(1) Crystal structure measurement (XRD measurement)
The crystal structure of the particles was measured and evaluated using an X-ray diffractometer (RINT-2500, manufactured by Rigaku Corporation) and integrated powder X-ray analysis software “PDXL2”. The measurement conditions were a Cu radiation source (40 kV, 30 mA).

(2) BET specific surface area A sample pretreated at about 130 ° C. for about 30 minutes in a nitrogen gas atmosphere using an 8-station preheating unit (manufactured by MOUNTECH) was used as a BET specific surface area measurement device Macsorb HM Model-1208 ( The BET specific surface area (m ² / g) was measured by a nitrogen gas adsorption method using MOUNTECH).

(3) 50% cumulative diameter and 90% cumulative diameter Take 50 mL of ethanol into a 100 mL beaker, add about 0.2 g of a sample, apply 3 minutes of ultrasonication (UD-201 manufactured by Tomy Seiko Co., Ltd.), and disperse The solution was prepared. The dispersion was measured using a laser diffraction method-particle size distribution analyzer (Microtrac HRA Model 9320-X100 manufactured by Nikkiso Co., Ltd.), and the 50% cumulative diameter (d ₅₀ ) on a volume basis in the obtained particle size distribution (μm) ) And a cumulative 90% diameter (d ₉₀ ) (μm) were determined.

(4) Particle Shape The shape of the particles was evaluated by obtaining an observation image at a magnification of 5000 using an SEM (manufactured by Hitachi High-Technologies Corporation, “Field emission scanning electron microscope S-4700”). FIG. 1 shows a SEM photograph of tie chait particles of Example 1.

(5) Evaluation of PMMA resin molded body PMMA (polymethyl methacrylate) resin (trade name: Sumipex MGSS, manufacturer: Sumitomo Chemical Co., Ltd.) was used. 100 parts by mass of particles are added to 100 parts by mass of PMMA resin, and the kneaded product obtained by melt-kneading for 5 minutes at 220 ° C. with a laboplast mill (manufactured by Toyo Seiki Co., Ltd.) is 125 mm × 13 mm × space of 3 mm in thickness The resultant was placed in a mold having a shape and pressed at 220 ° C. to form a 125 mm long × 13 mm wide × 3 mm thick molded article.

After that, the following three types of evaluations were performed using this molded body. Evaluation with resin alone was also performed.

(5-1) Transparency The formed body was placed on A4 size paper on which characters (line thickness 0.5 mm, size 5 mm × 5 mm) were printed, and the transparency was visually confirmed. The case where the character was transparent and was distinguishable was evaluated as "○", and the case where it could not be seen at all or indistinguishable was evaluated as "x".

(5-2) Flexural Modulus The flexural modulus (N / mm ² ) of the molded body was measured based on JIS K7171. Specifically, using autograph AG-5000A manufactured by Shimadzu Corporation, method A is used as a test method without changing the strain rate, distance between supporting points 40 mm, test speed 10 mm / min, radius of indenter R1 = 2 mm, It carried out on the conditions of radius R2 = 2 mm of a support stand. The target value was determined to be good in the reinforcing property if the flexural modulus was 13000 N / mm ² or more.

(5-3) Heat Resistance A formed body was sandwiched in a press heated to 190 ° C., and pressed at 1 MPa for 1 minute. The case where it did not deform | transform at all was evaluated as "O", and the case where it deform | transformed was evaluated as "x."

(6) Evaluation of EVA resin molded product EVA (ethylene vinyl alcohol) resin (trade name: EV-180, manufacturer: Mitsui DuPont) was used. 20 parts by mass of particles are added to 100 parts by mass of EVA resin, and a kneaded product obtained by melt-kneading for 5 minutes at 180 ° C. with a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) is press-molded at 180 ° C. A sheet molding of

Then, the following three types of evaluations were performed using this molded object. Evaluation with resin alone was also performed.

(6-1) Transparency The formed product was placed on A4 size paper on which characters (line thickness 0.5 mm, size 5 mm × 5 mm) were printed, and the transparency was visually confirmed. The case where the character was transparent and was distinguishable was evaluated as "○", and the case where it could not be seen at all or indistinguishable was evaluated as "x".

