CN108314068B - Heat-resistant aluminum hydroxide and method for producing same - Google Patents
Heat-resistant aluminum hydroxide and method for producing same Download PDFInfo
- Publication number
- CN108314068B CN108314068B CN201810239378.5A CN201810239378A CN108314068B CN 108314068 B CN108314068 B CN 108314068B CN 201810239378 A CN201810239378 A CN 201810239378A CN 108314068 B CN108314068 B CN 108314068B
- Authority
- CN
- China
- Prior art keywords
- aluminum hydroxide
- heat
- mass
- less
- resistant aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
Abstract
The present invention relates to a heat-resistant aluminum hydroxide containing 100 parts by mass of an aluminum hydroxide powder containing a boehmite precursor in an amount of 0.1 to 10% by mass, and 0.01 to 5 parts by mass of a fluorine atom-containing complex.
Description
This application is a divisional application of an invention patent application entitled "Heat-resistant aluminum hydroxide and method for producing the same" having international filing date of 2015, 4-month, 23-day, and national application number of 201580028081.9.
Technical Field
The present invention relates to aluminum hydroxide having heat resistance and a method for producing the same.
Background
The gibbsite-type aluminum hydroxide is used as a flame retardant for imparting flame retardancy to be incorporated into various polymer materials used in electronic parts such as printed circuit boards, electric wire coating materials, insulating materials, and the like, by utilizing a mechanism of dehydrating water contained in crystals by heating. On the other hand, as shown below, the gibbsite type aluminum hydroxide starts to dehydrate from around 220 to 230 ℃, and depending on the type of resin, the dehydration region may be difficult to use as a flame retardant due to the temperature region corresponding to the processing.
Dehydration of gibbsite-type aluminum hydroxide (alumina trihydrate) generated during gradual heating in an atmospheric atmosphere is known to be caused by the following two points.
(1) Is dehydrated from gibbsite-type aluminum hydroxide to boehmite as alumina monohydrate, and (2) is dehydrated to alumina. In general, dehydration (1) is likely to occur from the low temperature side (about 220 ℃), (2) is started simultaneously with (1) or from the high temperature side (about 230 ℃). Therefore, in order to improve the heat resistance of the gibbsite-type aluminum hydroxide, the heat treatment is performed under various conditions, and the dehydration (1) and the dehydration (2) are performed in advance on the low temperature side.
For example, patent document 1 describes that Al is obtained by heating aluminum hydroxide having an average particle size of 0.3 to 4.5 μm to partially dehydrate it in advance2O3·nH2Aluminum hydroxide represented by O (wherein n represents the amount of water of hydration) is excellent in heat resistance.
Patent document 2 discloses the following method: the aluminum hydroxide particles are subjected to heating treatment at 230-270 ℃ in the atmospheric atmosphere, so that chi-alumina is generated, and the heat resistance is improved. Further, in the examples of patent document 2, it is described that aluminum hydroxide is heat-treated in an atmospheric atmosphere at 260 ℃ for a retention time of 30 minutes using a tray dryer.
Patent document 3 describes that, by subjecting a gibbsite-type aluminum hydroxide produced by the bayer process to a heat treatment under a pressure of not less than atmospheric pressure and not more than 0.3MPa and under a condition in which the mole fraction of water vapor is not less than 0.03 and not more than 1, the heat history can be imparted while suppressing the generation of defects on the outermost surface, thereby improving the heat resistance of the aluminum hydroxide.
On the other hand, as a means for further improving the heat resistance, a method using various additives has been proposed. For example, patent document 4 describes that aluminum hydroxide and a reaction retarder for retarding boehmite are mixed, and the mixture is subjected to pressure and heating in a pressure vessel under hydrothermal treatment or a water vapor atmosphere, whereby heat history can be imparted while suppressing only partial boehmite generation in an environment where complete phase transition to boehmite originally occurs, and the heat resistance of aluminum hydroxide can be improved.
Further, patent document 5 describes a method of subjecting aluminum hydroxide particles to a heat treatment at 200 to 270 ℃ in a gas atmosphere containing fluorine; and a method in which aluminum hydroxide particles are treated with a solution containing fluorine ions to replace a part of the hydroxyl groups of the particles with fluorine, and then heat treatment is performed at 200 to 270 ℃. According to these methods, aluminum hydroxide having high heat resistance, which cannot be obtained by only heat treatment, can be obtained.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2002-211918
Patent document 2: japanese patent laid-open publication No. 2011-84431
Patent document 3: international publication No. 2014/133049
Patent document 4: international publication No. 2004/080897
Patent document 5: japanese patent laid-open publication No. 2013-10665.
Disclosure of Invention
Problems to be solved by the invention
However, in the method of patent document 4, it is necessary to heat-treat aluminum hydroxide and additives in an expensive pressure vessel. Further, the method of patent document 5 requires heat treatment together with a harmful fluorine gas or heat treatment after harmful hydrofluoric acid treatment of the surface of aluminum hydroxide, and has a problem of safety and low productivity. Therefore, it has been difficult to produce heat-resistant aluminum hydroxide safely and with high productivity by the conventional method.
Further, the aluminum hydroxide produced by the methods described in patent documents 4 and 5 is suitable for engineering plastics having a very high melting point because of its very high dehydration temperature, but has excessive heat resistance for general-purpose resins having a relatively low melting point such as polyethylene and polypropylene. On the other hand, in the aluminum hydroxide produced by the methods described in patent documents 1 to 3, a dehydration reaction occurs at a processing temperature for processing a general-purpose resin, and heat resistance is sometimes insufficient.
Accordingly, an object of the present invention is to produce aluminum hydroxide having heat resistance sufficient for use in general-purpose resins and to produce heat-resistant aluminum hydroxide with safety and high productivity.
Means for solving the problems
The present inventors have made extensive and intensive studies to solve the above problems and, as a result, have reached the present invention.
That is, the present invention includes the following preferred embodiments.
[1] A heat-resistant aluminum hydroxide which comprises 100 parts by mass of an aluminum hydroxide powder having a boehmite precursor content of 10% by mass or less and 0.01 part by mass or more and 5 parts by mass or less of a fluorine atom-containing complex.
[2] The heat-resistant aluminum hydroxide according to item [1], wherein the aluminum hydroxide powder has an average particle size of 0.5 to 15 μm.
[3]According to [1]Or [2]]The heat-resistant aluminum hydroxide is prepared by mixing aluminum hydroxide powder and sodium hydroxide powder, wherein the total sodium content of the aluminum hydroxide powder is Na2O is 0.01 to 0.1 mass% in terms of O.
[4] The heat-resistant aluminum hydroxide according to any one of [1] to [3], wherein the fluorine atom-containing complex is a solid at 25 ℃ and 100 kPa.
[5] The heat-resistant aluminum hydroxide according to any one of [1] to [4], wherein a central element of the fluorine atom-containing complex is boron (B), aluminum (Al) or phosphorus (P).
[6] The heat-resistant aluminum hydroxide according to any one of [1] to [5], wherein the fluorine atom-containing complex is aluminum fluoride or sodium phosphate fluoride.
[7] The heat-resistant aluminum hydroxide has a time to decrease by 1 mass% at 230 ℃ of 5 to 60 minutes.
[8] The heat-resistant aluminum hydroxide according to any one of [1] to [7], wherein the average particle diameter is 0.5 μm or more and 15 μm or less.
[9]According to [1]~[8]The heat-resistant aluminum hydroxide according to any one of the above, wherein the BET specific surface area is 0.5m21.8 m/g or more2The ratio of the carbon atoms to the carbon atoms is less than g.
[10] The heat-resistant aluminum hydroxide according to any one of [1] to [9], wherein the boehmite content is 15% by mass or less.
[11] A resin composition comprising a resin and the heat-resistant aluminum hydroxide according to any one of [1] to [10 ].
[12] A method for producing the heat-resistant aluminum hydroxide according to any one of [1] to [10], which comprises mixing 100 parts by mass of an aluminum hydroxide powder having a boehmite precursor content of 10% by mass or less and 0.01 part by mass or more and 5 parts by mass or less of a fluorine atom-containing complex.
[13] The method according to [12], wherein the aluminum hydroxide powder is produced by a Bayer process.
Effects of the invention
According to the present invention, aluminum hydroxide having heat resistance sufficient for use in general-purpose resins can be provided. Further, according to the present invention, heat-resistant aluminum hydroxide that can withstand the processing temperature of general-purpose resins can be produced safely and with high productivity without the need for heat treatment together with harmful fluorine-containing additives.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The heat-resistant aluminum hydroxide of the present invention comprises an aluminum hydroxide powder and a complex containing a fluorine atom. In the present invention, the boehmite precursor content of the aluminum hydroxide powder is 10% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. If the boehmite precursor content of the aluminum hydroxide powder is not more than the above upper limit, boehmite is less likely to be generated when the heat-melted resin and the heat-resistant aluminum hydroxide are kneaded, and therefore the heat-resistant aluminum hydroxide can further exhibit excellent heat resistance. The lower limit of the boehmite precursor content of the aluminum hydroxide powder is usually 0 mass% or more, for example, 0.1 mass% or more.
The heat-resistant aluminum hydroxide of the present invention contains 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 1 part by mass or less of a fluorine atom-containing complex per 100 parts by mass of the aluminum hydroxide powder. When the content of the fluorine atom-containing complex in the heat-resistant aluminum hydroxide of the present invention is not less than the lower limit, the aluminum hydroxide powder and the fluorine atom-containing complex can be brought into sufficient contact with each other, and the heat resistance of the heat-resistant aluminum hydroxide can be further improved. In addition, if the content of the fluorine atom-containing complex in the heat-resistant aluminum hydroxide of the present invention is not more than the above upper limit, the content ratio of the aluminum hydroxide powder in the heat-resistant aluminum hydroxide is not excessively low, and the heat-resistant aluminum hydroxide can further exhibit high heat resistance.
In the heat-resistant aluminum hydroxide of the present invention, the time taken for the mass to decrease by 1 mass% at 230 ℃ is preferably 5 minutes or longer, more preferably 7 minutes or longer, and still more preferably 10 minutes or longer, and is preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and still more preferably 20 minutes or shorter.
The aluminum hydroxide powder can impart flame retardancy to the resin by being blended in the resin. On the other hand, when the resin is blended, it is necessary to knead the resin with a heated and melted resin. The temperature for heating and melting varies depending on the resin composition and compounding composition, but if it is a general-purpose resin such as polypropylene or polyethylene, it is about 230 ℃ or less, and therefore the compounded material is preferably not decomposed when kneaded at 230 ℃. The time for melt kneading varies depending on the resin composition and compounding composition, but in order to ensure the uniformity of the resin and the aluminum hydroxide powder in the resin composition, it is preferable to carry out kneading for at least 5 minutes. Therefore, if the time taken for the heat-resistant aluminum hydroxide of the present invention to decrease by 1 mass% at 230 ℃ is not less than the lower limit, the heat-resistant aluminum hydroxide is less likely to decompose during kneading with a resin. In addition, if the time until the heat-resistant aluminum hydroxide of the present invention is reduced by 1 mass% at 230 ℃ is not more than the above upper limit, the resin composition containing the resin and the heat-resistant aluminum hydroxide can exhibit excellent flame retardancy without a decrease in the moisture release rate.
In the present invention, the average particle size of the aluminum hydroxide powder contained in the heat-resistant aluminum hydroxide is preferably 0.5 μm or more, more preferably 1.0 μm or more, and still more preferably 2.0 μm or more, and is preferably 15.0 μm or less, more preferably 10.0 μm or less, and still more preferably 7.0 μm or less. When the average particle diameter of the aluminum hydroxide powder is not more than the above upper limit, the resin composition comprising the resin and the heat-resistant aluminum hydroxide is particularly excellent in flame retardancy, and when used for an electric wire coating material, a printed wiring board, or the like, the surface smoothness is less likely to decrease. Further, if the average particle diameter of the aluminum hydroxide powder is not less than the lower limit value, the uniformity of the complex of the aluminum hydroxide powder and the fluorine-containing atom can be ensured, and the heat resistance of the heat-resistant aluminum hydroxide can be further improved.