(6-2) Infrared Absorption Ability The infrared absorption ability at a wavelength of 5 to 12 μm was measured using FT-IR (apparatus name: Spectrum One, method: ATR method). FIG. 2 shows IR spectra of Example 1, Comparative Example 1 and EVA resin alone. The target value is set at 65% T · μm or more in peak integrated area. The peak integrated area was determined by integrating over a wavelength of 5 to 12 μ, where the absorptivity is (T−100) [%] for the transmittance T [%].

(6-3) Anti-blocking property Two sheets of the sheet molding were stacked in a normal temperature press and sandwiched, and pressed at 5 MPa for 1 minute. Thereafter, the two sheets were peeled off by hand to confirm antiblocking properties. The case where it peeled off smoothly was evaluated as "x", the case where it was not able to peel, the case where it could not be peeled, or the sheet was broken and only a part was peeled.

(6-4) Surface Appearance The touch of the surface of the sheet molding was confirmed. Those that were smooth and smooth with a finger were evaluated as "o" and those that were rough were evaluated as "x".

From Table 1, in the examples, tie-chaet particles having a large BET specific surface area and a small particle size were obtained. Moreover, in the PMMA resin molded object formed with the resin composition which mix | blended tie-chait particle | grains, transparency and reinforcement property were high with respect to the comparative example, and it was excellent also in heat resistance. Even the EVA resin molded body was superior to any of the comparative examples in any of the transparency, the infrared ray absorbing ability, the antiblocking property and the appearance. On the other hand, in the comparative example 1, tiechaite particles having a small BET specific surface area and a large particle diameter were produced. This is presumed to be due to the use of magnesium sulfate heptahydrate instead of basic magnesium carbonate as the magnesium raw material. In Comparative Example 2, no tie chait particles were obtained because the sulfate ion source was not present. In Comparative Example 3, since the SO ₄ ²⁻ / Mg ²⁺ ratio was less than 1, a part of the basic magnesium carbonate was partially converted to the aiterite phase without being converted to the tie chayte phase. In Comparative Example 4, since the SO ₄ ²⁻ / Mg ²⁺ ratio was 0 (ie, the sulfate ion source was not input), the entire amount of basic magnesium carbonate was converted to the aiterite phase. Iterite particles are octahedral, and evaluations other than transparency were good. The reason why the transparency evaluation was not satisfied is that the eyelite particles have two different refractive indices (birefringence), and because these refractive indices are not close to the resin, the result is that they are transparent. It is presumed that the sex decreased. In Example 2, since the glass beads were added in the raw material mixing step and the pulverizing treatment was carried out, tie-chaet particles having a smaller particle size than Example 1 were obtained.

Claims (12)

A particle having a BET specific surface area of 0.5 m ² / g or more. 2. The particles according to claim 1, wherein a cumulative 50% diameter (d ₅₀ ) on a volume basis in a particle size distribution obtained by a laser diffraction type particle size distribution analyzer is 15 μm or less. The tie-chatite particles according to claim 1 or 2, wherein a cumulative 90% diameter (d ₉₀ ) on a volume basis in a particle size distribution obtained by a laser diffraction type particle size distribution analyzer is 30 μm or less. The particles according to any one of claims 1 to 3, wherein the particles are octahedral in shape. A method for producing Thaichite particles, comprising a mixing step of mixing a magnesium raw material and a sodium raw material,
The magnesium source comprises basic magnesium carbonate,
The method for producing taiichite particles, wherein the ratio of the number of moles of sulfate ions to the number of moles of magnesium ions in the mixture is 1 or more. The method for producing Thaichaite particles according to claim 5, wherein the mixing step is performed under heating. The method according to claim 6, wherein the heating temperature is 70 ° C or higher. The method for producing Thaichaite particles according to any one of claims 5 to 7, wherein the sodium raw material contains sodium sulfate. 9. The method of producing tie-chite particles according to any one of claims 5 to 8, wherein a ratio of the number of moles of sodium ions to the number of moles of magnesium ions in the mixture is 5 or more and 20 or less. A resin composition comprising 0.1 to 600 parts by mass of the particles according to any one of claims 1 to 4 with respect to 100 parts by mass of the resin. 10. The resin according to claim 10, wherein the resin is at least one of an acrylic resin, an ABS resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polycarbonate resin, a polyphenylene resin, a polyester resin, and a polyamide resin. The resin composition as described in. The molded object containing the resin composition of Claim 10 or 11.

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