In the present invention, the total sodium content of the aluminum hydroxide powder is Na2The content is preferably 0.1% by mass or less in terms of O, and more preferably 0.05% by mass or less. If the total sodium content of the aluminum hydroxide powder in the present invention is not more than the above upper limit, the heat resistance of the obtained heat-resistant aluminum hydroxide can be further improved. The lower limit of the total sodium content of the aluminum hydroxide powder in the present invention is usually 0.01 mass% or more, for example, 0.03 mass% or more. The total sodium content can be measured by a spectroscopic analysis method such as that described in JIS-R9301-3-9.
In the present invention, the BET specific surface area of the aluminum hydroxide powder contained in the heat-resistant aluminum hydroxide is preferably 0.5m2A value of at least g, more preferably 0.7m2A value of 1.0m or more, preferably2A ratio of 8.0m or more per g2A ratio of the total amount of the components to the total amount of the components is 5.0m or less2A ratio of 3.0m or less per gram2The ratio of the carbon atoms to the carbon atoms is less than g. When the BET specific surface area of the aluminum hydroxide powder is not more than the above upper limit, the amount of water adsorbed on the surface of the aluminum hydroxide powder is suppressed, and foaming due to dehydration can be suppressed during processing and use. Further, if the BET specific surface area of the aluminum hydroxide powder is not less than the above lower limit value, the flame retardancy of the resin composition comprising the resin and the heat-resistant aluminum hydroxide is further improved.
The aluminum hydroxide powder contained in the heat-resistant aluminum hydroxide of the present invention may be a coupling agent such as a silane coupling agent or a titanate coupling agent for the purpose of improving affinity with a resin and improving filling properties; aliphatic carboxylic acids such as oleic acid and stearic acid; aromatic carboxylic acids such as benzoic acid and esters thereof; silicate and silicone, etc. The surface treatment may be performed by either a dry or wet treatment method.
As the dry surface treatment method, for example, a method of mixing aluminum hydroxide powder and an additive in a henschel mixer or a Lodige (Lodige) mixer, and a method of charging a mixture of aluminum hydroxide powder and an additive into a pulverizer and pulverizing the mixture in order to uniformly apply the additive may be mentioned.
Examples of the wet surface treatment method include a method in which an additive is dispersed or dissolved in a solvent, aluminum hydroxide powder is dispersed in the obtained solution, and the obtained dispersion liquid is dried.
The fluorine atom-containing complex in the present invention is preferably solid at 25 ℃ and 100 kPa. If the fluorine atom-containing complex is a gas or a liquid at 25 ℃ and 100kPa, it is difficult to fix the fluorine atom-containing complex to the aluminum hydroxide powder, and fluorine gas or hydrofluoric acid is generated in the production step and eluted, thereby impairing the safety.
The fluorine atom-containing complex in the present invention is, for example, fluorine (F) based on a central element (M) and a ligand by the chemical formula MFn(wherein n represents an integer of 1 or more). Examples of the central element M include boron (B), aluminum (Al), silicon (Si), phosphorus (P), titanium (Ti), zirconium (Zr), and the like. The central element M is preferably boron (B), aluminum (Al), or phosphorus (P), and more preferably aluminum (Al) or phosphorus (P), from the viewpoint of safety during production or use.
As MFnSpecific examples of the fluorine atom-containing complex include Boron Fluoride (BF)3) Aluminum fluoride (AlF)3) And Phosphorus Fluoride (PF)3) And the like.
Further, the fluorine atom-containing complex in the present invention may be H based on the central element (M), fluorine (F) of the ligand, and water (H)pMFq(wherein p and q each independently represents an integer of 1 or more), or a neutralized salt thereof. Examples of the element contained in the neutralized salt include alkali metals and alkaline earth metals, and specifically, lithium, sodium, potassium, magnesium, calcium, and the like. Examples of the acid and the neutralized salt thereof includeSuch as fluorinated boronic acids (HBF)4) Lithium fluoroborate (LiBF)4) Sodium fluoborate (NaBF)4) Fluorinated aluminic acid (H)3AlF6) Lithium fluoroaluminate (Li)3AlF6) Sodium fluoride aluminate (Na)3AlF6) Fluorinated phosphoric acid (H)3PF6) Lithium fluorophosphate (Li)3PF6) And sodium phosphate fluoride (Na)3PF6) And the like.
The fluorine atom-containing complex is more preferably aluminum fluoride or sodium phosphate fluoride having low toxicity from the viewpoint of safety during production and use.
The aluminum fluoride is solid at 25 ℃ and 100 kPa. When aluminum fluoride is used, it is preferably used by pulverizing. The activity of aluminum fluoride can be improved by pulverization, and the heat resistance of aluminum hydroxide can be further improved. The grinding method is not particularly limited, and either of dry and wet treatment methods can be used.
As aluminum fluoride, a hydrate may be used, but AlF is preferable3Anhydrates shown. When a hydrate is used as the aluminum fluoride, the content of the fluorine atom-containing complex in the heat-resistant aluminum hydroxide is calculated as an anhydride.
The average particle diameter of the aluminum fluoride is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and particularly preferably 0.2 μm or more, and preferably 5 μm or less, more preferably 1 μm or less, further preferably 0.8 μm or less, and particularly preferably 0.5 μm or less. If the average particle size of aluminum fluoride is not less than the lower limit, aggregation of aluminum fluoride is less likely to occur, and mixing with aluminum hydroxide powder is easy. Further, if the average particle size of the aluminum fluoride is not more than the above upper limit, the aluminum fluoride can be sufficiently brought into contact with the aluminum hydroxide powder, and the heat resistance can be further improved.
The BET specific surface area of aluminum fluoride is preferably 10m2A value of at least g, more preferably 20m2A value of 30m or more, preferably 30m2More preferably 35 m/g or more2A ratio of 300m or more2A, below, more preferably 200m2Less than g, one is addedThe step is preferably 100m2A concentration of 70m or less, more preferably2The ratio of the carbon atoms to the carbon atoms is less than g. When the BET specific surface area of aluminum fluoride is not less than the lower limit value, aluminum fluoride can be brought into sufficient contact with aluminum hydroxide powder, and the heat resistance can be further improved. When the BET specific surface area of aluminum fluoride is not more than the above upper limit, the amount of water adsorbed on the surface of aluminum fluoride is suppressed, and foaming due to dehydration can be suppressed during processing and use.
Sodium fluoride phosphate was a solid at 25 ℃ under 100 kPa. When sodium fluoride is used, it may be used by pulverizing. The dispersibility of the sodium fluoride phosphate can be improved by pulverization, and the heat resistance of the aluminum hydroxide can be further improved. The grinding method is not particularly limited, and either dry or wet treatment methods can be used, but dry grinding is preferred because of high solubility of sodium phosphate fluoride in water and alcohols such as methanol and ethanol.
When sodium phosphate fluoride is used by wet treatment such as wet pulverization or wet mixing, a part or all of the sodium phosphate fluoride exists in a state of being ionized into phosphate fluoride ions and sodium ions because of its high solubility in water and alcohols such as methanol and ethanol. At this time, the solvent is removed by drying, whereby sodium fluoride can be recrystallized.
The average particle diameter of the sodium fluoride is preferably 0.01 μm or more, more preferably 0.05 μm or more, and preferably 500 μm or less, more preferably 100 μm or less. When the average particle size of the sodium phosphate fluoride is not less than the lower limit, the sodium phosphate fluoride is less likely to aggregate, and the sodium phosphate is easily mixed with the aluminum hydroxide powder. Further, if the average particle size of the sodium phosphate fluoride is not more than the above upper limit, the sodium phosphate fluoride can be sufficiently brought into contact with the aluminum hydroxide powder, and the heat resistance can be further improved.
The BET specific surface area of the sodium phosphate fluoride is preferably 0.01m2A value of 1m or more, more preferably 1 g or more2A total of 10m or more, preferably 10m2More preferably 35 m/g or more2A ratio of 300m or more2A, below, more preferably 200m2A ratio of 100m or less in terms of/g2/gHereinafter, more preferably 70m2The ratio of the carbon atoms to the carbon atoms is less than g. When the BET specific surface area of the sodium phosphate fluoride is not less than the lower limit value, the sodium phosphate fluoride can be sufficiently brought into contact with the aluminum hydroxide powder, and the heat resistance can be further improved. When the BET specific surface area of the sodium phosphate fluoride is not more than the above upper limit, the amount of water adsorbed on the surface of the sodium phosphate fluoride is suppressed, and foaming due to dehydration can be suppressed during processing and use.
The average particle size of the heat-resistant aluminum hydroxide of the present invention is preferably 0.5 μm or more, more preferably 1.0 μm or more, and still more preferably 2.0 μm or more, and is preferably 15 μm or less, more preferably 10.0 μm or less, and still more preferably 7.0 μm or less. When the average particle diameter of the heat-resistant aluminum hydroxide is not more than the above upper limit, the resin composition comprising the resin and the heat-resistant aluminum hydroxide is particularly excellent in flame retardancy, and when used for an electric wire coating material, a printed wiring board, or the like, the surface smoothness is less likely to decrease. Further, if the average particle diameter of the heat-resistant aluminum hydroxide is not less than the lower limit, the viscosity of the resin composition containing the resin and the heat-resistant aluminum hydroxide does not become excessively high, and the uniformity of the resin in the resin composition can be ensured, and the resin composition can be suitably produced. In the present invention, the average particle diameter is a particle diameter at which the particle size distribution measured by the laser light scattering method reaches 50% on a volume basis.
The BET specific surface area of the heat-resistant aluminum hydroxide of the present invention is preferably 0.5m2A value of at least g, more preferably 0.7m2A value of 1.0m or more, preferably2A ratio of 8.0m or more per g2A ratio of the total amount of the components to the total amount of the components is 3.0m or less2A ratio of 1.8m or less per gram2The ratio of the carbon atoms to the carbon atoms is less than g. When the BET specific surface area of the heat-resistant aluminum hydroxide is not more than the above upper limit, the amount of water adsorbed on the surface of the heat-resistant aluminum hydroxide is suppressed, and foaming due to dehydration can be suppressed during processing and use. Further, if the BET specific surface area of the heat-resistant aluminum hydroxide is not less than the above lower limit value, the flame retardancy of the resin composition comprising the resin and the heat-resistant aluminum hydroxide is further improved.
The boehmite content of the heat-resistant aluminum hydroxide of the present invention is preferably 15% by mass or less, more preferably 11% by mass or less, further preferably 5% by mass or less, further more preferably 1% by mass or less, particularly preferably 0.7% by mass or less, and very preferably 0.5% by mass or less. When the boehmite content of the heat-resistant aluminum hydroxide is not more than the above upper limit, the transparency peculiar to aluminum hydroxide is not impaired when blended in the resin, and the resin composition can exhibit excellent flame retardancy. The lower limit of the boehmite content of the heat-resistant aluminum hydroxide is usually 0 mass% or more, for example, 0.01 mass% or more.
The heat-resistant aluminum hydroxide of the present invention can be produced by a method comprising a step of mixing an aluminum hydroxide powder with a complex containing a fluorine atom (also referred to as the production method of the present invention).
In the production method of the present invention, 100 parts by mass of the aluminum hydroxide powder and 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, and further 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 1 part by mass or less of the fluorine atom-containing complex are mixed. Further, if the amount of the fluorine atom-containing complex is not less than the lower limit, the obtained heat-resistant aluminum hydroxide can be sufficiently contacted with the aluminum hydroxide powder, and the heat resistance can be further improved. Further, if the amount of the fluorine atom-containing complex is not more than the above upper limit, the content ratio of the aluminum hydroxide powder in the obtained heat-resistant aluminum hydroxide is not excessively low, and the heat-resistant aluminum hydroxide can further exhibit high heat resistance.
In the production method of the present invention, the boehmite precursor content of the aluminum hydroxide powder is 10% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. If the boehmite precursor content of the aluminum hydroxide powder is not more than the above upper limit, boehmite is less likely to be generated when the heat-melted resin and the obtained heat-resistant aluminum hydroxide are kneaded, and therefore the heat-resistant aluminum hydroxide can further exhibit excellent heat resistance. The lower limit of the boehmite precursor content of the aluminum hydroxide powder is usually 0.1 mass% or more, for example, 0.3 mass% or more.
The method for producing the aluminum hydroxide powder is not particularly limited, and the production method of the present invention preferably includes producing the aluminum hydroxide powder by the bayer process from the viewpoint of production cost. The bayer process is a process for producing a supersaturated sodium aluminate aqueous solution, and precipitating an aluminum component contained in the aqueous solution by adding seeds to the aqueous solution, and the obtained slurry containing aluminum hydroxide is washed and dried to obtain aluminum hydroxide powder.
The boehmite precursor content in the aluminum hydroxide powder corresponds to the amount of intragranular defects contained in the gibbsite-type aluminum hydroxide powder produced by the bayer process. The aluminum hydroxide powder of gibbsite type has internal particle defects that disappear while gradually generating boehmite by being subjected to heat at about 220 ℃ in an atmospheric atmosphere. Therefore, although the intra-granular defects can be reduced by performing the heat treatment in advance, it is preferable to use an aluminum hydroxide powder having less intra-granular defects even without performing the heat treatment. The aluminum hydroxide powder preferably contains a boehmite precursor in a smaller amount, but requires a high level of technology, and therefore the production cost of the aluminum hydroxide powder increases. If the amount is too large, the effect of improving heat resistance by the fluorine atom-containing complex to be mixed is small.
The aluminum hydroxide powder produced by the Bayer process is a gibbsite-type aluminum hydroxide powder having a crystal structure of Al (OH)3Or Al2O3·3H2O is represented by the formula. The aluminum hydroxide powder in the present invention may be a mixture obtained by partially generating boehmite by performing heat treatment in advance. The aluminum hydroxide powder may be mixed with the fluorine atom-containing complex not only in the form of powder but also in the form of a cake containing water or an aqueous slurry.
When the boehmite precursor in the aluminum hydroxide powder is reduced by the heat treatment in advance, the heat treatment is usually performed at a pressure of 0.3MPa or more and preferably 0.2MPa or less under an atmospheric pressure and at a temperature of 180 ℃ to 300 ℃, preferably 200 ℃ to 280 ℃, and more preferably 220 ℃ to 260 ℃.
The method of mixing the aluminum hydroxide powder and the fluorine atom-containing complex is not particularly limited, and either dry or wet treatment may be carried out.
Examples of the dry surface treatment method include a method of mixing in a henschel mixer or a ladybug mixer, and a method of charging a mixture of aluminum hydroxide powder and a fluorine-containing complex into a pulverizer and pulverizing the mixture for uniform mixing. Examples of the wet surface treatment method include a method in which a fluorine-containing complex is dispersed or dissolved in a liquid, and the obtained solution is sprayed onto aluminum hydroxide powder to dry the obtained wet cake. The liquid to be the dispersion medium is not particularly limited, and is preferably water which can be easily removed by drying. When the fluorine atom-containing complex is soluble in the dispersion medium, the aluminum hydroxide powder can be uniformly treated with the fluorine atom-containing complex regardless of the average particle size and BET specific surface area of the fluorine atom-containing complex.
The heat-resistant aluminum hydroxide of the present invention may be used with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to improve the affinity with the resin and to improve the filling property; aliphatic carboxylic acids such as oleic acid and stearic acid; aromatic carboxylic acids such as benzoic acid and esters thereof; silicate and silicone, etc. The surface treatment may be performed by either a dry or wet treatment method.
As the dry surface treatment method, for example, a method of mixing aluminum hydroxide powder and an additive in a henschel mixer or a Lodige (Lodige) mixer, and a method of charging a mixture of heat-resistant aluminum hydroxide and an additive into a pulverizer and pulverizing the mixture in order to uniformly apply the additive may be mentioned.
Examples of the wet surface treatment method include a method in which an additive is dispersed or dissolved in a solvent, heat-resistant aluminum hydroxide is dispersed in the obtained solution, and the obtained dispersion is dried.
The heat-resistant aluminum hydroxide of the present invention has high heat resistance and a small amount of adsorbed water, and is suitable as a filler for resins and can be used as a filler for resins. The resin is not particularly limited, and examples thereof include thermoplastic resins such as rubber, polypropylene and polyethylene, and thermosetting resins such as epoxy resins. The heat-resistant aluminum hydroxide of the present invention has excellent heat resistance at 230 ℃, and therefore the resin is preferably a general-purpose thermoplastic resin having a temperature of heat melting of about 230 ℃ or lower. Examples of such general-purpose thermoplastic resins include polyolefins such as polypropylene and polyethylene, polyamides, polystyrene, polyvinylidene chloride, and ABS (acrylonitrile-butadiene-styrene) resins. The heat-resistant aluminum hydroxide of the present invention can be suitably used as a filler for general-purpose resins having a heat-melting temperature of about 230 ℃ or lower.
The resin composition comprising the heat-resistant aluminum hydroxide of the present invention and a resin can be obtained by mixing the heat-resistant aluminum hydroxide and the resin using a conventionally used known method.
The resin composition containing the heat-resistant aluminum hydroxide of the present invention and a resin includes, for example, a member of an electronic device such as a printed wiring board and a prepreg constituting the same, and further includes a wire coating material, a polyolefin molding material, a building material such as a tire and an artificial marble, and particularly preferably used are a member of an electronic device such as a printed wiring board and a sealing material, which are required to have high heat resistance during processing and use, and a wire coating material.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples.
The aluminum hydroxide powders in examples and comparative examples were measured for the average particle size, BET specific surface area, total sodium content, boehmite precursor content, and boehmite content according to the measurement methods shown below. Further, the average particle diameter, BET specific surface area, boehmite content, and heat resistance were measured for the heat-resistant aluminum hydroxide in examples and comparative examples according to the methods shown below.
(1) Average particle diameter
As the measuring apparatus, a laser scattering particle size distribution measuring apparatus ("マイクロトラック MT-3300 EXII" manufactured by Nikkiso Co., Ltd.) was used. The sample was added to a 0.2 mass% aqueous solution of sodium hexametaphosphate, adjusted to a measurable concentration, and then irradiated with ultrasonic waves at an output of 25W for 120 seconds, and then measured with the number of samples being 2, and the particle size distribution curve were determined from the average values thereof. The average particle diameter was determined as a particle diameter (D50(μm)) corresponding to 50 mass%. In addition, when the average particle size obtained by the above method is 2 μm or less, the measurement conditions are changed, and a value measured after irradiating ultrasonic waves with an output of 40W for 300 seconds is used.
(2) BET specific surface area
The BET specific surface area of the sample was determined by a nitrogen adsorption method using a full-automatic specific surface area measuring apparatus ("Macsorb HM-1201" manufactured by Mountech) according to the method prescribed in JIS-Z-8830.
(3) Total sodium content
The total sodium content of the sample was determined by ICP emission Spectroscopy defined in JIS-R9301-3-9.
(4) Boehmite precursor content
10g of the sample was charged into a hot air dryer having an internal volume of 216L and an ambient temperature of 220 ℃ and subjected to heat treatment in an atmospheric atmosphere for 4 hours, whereby the boehmite precursor was completely crystallized and converted into boehmite.
Next, the boehmite precursor content was measured under the following measurement conditions in a powder X-ray diffraction measuring apparatus ("RINT-2000" manufactured by リガク) using Cu as an X-ray source.
Step width: 0.02deg
Scanning speed: 0.04 deg/s
Acceleration voltage: 40kV
Accelerating current: 30 mA.
The results of the measurement under the above-mentioned measurement conditions were compared with JCPDS cards 70-2038 (corresponding to gibbsite-type aluminum hydroxide), the peak area S (002) corresponding to the (002) plane of the gibbsite-type aluminum hydroxide was calculated, and the results of the measurement were compared with JCPDS cards 83-1505 (corresponding to boehmite) in the same manner to determine the peak area S (020) corresponding to the (020) plane of boehmite. The boehmite content was calculated using the two peak areas and the following formula.
The boehmite content (% by mass) is { S (020)/[ S (020) + S (002) } × 100.
The boehmite precursor content contained in the sample before the heat treatment was calculated using the obtained boehmite content and the following formula.
Boehmite precursor content (% by mass) { (boehmite content × 78/60)/[ boehmite content × 78/60) + (100-boehmite content) ] } × 100.
(5) Boehmite content
The boehmite content of the sample was measured using Cu as an X-ray source under the following measurement conditions in a powder X-ray diffraction measuring apparatus "RINT-2000" manufactured by リガク.
Step width: 0.02deg
Scanning speed: 0.04 deg/s
Acceleration voltage: 40kV
Accelerating current: 30 mA.
The results of the measurement under the above-mentioned measurement conditions were compared with JCPDS cards 70-2038 (corresponding to gibbsite-type aluminum hydroxide), the peak area S (002) corresponding to the (002) plane of the gibbsite-type aluminum hydroxide was calculated, and the results of the measurement were compared with JCPDS cards 83-1505 (corresponding to boehmite) in the same manner to determine the peak area S (020) corresponding to the (020) plane of boehmite. The boehmite content was calculated using the two peak areas and the following formula.
The boehmite content (% by mass) is { S (020)/[ S (020) + S (002) } × 100.
(6) Heat resistance
The measurement was carried out using about 10mg of a sample in a differential thermogravimetric analyzer [ リガク "Thermo Plus TG 8120". Air having a dew point temperature of-20 ℃ or lower was circulated at a flow rate of 100 ml/min, and the temperature was raised from room temperature to 230 ℃ at a temperature raising rate of 10 ℃/min, and the temperature was maintained. The heat resistance was evaluated by measuring the time taken for 1% weight loss based on the time taken for 230 ℃.
Example 1
An aluminum hydroxide powder ("CL-303" manufactured by Sumitomo chemical Co., Ltd.) used as a raw material in comparative example 4 described later was used "]According to WO2014/133049[ example 1]The aluminum hydroxide powders shown in Table 1 were prepared by the methods described above. 100 parts by mass of the aluminum hydroxide powder shown in Table 1 and 5 parts by mass of pulverized aluminum fluoride (manufactured by SENDA CHEMICAL INDUSTRIAL Co., Ltd.)]The powder obtained had a BET specific surface area of 36m2(iv)/g, 10 mass% water slurry of fine powder having an average particle diameter of 0.3 μm was wet-shaken and mixed in a polymer bag, and dried at 120 ℃ to obtain heat-resistant aluminum hydroxide (1). The physical properties of the heat-resistant aluminum hydroxide (1) were measured by the above-mentioned measuring methods. The results are shown in Table 1.
Example 2
100 parts by mass of the aluminum hydroxide powder shown in Table 1 prepared in example 1, 0.3 part by mass of sodium phosphate fluoride [ manufactured by Wako pure chemical industries, Ltd. ] powder, and 1.5 parts by mass of pure water were mixed in a polymer bag by wet shaking, and dried at 120 ℃ to obtain heat-resistant aluminum hydroxide (2). The physical properties of the heat-resistant aluminum hydroxide (2) were measured by the above-mentioned measuring methods. The results are shown in Table 1.
Example 3
100 parts by mass of the aluminum hydroxide powder shown in Table 1 prepared in example 1, and 0.3 part by mass of sodium phosphate fluoride (Wako pure chemical industries, Ltd.) (manufactured by Wako pure chemical industries, Ltd.) were mixed]Powder, 0.6 part by mass of methyl silicate (MS-51 manufactured by Mitsubishi chemical Co., Ltd., SiO2The silicon content is 51 mass%, and the mass average molecular weight is 500-700]0.9 part by mass of ethanol was mixed in a polymer bag by wet shaking, and dried at 120 ℃ to obtain heat-resistant aluminum hydroxide (3). The physical properties of the heat-resistant aluminum hydroxide (3) were measured by the above-mentioned measuring methods. The results are shown in Table 1.
Example 4
Heat-resistant aluminum hydroxide (4) was obtained in the same manner as in example 1 except that the aluminum hydroxide powders [ CL-310 manufactured by Sumitomo chemical Co., Ltd ] shown in Table 1 were used. The physical properties of the heat-resistant aluminum hydroxide (4) were measured by the above-mentioned measuring methods. The results are shown in Table 1.
Example 5
Heat-resistant aluminum hydroxide (5) was obtained in the same manner as in example 2, except that the aluminum hydroxide powders [ CL-310 manufactured by Sumitomo chemical Co., Ltd ] shown in Table 1 were used. The physical properties of the heat-resistant aluminum hydroxide (5) were measured by the above-mentioned measuring methods. The results are shown in Table 1.
Example 6
Heat-resistant aluminum hydroxide (6) was obtained in the same manner as in example 2, except that the aluminum hydroxide powders [ C-301N manufactured by Sumitomo chemical Co., Ltd ] shown in Table 1 were used. The physical properties of the heat-resistant aluminum hydroxide (6) were measured by the above-mentioned measuring methods. The results are shown in Table 1.
Comparative example 1
The aluminum hydroxide powder shown in table 1 prepared in example 1 was used as the aluminum hydroxide (1), and the physical properties of the aluminum hydroxide (1) were measured by the above-described measurement method. The results are shown in Table 1.
Comparative example 2
The aluminum hydroxide powder used as a raw material in example 4 ("CL-310" manufactured by sumitomo chemical corporation) was used as the aluminum hydroxide (2), and the physical properties of the aluminum hydroxide (2) were measured according to the above-described measurement methods. The results are shown in Table 1.
Comparative example 3
The aluminum hydroxide powder used as a raw material in example 6 ("C-301N" manufactured by sumitomo chemical corporation) was used as the aluminum hydroxide (3), and the physical properties of the aluminum hydroxide (3) were measured according to the above-described measurement methods. The results are shown in Table 1.
Comparative example 4
Aluminum hydroxide (4) was obtained in the same manner as in example 2, except that the aluminum hydroxide powders [ CL-303, manufactured by Sumitomo chemical Co., Ltd ] shown in Table 1 were used. The physical properties of the aluminum hydroxide (4) were measured according to the above-mentioned measuring methods. The results are shown in Table 1.
Comparative example 5
The aluminum hydroxide powder used as a raw material in comparative example 4 ("CL-303" manufactured by sumitomo chemical corporation) was used as the aluminum hydroxide (5), and the physical properties of the aluminum hydroxide (5) were measured according to the above-described measurement methods. The results are shown in Table 1.
Comparative example 6
Aluminum hydroxide (6) was obtained in the same manner as in example 2, except that the aluminum hydroxide powders [ C-303, manufactured by Sumitomo chemical Co., Ltd ] shown in Table 1 were used. The physical properties of the aluminum hydroxide (6) were measured according to the above-mentioned measuring methods. The results are shown in Table 1.
Comparative example 7
The aluminum hydroxide powder used as a raw material in comparative example 6 ("C-303" manufactured by sumitomo chemical corporation) was used as the aluminum hydroxide (7), and the physical properties of the aluminum hydroxide (7) were measured according to the above-described measurement methods. The results are shown in Table 1.
The heat-resistant aluminum hydroxides (1) to (6) obtained in examples 1 to 6 exhibited high heat resistance as a result of their long time required to decrease by 1 mass% at 230 ℃. On the other hand, the aluminum hydroxides (1) to (7) in comparative examples 1 to 7 showed low heat resistance because the time required for the reduction by 1 mass% at 230 ℃ was short.
Claims (4)
1. A heat-resistant aluminum hydroxide having a BET specific surface area of 0.5m, a time to 1 mass% reduction at 230 ℃ of 5 to 60 minutes21.8 m/g or more2The ratio of the carbon atoms to the carbon atoms is less than g.
2. The heat-resistant aluminum hydroxide according to claim 1, wherein the average particle diameter is 0.5 to 15 μm.
3. The heat-resistant aluminum hydroxide according to claim 1 or 2, wherein the boehmite content is 15% by mass or less.
4. A resin composition comprising a resin and the heat resistant aluminum hydroxide according to any one of claims 1 to 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014110909 | 2014-05-29 | ||
| JP2014-110909 | 2014-05-29 | ||
| CN201580028081.9A CN106458619B (en) | 2014-05-29 | 2015-04-23 | heat-resisting aluminium hydroxide and its manufacturing method |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580028081.9A Division CN106458619B (en) | 2014-05-29 | 2015-04-23 | heat-resisting aluminium hydroxide and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108314068A CN108314068A (en) | 2018-07-24 |
| CN108314068B true CN108314068B (en) | 2021-01-29 |
Family
ID=54698646
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810239378.5A Active CN108314068B (en) | 2014-05-29 | 2015-04-23 | Heat-resistant aluminum hydroxide and method for producing same |
| CN201580028081.9A Active CN106458619B (en) | 2014-05-29 | 2015-04-23 | heat-resisting aluminium hydroxide and its manufacturing method |
| CN201580028104.6A Active CN106458620B (en) | 2014-05-29 | 2015-05-22 | The manufacturing method of heat-resisting aluminium hydroxide |
| CN201810239775.2A Active CN108408750B (en) | 2014-05-29 | 2015-05-22 | Method for producing heat-resistant aluminum hydroxide |
Family Applications After (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580028081.9A Active CN106458619B (en) | 2014-05-29 | 2015-04-23 | heat-resisting aluminium hydroxide and its manufacturing method |
| CN201580028104.6A Active CN106458620B (en) | 2014-05-29 | 2015-05-22 | The manufacturing method of heat-resisting aluminium hydroxide |
| CN201810239775.2A Active CN108408750B (en) | 2014-05-29 | 2015-05-22 | Method for producing heat-resistant aluminum hydroxide |
Country Status (6)
| Country | Link |
|---|---|
| JP (2) | JPWO2015182305A1 (en) |
| KR (2) | KR102384088B1 (en) |
| CN (4) | CN108314068B (en) |
| DE (2) | DE112015002531T5 (en) |
| TW (2) | TW201900560A (en) |
| WO (2) | WO2015182305A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502615B (en) * | 2018-12-10 | 2021-06-04 | 贵州博汇联润铝业有限公司 | Method for enhancing heat resistance of superfine and ultra-white aluminum hydroxide micro powder |
| JP7135921B2 (en) * | 2019-02-14 | 2022-09-13 | 日本軽金属株式会社 | Aluminum hydroxide powder and method for producing the same |
| IT202100012788A1 (en) * | 2021-05-18 | 2022-11-18 | Nuova Sima S R L | POLYMER COMPOSITION HAVING FLAME RETARDANT PROPERTIES |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59204632A (en) * | 1983-05-06 | 1984-11-20 | Sumitomo Alum Smelt Co Ltd | Molded article of heat-resistant resin |
| JP2002211918A (en) | 2000-11-17 | 2002-07-31 | Showa Denko Kk | Aluminum hydroxide, method for producing the same, resin composition containing the same and printed wiring board using the resin composition |
| DE10248174C1 (en) * | 2002-10-16 | 2003-11-13 | Nabaltec Gmbh | Flame-retardant thermoplastic, thermoset or thermosetting and/or elastomeric polymer composition, for producing coated electrical wire or cable by extrusion, contains aluminum hydroxide with specified properties as flame retardant |
| WO2004080897A1 (en) * | 2003-03-10 | 2004-09-23 | Kawai-Lime Ind. Co., Ltd. | Heat-resistant aluminum hydroxide and method for preparation thereof |
| JP4940556B2 (en) * | 2004-09-07 | 2012-05-30 | 日産自動車株式会社 | Resin composition |
| WO2007074562A1 (en) * | 2005-12-26 | 2007-07-05 | Nippon Light Metal Company, Ltd. | Finely particulate low-soda aluminum hydroxide and process for producing the same |
| CN100391846C (en) * | 2006-08-29 | 2008-06-04 | 惠州学院 | Method for prepring and modifying high heat-resistant aluminium hydroxide |
| JP2009035430A (en) * | 2007-07-31 | 2009-02-19 | Asahi Kagaku Kogyo Co Ltd | METHOD FOR PRODUCING FLAKY alpha-ALUMINA |
| US8629077B2 (en) * | 2007-08-29 | 2014-01-14 | Yunkui Li | Rare earth alumina particulate manufacturing method and application |
| JP5038972B2 (en) * | 2008-05-14 | 2012-10-03 | 日東電工株式会社 | Semiconductor sealing resin composition, method for producing the same, and semiconductor device using the same |
| JP5310472B2 (en) | 2009-10-15 | 2013-10-09 | 日立化成株式会社 | High heat-resistant aluminum hydroxide particles, production method thereof, resin composition containing the particles, and printed wiring board using the resin composition |
| JP5779962B2 (en) * | 2011-04-27 | 2015-09-16 | 日立化成株式会社 | Resin composition for package substrate and prepreg and laminate using the same |
| JP5834540B2 (en) * | 2011-06-29 | 2015-12-24 | 日立化成株式会社 | Heat resistant aluminum hydroxide particles and production method thereof, resin composition, prepreg, laminate |
| JP6346421B2 (en) | 2012-08-23 | 2018-06-20 | 日揮触媒化成株式会社 | Crystalline alumina laminated particle and method for producing the crystalline alumina laminated particle |
| JP5636072B2 (en) * | 2013-02-26 | 2014-12-03 | 住友化学株式会社 | Method for producing heat-resistant aluminum hydroxide |
-
2015
- 2015-04-23 JP JP2016523389A patent/JPWO2015182305A1/en active Pending
- 2015-04-23 CN CN201810239378.5A patent/CN108314068B/en active Active
- 2015-04-23 WO PCT/JP2015/062443 patent/WO2015182305A1/en active Application Filing
- 2015-04-23 CN CN201580028081.9A patent/CN106458619B/en active Active
- 2015-04-23 KR KR1020167033157A patent/KR102384088B1/en active IP Right Grant
- 2015-04-23 DE DE112015002531.6T patent/DE112015002531T5/en not_active Withdrawn
- 2015-05-22 WO PCT/JP2015/064725 patent/WO2015182504A1/en active Application Filing
- 2015-05-22 KR KR1020167033177A patent/KR102375076B1/en active IP Right Grant
- 2015-05-22 JP JP2016523464A patent/JP6679477B2/en active Active
- 2015-05-22 CN CN201580028104.6A patent/CN106458620B/en active Active
- 2015-05-22 CN CN201810239775.2A patent/CN108408750B/en active Active
- 2015-05-22 DE DE112015002520.0T patent/DE112015002520T5/en not_active Withdrawn
- 2015-05-28 TW TW107125301A patent/TW201900560A/en unknown
- 2015-05-28 TW TW104117160A patent/TWI657049B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| KR102375076B1 (en) | 2022-03-15 |
| JPWO2015182504A1 (en) | 2017-04-20 |
| DE112015002531T5 (en) | 2017-02-23 |
| CN106458619B (en) | 2018-06-05 |
| CN108314068A (en) | 2018-07-24 |
| JP6679477B2 (en) | 2020-04-15 |
| KR20170012267A (en) | 2017-02-02 |
| TW201609548A (en) | 2016-03-16 |
| CN108408750B (en) | 2020-11-20 |
| CN106458620B (en) | 2018-06-05 |
| KR20170009880A (en) | 2017-01-25 |
| WO2015182504A1 (en) | 2015-12-03 |
| CN106458620A (en) | 2017-02-22 |
| CN106458619A (en) | 2017-02-22 |
| TWI657049B (en) | 2019-04-21 |
| TW201900560A (en) | 2019-01-01 |
| WO2015182305A1 (en) | 2015-12-03 |
| DE112015002520T5 (en) | 2017-03-02 |
| KR102384088B1 (en) | 2022-04-06 |
| JPWO2015182305A1 (en) | 2017-04-20 |
| CN108408750A (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7977410B2 (en) | Fine pore formation agent for porous resin film and composition containing the same for porous resin film | |
| JP5771055B2 (en) | Method for producing spherical alumina powder | |
| US20110213065A1 (en) | Synthetic inorganic flame retardants, methods for their preparation, and their use as flame retardants | |
| KR20070051833A (en) | Flame retarding composition with monomodal particle size distribution based on metal hydroxide and clay | |
| CN108314068B (en) | Heat-resistant aluminum hydroxide and method for producing same | |
| KR20220144809A (en) | Hollow Silica Particles and Manufacturing Method Thereof | |
| MX2008015384A (en) | Process for the production of aluminum hydroxide. | |
| TWI601691B (en) | Heat-resistant aluminum hydroxide manufacturing method | |
| TWI593787B (en) | Flame retardant, flame retardant composition and compact | |
| AU2009217065A1 (en) | A process for the production of nanodispersible boehmite and the use thereof in flame retardant synthetic resins | |
| KR20160111480A (en) | Alumina compositions and methods for producing same | |
| US20220219999A1 (en) | Spherical magnesium oxide, manufacturing method thereof, thermal conductive filler and resin composition | |
| JP6778320B2 (en) | Alumina hydrate particles, flame retardants, resin compositions and electric wires / cables |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |