WO2018168496A1 - ハイドロタルサイト類組成物、および、該組成物を含む樹脂添加剤 - Google Patents
ハイドロタルサイト類組成物、および、該組成物を含む樹脂添加剤 Download PDFInfo
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- WO2018168496A1 WO2018168496A1 PCT/JP2018/007776 JP2018007776W WO2018168496A1 WO 2018168496 A1 WO2018168496 A1 WO 2018168496A1 JP 2018007776 W JP2018007776 W JP 2018007776W WO 2018168496 A1 WO2018168496 A1 WO 2018168496A1
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- Prior art keywords
- composition
- hydrotalcite
- surface treatment
- calcium
- weight
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Classifications
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- 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
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- 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
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
Definitions
- the present invention relates to a hydrotalcite composition and a resin additive containing the composition.
- hydrotalcites have an excellent anion exchange function, they are widely used as catalysts, pharmaceuticals, additives for resins (compositions), and the like.
- hydrotalcites are used for polyurethane elastic fibers for the purpose of preventing deterioration due to chlorine (Patent Document 1).
- the present invention has been made to solve the above-mentioned problems, and its main purpose is to provide a hydrotalcite composition having excellent dispersibility in a resin composition, particularly a urethane resin composition containing an amide solvent. It is to provide.
- hydrotalcite composition containing a surface treating agent While the inventors have repeatedly studied the means for improving the dispersibility of hydrotalcites (particularly, the dispersibility in the polyurethane resin composition), It has been found that calcium extracted with hot toluene affects dispersibility.
- the hydrotalcite composition of the present invention is a composition containing hydrotalcite and a surface treatment agent containing an organic compound. At least a part of the hydrotalcites is in a state of being coated with the surface treatment agent.
- the extract extracted by hot toluene treatment is 1% by weight or less of the composition, and the calcium contained in the extract is 500 ppm of the weight of the hydrotalcite composition. It is as follows. In one embodiment, the calcium contained in the extract is 200 ppm or less by weight of the composition. In one embodiment, the hydrotalcites have been decrystallized water treated.
- the surface treatment agent is at least one selected from higher fatty acids, metal salts of higher fatty acids and metals other than calcium, anionic surfactants, phosphate esters, and coupling agents. .
- an additive is provided.
- the additive of the present invention contains the hydrotalcite composition.
- a resin composition is provided.
- the resin composition of the present invention contains a urethane-based resin, an amide-based solvent, and the above additives.
- a hydrotalcite composition having excellent dispersibility can be provided.
- calcium extracted with hot toluene can affect dispersibility in the resin composition.
- the dispersibility of the hydrotalcite in the resin composition can be stably increased.
- Calcium contained in hydrotalcites is an industrial metal compound that is a general raw material (for example, light-burned magnesium, which is a starting material for magnesium compounds, or slaked lime, quick lime, etc. added to seawater or ionic bitter juice) Derived from the obtained magnesium hydroxide). Therefore, producing hydrotalcites substantially free of calcium can lead to an increase in production cost.
- the hydrotalcite composition of the present invention can improve the quality and productivity in the production of a resin composition and a product (for example, fiber) using the resin composition.
- the hydrotalcite composition of the present invention includes hydrotalcite and a surface treatment agent containing an organic compound.
- the hydrotalcites are in a state where at least a part of the surface is coated with the surface treatment agent.
- the extract extracted by hot toluene treatment (hereinafter referred to as hot toluene extract) is 1% by weight or less of the composition, and the calcium contained in the hot toluene extract is not contained. It is 500 ppm or less of the weight of this composition.
- hot toluene extract is 1% by weight or less of the composition and the content of calcium contained in the hot toluene extract is 500 ppm or less of the weight of the composition, high dispersibility can be exhibited.
- the extract extracted by a hot toluene process means the extract extracted by the hot toluene extraction method as described in the Example of this specification.
- the hydrotalcite composition at least a part of the hydrotalcite is coated with a surface treatment agent.
- the hydrotalcites can exhibit higher dispersibility in the resin composition.
- the hot toluene extract of the hydrotalcite composition is 1% by weight or less, preferably 0.8% by weight or less, more preferably 0.5% by weight or less of the hydrotalcite composition.
- the hot toluene extract is 1% by weight or less, stable dispersibility in the resin composition can be obtained.
- the hot toluene extract may be, for example, 0.1% by weight or more of the hydrotalcite composition.
- the amount of calcium contained in the hot toluene extract is 500 ppm or less, preferably 400 ppm or less, particularly preferably 200 ppm or less, based on the weight of the composition.
- the hydrotalcite composition can be prevented from swelling (gelling) in the resin composition, and a stable dispersion state can be maintained over time.
- the calcium content is preferably below the detection limit.
- Calcium contained in the hydrotalcite composition is not particularly limited as long as the hot toluene extract and the calcium contained in the hot toluene extract are within the above ranges.
- Calcium contained in the hydrotalcite composition is, for example, 1000 ppm or less, and preferably 750 ppm or less.
- the calcium contained in the hydrotalcite composition may be, for example, 100 ppm or more from the viewpoint of achieving both cost and quality.
- calcium is a divalent metal ion, it can be contained as a divalent metal ion constituting hydrotalcite.
- calcium that is not extracted by the hot toluene extraction is present in a stable state in the hydrotalcite, it is considered that it does not cause the swelling or the like.
- Hydrotalcite Any appropriate hydrotalcite can be used as the hydrotalcite.
- Hydrotalcites are represented by the general formula M 2+ 1-x M 3+ x (OH) 2 A n ⁇ x / n ⁇ mH 2 O.
- M 2+ represents at least one divalent metal ion selected from the group consisting of Mg 2+ , Zn 2+ , Fe 2+ , Mn 2+ , Co 2+ , Ni 2+ and Cu 2+ .
- M 3+ represents at least one trivalent metal ion selected from the group consisting of Al 3+ , Fe 3+ , Cr 3+ and Co 3+ .
- a n ⁇ represents at least one anion selected from the group consisting of OH ⁇ , CO 3 2 ⁇ , SO 4 2 ⁇ , NO 3 ⁇ and Cl ⁇ .
- x is a number 0 ⁇ x ⁇ 0.5
- m is a number 0 ⁇ m ⁇ 1
- n is 1 ⁇ n ⁇ 3.
- Hydrotalcites may be natural products or synthetic products.
- a synthetic product is preferable from the viewpoint that the calcium content can be adjusted to a desired amount.
- hydrotalcites include Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, Mg 4 Al 2 (OH ) 12 CO 3 .3H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 Mg 3.5 ZnAl 2 (OH) 13 CO 3 .3.5H 2 O, and the like. Only one type of hydrotalcite may be used, or two or more types may be used in combination.
- hydrotalcites When hydrotalcites are synthesized, they can be synthesized by any appropriate method. For example, after preparing a slurry containing a hydroxide, oxide, carbonate, etc. of a metal constituting hydrotalcite such as magnesium and aluminum, the slurry is subjected to wet pulverization treatment if necessary, and then carbon dioxide gas Alternatively, it can be synthesized by adding a salt such as hydrogen carbonate and carbonate and heating and mixing. Another method includes hydrothermal treatment of a magnesium compound and an aluminum compound in an aqueous solution containing carbonate ions in the presence of an alkali.
- the magnesium source When hydrothermal treatment is performed, the magnesium source includes water-soluble salts such as magnesium sulfate, magnesium chloride, and magnesium nitrate and / or non-magnesium oxide, magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, and the like having an average particle size of 10 ⁇ m or less. It is preferable to use a water-soluble magnesium compound.
- the aluminum source it is preferable to use water-soluble salts such as aluminum sulfate and aluminum chloride and / or aluminum hydroxide having an average particle diameter of 10 ⁇ m or less.
- water used for preparing the slurry and the aqueous solution ion-exchanged water or distilled water is preferably used.
- the amount of calcium contained in hydrotalcites can be reduced.
- wet crushers such as a bead mill
- dry crushers such as a hammer mill and a jet mill.
- pulverizing only one type may be subjected to the pulverization step, or two or more compounds may be simultaneously subjected to the pulverization step.
- a metal hydroxide, oxide, carbonate, etc. constituting the hydrotalcite as well as a magnesium compound and an aluminum compound having a low calcium content.
- a calcium content of less than 100 ppm.
- the hydrogen carbonate and / or carbonate used for introducing carbonate ions into the hydrotalcites preferably have a low calcium content. Therefore, what was prepared using the carbon dioxide gas can be used preferably. By synthesizing using these, the amount of calcium that can be contained in hydrotalcites can be reduced. In addition, it is also useful to reduce the calcium contained in hydrotalcites by using carbon dioxide in combination with the use of bicarbonate and / or carbonate.
- the median diameter (d50) is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 3 ⁇ m.
- the median diameter is a value measured using a laser diffraction particle size distribution meter.
- Hydrothermal treatment can be performed by any appropriate method, and is usually performed in a pressure vessel such as an autoclave.
- the treatment temperature (slurry temperature) is usually 120 ° C. to 250 ° C., preferably 130 ° C. to 230 ° C., more preferably 140 ° C. to 230 ° C. Depending on the apparatus used for processing, the temperature may not be measured. In that case, you may adjust the said process reaction with the pressure in a container. In that case, the pressure is, for example, 0.1 MPa to 10 MPa, preferably 0.2 MPa to 4 MPa.
- the treatment time is, for example, 1 hour to 10 hours, preferably 1 hour to 4 hours.
- the slurry after the hydrothermal treatment is separated by filtration, then the solid (wet cake) containing hydrotalcite and the filtrate are separated, and the recovered solid is washed with water. Washing with water may be performed only once or multiple times.
- the water used for washing is preferably ion-exchanged water or distilled water. By using ion-exchanged water or distilled water, calcium contained in the obtained hydrotalcites can be reduced. In addition, you may perform the surface treatment mentioned later using the cake after the said water washing.
- the hydrotalcite can be obtained by collecting the solid content separated by filtration, drying by heating in an oven or the like, and if necessary, dry-grinding the solid content after drying.
- hydrotalcites have been decrystallized water treated. By being treated with decrystallized water, the effect of improving dispersibility can be further exhibited.
- the decrystallization water treatment can be performed by any appropriate method. For example, the decrystallized water treatment can be performed by baking at 200 to 350 ° C. for 0.5 to 24 hours. The decrystallization water treatment may be performed only with hydrotalcites or after the composition is prepared.
- Surface treatment agent Any appropriate surface treatment agent can be used as the surface treatment agent. Examples include higher fatty acids, metal salts of higher fatty acids and metals other than calcium, anionic surfactants, phosphate esters, silane coupling agents, titanium coupling agents, and aluminum coupling agents.
- higher fatty acids such as stearic acid, oleic acid, erucic acid, palmitic acid and lauric acid, metal salts such as lithium salts, sodium salts and potassium salts of these higher fatty acids, higher alcohols such as stearyl alcohol and oleyl alcohol
- Anionic surfactants such as sulfate ester salts of polyethylene glycol ethers, sulfate ester salts of amide bonds, ether bond sulfonates, ester bond sulfonates, amide bond alkyl aryl sulfonates, ether bond alkyl aryl sulfonates, etc.
- Mono- or diesters such as orthophosphoric acid and oleyl alcohol, stearyl alcohol or mixtures thereof, phosphoric acid esters such as acid forms or alkali metal salts or amine salts, vinylethoxysilane, ⁇ -methacryloxy Silane coupling agents such as propyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, ⁇ -aminopropyltrimethoxysilane, isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltridecylbenzenesulfonyl titanate And the like, and alkali coupling agents such as acetoalkoxyaluminum diisopropylate.
- the surface treatment agent is preferably a higher fatty acid or a metal salt of a higher fatty acid and a metal other than calcium, more preferably stearic acid and stearic acid, from the viewpoint of dispersibility in the resin, handleability, and cost.
- the hot toluene extract is 1% by weight or less of the hydrotalcite composition.
- This hot toluene extract is typically a metal salt of an organic compound and calcium contained in the surface treatment agent.
- calcium stearate can be extracted as at least part of the hot toluene extract.
- This calcium salt can contribute to a decrease in the dispersibility of hydrotalcites.
- a metal soap such as calcium stearate is used when producing a polyurethane elastic fiber as an additive for improving the spinnability (for example, Japanese Patent Application Laid-Open No. 2007-1000024).
- the surface treatment agent can be used in any appropriate amount depending on the purpose.
- the amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 3.5 parts by weight with respect to 100 parts by weight of the hydrotalcite. If it is in the said range, the improvement effect of the dispersibility by using a surface treating agent can fully be acquired. Moreover, generation
- hydrotalcite composition of the present invention can be produced by any appropriate method. For example, it can be produced by mixing any appropriate hydrotalcite and a surface treatment agent.
- hydrotalcites are at least partially coated with a surface treatment agent.
- a method (surface treatment method) for coating hydrotalcites with a surface treatment agent any appropriate method can be used, and examples thereof include a wet method and a dry method.
- a surface treatment agent is added as a solution or an emulsion to a slurry containing hydrotalcites, and after stirring, is sufficiently mixed while heating to a temperature up to 100 ° C. as necessary. Thereafter, the hydrotalcite can be filtered, washed with water and dried.
- the surface treatment agent is used as a solution or an emulsion, it is preferable to use ion exchange water or distilled water as a dispersion medium.
- the heating and mixing time after addition of the surface treatment agent can be set to any appropriate time, and is preferably 24 hours or longer.
- the longer the heating and mixing time the more the hot toluene extract from the hydrotalcite composition tends to decrease.
- the heating and mixing time is, for example, 100 hours or less. This is because the effect of reducing the hot toluene extract is small, and there is little advantage of performing heating and mixing over 100 hours.
- the surface treatment is preferably performed in the presence of a sodium compound, more preferably in the presence of a water-soluble sodium compound.
- a sodium compound By performing the surface treatment in the presence of a sodium compound, the hot toluene extract from the hydrotalcite composition tends to be reduced.
- Arbitrary appropriate sodium compounds can be used as a sodium compound, For example, fatty acid sodium, such as sodium carbonate, sodium hydrogencarbonate, sodium chloride, sodium hydroxide, sodium phosphate, sodium stearate, etc. are mentioned.
- the surface treatment When performing the surface treatment by a wet method, for example, the surface treatment is performed after adjusting the pH of the solution or emulsion containing the surface treatment agent to pH 7 to pH 14. By performing the surface treatment under such conditions, the hot toluene extract from the hydrotalcite composition tends to be reduced.
- the slurry containing hydrotalcite used for the surface treatment may be prepared for the surface treatment step. That is, the surface treatment may be performed by adding a surface treatment agent to a slurry in which a wet cake obtained in the synthesis process of hydrotalcites is dispersed in water. The surface treatment may be performed by directly adding a surface treatment agent to the slurry obtained by the heat mixing treatment or hydrothermal treatment.
- the additive of the present invention contains the hydrotalcite composition. Since the hydrotalcites of the present invention are excellent in dispersibility in a resin composition, they have excellent characteristics as additives for resin compositions.
- the additive of the present invention may contain any appropriate other component such as an antioxidant depending on the application.
- the additive of the present invention may be used in a solid state or may be used in a state dispersed in any appropriate solvent.
- the resin composition of the present invention contains a urethane resin, an amide solvent, and the above-mentioned additives.
- Conventional hydrotalcites have a problem that it is difficult to uniformly disperse them in an amide solvent used in the production of polyurethane fibers. Since the hydrotalcite composition of the present invention can be dispersed well even in an amide solvent, the hydrotalcite is well dispersed and changes over time such as solid-liquid separation are less likely to occur in the solvent. Therefore, a resin composition with little deterioration with time can be provided.
- the content of the additive contained in the resin composition of the present invention can be set to any appropriate range.
- the content of the additive in the resin composition is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. If it is such content, the effect by adding hydrotalcite can fully be acquired.
- the urethane resin is obtained, for example, by reacting an active hydrogen-containing compound with a prepolymer obtained by reacting a polymer diol and diisocyanate.
- any appropriate diol can be used, and examples thereof include polyester diol, polycarbonate diol, and polyether diol.
- Polyether diol is preferable. Only one type of polymer diol may be used, or two or more types may be used in combination.
- any appropriate diisocyanate can be used as the diisocyanate.
- examples thereof include aliphatic, alicyclic or aromatic organic diisocyanates having two isocyanate groups in the molecule. Specifically, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4 An organic diisocyanate such as 4,4'-dicyclohexylmethane diisocyanate is exemplified, and 4,4'-diphenylmethane diisocyanate is preferable. Only one diisocyanate may be used, or two or more diisocyanates may be used in combination.
- any appropriate compound can be used as the active hydrogen-containing compound.
- a low molecular compound having a molecular weight of 500 or less and containing at least two hydrogen atoms capable of reacting with isocyanate can be used.
- diamines such as ethylenediamine, propylenediamine, tolylenediamine, m-xylylenediamine, 1,3-diaminocyclohexane, isophoronediamine, hydrazine, 4,4'-diaminodiphenylmethane, dihydrazide, piperazine, ethylene glycol And diols such as propylene glycol and 1,4-butanediol, preferably ethylenediamine and 1,2-propylenediamine. These compounds may be used alone or in combination of two or more.
- amide solvent Any appropriate solvent can be used as the amide solvent.
- amide solvent include dimethylacetamide and dimethylformamide. Preferred is dimethylacetamide.
- the resin composition of the present invention may contain any appropriate other additive depending on the intended use, in addition to the additive containing the hydrotalcite composition.
- other additives include an ultraviolet ray inhibitor, an antioxidant, a pigment, a filler, an antistatic agent, a disinfectant, a deodorant, and a lubricant.
- the amount of these other additives used is set to any appropriate value depending on the purpose.
- the resin composition of the present invention can be prepared by any appropriate method.
- the method etc. which add and mix the said additive to the solution containing urethane type resin and arbitrary solvents are mentioned.
- Mixing can be performed using any appropriate means, and for example, mixing is performed using a homomixer.
- An example of the use of the resin composition of the present invention is the production of polyurethane fibers.
- a method for spinning using the resin composition a wet spinning method or a dry spinning method may be used.
- the hydrotalcites of the present invention can be favorably dispersed even when an amide solvent is used as the solvent. Therefore, the resin composition of the present invention can prevent the occurrence of a problem of reducing productivity even when used in the dry spinning method.
- magnesium hydroxide product name: 200-06H, manufactured by Kyowa Chemical Industry Co., Ltd., calcium content: 30 ppm
- sodium hydrogen carbonate sodium hydroxide (manufactured by AGC Asahi Glass Co., Ltd., calcium content 20 ppm)
- sodium hydrogen carbonate sodium hydroxide, manufactured by Iwatani Sangyo Co., Ltd.
- sodium bicarbonate 60 % By weight sodium bicarbonate 60 % By weight
- the slurry was transferred to an autoclave and hydrothermally treated at 190 ° C. for 4 hours (pressure: 1.3 MPa). The obtained slurry was filtered and further washed with 15 L of ion exchange water.
- a surface treatment agent (trade name: LUNAC S70 industrial stearic acid (less than the lower limit of calcium content measurement)) is added to 1 L of ion-exchanged water, and adjusted to pH 10 with 48% aqueous sodium hydroxide solution.
- a surface treatment agent solution was prepared. While maintaining the obtained slurry at 95 ° C., the prepared surface treating agent solution was added and surface treatment was performed for 48 hours. Next, the solid was filtered off from the slurry, and then the filter cake was washed with 35 ° C. and 15 L of ion exchange water. The obtained water-washed cake was dried at 100 ° C. for 24 hours and pulverized to obtain a hydrotalcite composition (sample A) as a solid product.
- Example 2 Put 400 ml of ion-exchanged water in a 3 L reaction vessel, and under stirring, magnesium chloride hexahydrate (Tonda Pharmaceutical Co., Ltd., calcium content: 30 ppm) and aluminum sulfate salt (Pure Chemical Co., Ltd., calcium content 20 ppm) 800 ml of mixed aqueous solution (Mg content 33.0 g / L, Al content 17.0 g / L), caustic soda (sodium hydroxide) (AGC Asahi Glass Co., Ltd., calcium content 20 ppm) and sodium carbonate aqueous solution (sodium hydroxide) 800 ml of a mixed aqueous solution (NaOH content 166.2 g / L, Na 2 CO 3 content 170 g / L) with carbon dioxide gas (made by Iwatani Corp., adjusted to pH 11) was added to the mixture and stirred for 10 minutes
- the obtained product was hydrothermally synthesized in an autoclave at 180
- the obtained slurry was filtered and further washed with 15 L of ion exchange water (calcium content 5 ppm). Thereafter, the wet cake was collected, 3 L of ion exchange water was added to the wet cake, and the mixture was stirred until it became a slurry. While maintaining the obtained slurry at 95 ° C., 5 g of a surface treating agent (trade name: Lunac S70 industrial stearic acid (calculated below the calcium content measurement lower limit)) manufactured by Kao Corporation was added. Thereafter, a 48% aqueous sodium hydroxide solution was added to a pH of 10. The prepared surface treating agent solution was added and surface treatment was performed for 48 hours.
- a surface treating agent trade name: Lunac S70 industrial stearic acid (calculated below the calcium content measurement lower limit)
- Example 3 The hydrotalcite composition obtained in Example 2 was heat-treated at 250 ° C. for 3 hours using an oven to obtain a hydrotalcite composition (Sample B-1).
- Example 4 A hydrotalcite composition (sample C), which is a solid product, was obtained in the same manner as in Example 1 except that aluminum hydroxide having a median diameter (d50) of 7.0 ⁇ m was used.
- Example 1 Use of magnesium hydroxide having a calcium content of 1500 ppm (trade name: MAGSTAR # 4, manufactured by Tateho Chemical Industry Co., Ltd.), use of industrial water instead of ion-exchanged water, industrial sodium carbonate (sodium carbonate (A hydrotalcite composition (sample D), which was a solid product, was obtained in the same manner as in Example 3 except that Central Glass Co., Ltd., trade name: soda ash (heavy coal) was used.
- Comparative Example 2 A hydrotalcite composition which is a solid product in the same manner as in Comparative Example 1 except that magnesium hydroxide having a calcium content of 2000 ppm (trade name: MAGSTAR # 20, manufactured by Tateho Chemical Industry Co., Ltd.) was used. (Sample E) was obtained.
- Comparative Example 3 The hydrotalcite composition obtained in Comparative Example 2 was heat-treated at 250 ° C. for 3 hours using an oven to obtain a hydrotalcite composition (Sample E-1).
- the ratio of the weight of the hydrotalcite initially charged in the Soxhlet extractor with respect to the weight of the obtained dried product was calculated and used as the hot toluene extraction amount.
- Measurement of calcium content of hot toluene extract Put the above hot toluene extract, 2 ml of 60% nitric acid, 10 ml of ether and 30 ml of ion-exchanged water into a container and heat it using a hot plate with the plate surface set at 120 ° C. Was removed. Next, using the obtained liquid, the calcium content in the hot toluene extract was measured by ICP-MS (manufactured by Seiko Instruments Inc., product name: ICP1700HVR).
- the ratio with respect to the initially loaded hydrotalcite composition was measured, and was defined as the amount of calcium extracted with hot toluene. 3. Measurement of calcium content in hydrotalcite composition
- a hot plate with 0.2 g of the obtained hydrotalcite composition, 2 ml of 60% nitric acid, 2 ml of 90% sulfuric acid in a container and the plate surface set to 120 ° C. Heated to evaporate the water. Then, after cooling to room temperature and adding 2 ml of 60% nitric acid, the plate surface was heated on a hot plate set at 120 ° C. to evaporate the water. The operation of adding nitric acid and heating was repeated 5 times.
- ion-exchanged water was added to the sample from which water had been evaporated, and a 100 ml aqueous solution was prepared using a volumetric flask.
- the calcium content in the hydrotalcite composition was measured by ICP-MS (manufactured by Seiko Instruments Inc., product name: ICP1700HVR). 4). Viscosity and dispersibility evaluation (100 mesh metal net residue) Into a 500 ml glass beaker, 300 g of dimethylacetamide (DMAC) was added, and then 50 g of the obtained hydrotalcite composition was added, followed by stirring and mixing at 3000 rpm for 3 minutes with a high-speed stirring disper to obtain a slurry.
- DMAC dimethylacetamide
- the viscosity of the slurry immediately after the stirring was measured with a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: TVB-10). Thereafter, the slurry was left for 2 hours, the viscosity was measured again, and the state of the slurry was visually observed. The slurry that was a uniform and smooth slurry was judged as “good”, and there was an agglomerate that could be visually recognized. Next, the slurry after being allowed to stand for 2 hours was passed through a 100 mesh metal net. The residue remaining on the net was washed with 200 ml of ethanol, dried in an oven at 100 ° C. for 12 hours, and the weight was measured. Of 50 g of the added hydrotalcite composition, the amount that could not pass through the net (residual amount) was determined.
- the hydrotalcite composition of the present invention can be suitably used, for example, as an additive for resins.
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Abstract
Description
1つの実施形態においては、上記抽出物に含まれるカルシウムは、組成物の重量の200ppm以下である。
1つの実施形態においては、上記ハイドロタルサイト類は脱結晶水処理されたものである。
1つの実施形態においては、上記表面処理剤は高級脂肪酸、高級脂肪酸とカルシウム以外の金属との金属塩、アニオン界面活性剤、リン酸エステル、および、カップリング剤から選択される少なくとも1種である。
本発明の別の局面においては、添加剤が提供される。本発明の添加剤は、上記ハイドロタルサイト類組成物を含む。
本発明のさらに別の局面においては、樹脂組成物が提供される。本発明の樹脂組成物は、ウレタン系樹脂、アミド系溶媒、および、上記添加剤を含む。
本発明のハイドロタルサイト類組成物は、ハイドロタルサイト類と、有機化合物を含む表面処理剤とを含む。このハイドロタルサイト類は、表面の少なくとも一部が上記表面処理剤で被覆された状態である。このハイドロタルサイト類組成物は、熱トルエン処理により抽出される抽出物(以下、熱トルエン抽出物という)が該組成物の1重量%以下であり、かつ、熱トルエン抽出物に含まれるカルシウムが該組成物の重量の500ppm以下である。熱トルエン抽出物が組成物の1重量%以下であり、かつ、熱トルエン抽出物に含まれるカルシウムの含有量が組成物の重量の500ppm以下であることにより、高い分散性が発揮され得る。さらに、この高い分散性は、従来分散性に改善の余地があると考えられていた表面処理剤を用いた場合であっても得られるため、様々な表面処理剤の選択が可能になる。さらに、高価な表面処理剤を用いることなく、分散性を向上させることができる。また、これまで問題となっていた、ハイドロタルサイト類の生産バッチごとでの分散性のバラつきをも防止し得る。なお、本明細書において、熱トルエン処理により抽出される抽出物とは、本明細書の実施例に記載の熱トルエン抽出法により抽出された抽出物をいう。
ハイドロタルサイト類としては、任意の適切なハイドロタルサイト類を用いることができる。ハイドロタルサイト類は、一般式M2+ 1-xM3+ x(OH)2An- x/n・mH2Oで表される。この一般式において、M2+は、Mg2+、Zn2+、Fe2+、Mn2+、Co2+、Ni2+およびCu2+からなる群より選ばれた少なくとも1種の2価の金属イオンを表す。M3+は、Al3+、Fe3+、Cr3+およびCo3+からなる群より選ばれた少なくとも1種の3価の金属イオンを表す。An-は、OH-、CO3 2-、SO4 2-、NO3-およびCl-からなる群より選ばれた少なくとも1種の陰イオンを表す。xは0<x≦0.5の数であり、mは0≦m≦1の数であり、nは1≦n≦3である。ハイドロタルサイト類は、天然物であってもよく、合成品であってもよい。カルシウムの含有量を所望の量に調整できるという点からは、合成品が好ましい。
上記表面処理剤としては、任意の適切な表面処理剤を用いることができる。例えば、高級脂肪酸、高級脂肪酸とカルシウム以外の金属との金属塩、アニオン界面活性剤、リン酸エステル、シランカップリング剤、チタンカップリング剤、アルミニウムカップリング剤等のカップリング剤が挙げられる。具体的には、ステアリン酸、オレイン酸、エルカ酸、パルミチン酸、ラウリン酸等の高級脂肪酸、これら高級脂肪酸のリチウム塩、ナトリウム塩、カリウム塩等の金属塩、ステアリルアルコール、オレイルアルコール等の高級アルコールの硫酸エステル塩、ポリエチレングリコールエーテルの硫酸エステル塩、アミド結合硫酸エステル塩、エーテル結合スルホン酸塩、エステル結合スルホネート、アミド結合アルキルアリールスルホン酸塩、エーテル結合アルキルアリールスルホン酸塩等のアニオン界面活性剤、オルトリン酸とオレイルアルコール、ステアリルアルコール等のモノ又はジエステル又はこれらの混合物であって、それらの酸型又はアルカリ金属塩又はアミン塩等のリン酸エステル、ビニルエトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、γ-アミノプロピルトリメトキシシラン等のシランカップリング剤、イソプロピルトリイソステアロイルチタネート、イソプロピルトリス(ジオクチルパイロホスフェート)チタネート、イソプロピルトリデシルベンゼンスルホニルチタネート等のチタンカップリング剤、アセトアルコキシアルミニウムジイソプロピレート等のアルカリカップリング剤等が挙げられる。表面処理剤としては、樹脂への分散性、取扱い性、および、コストの点から、好ましくは高級脂肪酸または高級脂肪酸とカルシウム以外の金属との金属塩であり、より好ましくはステアリン酸、ならびに、ステアリン酸ナトリウムおよびステアリン酸マグネシウム等のステアリン酸とカルシウム以外の金属との金属塩である。
本発明のハイドロタルサイト類組成物は任意の適切な方法により製造することができる。例えば、任意の適切なハイドロタルサイト類と表面処理剤とを混合することにより製造することができる。
本発明の添加剤は、上記ハイドロタルサイト類組成物を含む。本発明のハイドロタルサイト類は樹脂組成物への分散性に優れるため、樹脂組成物用添加剤として優れた特性を有する。本発明の添加剤は、用途等に応じて、酸化防止剤等の任意の適切な他の成分を含んでいてもよい。
本発明の樹脂組成物は、ウレタン系樹脂、アミド系溶媒および上記添加剤を含む。従来のハイドロタルサイト類は、ポリウレタン系繊維の製造に用いられるアミド系溶媒中での均一な分散が難しいという課題がある。本発明のハイドロタルサイト類組成物は、アミド系溶媒中でも良好に分散させることができるため、ハイドロタルサイト類が良好に分散し、溶媒中で固液分離等の経時変化が起こりにくくなる。そのため、経時劣化の少ない樹脂組成物を提供することができる。
5Lの反応容器に、水酸化マグネシウム(製品名:200-06H、協和化学工業社製、カルシウム含有量:30ppm)111.8g、水酸化アルミニウム(製品名:HIGHLITE H-32、昭和電工社製、メジアン径(d50)=8.0μm、カルシウム含有量:20ppm)74.8gを入れ、全量が3Lになるようにイオン交換水を添加して、5分間攪拌し、スラリーを調製した。このスラリーを、湿式粉砕装置(製品名:ダイノーミルMULTILAB)で12分間(滞留時間)湿式粉砕処理した。その後、粉砕処理したスラリーに炭酸水素ナトリウム(苛性ソーダ(水酸化ナトリウム、AGC旭硝子社製、カルシウム含有量20ppm)に炭酸ガス(岩谷産業社製)を通気し、pH8にしたもの、炭酸水素ナトリウムとして60重量%)を、水酸化マグネシウム1モルに対して1/2モルとなるように添加し、10分間攪拌した。次いで、スラリーをオートクレーブに移し、190℃で4時間水熱処理した(圧力:1.3MPa)。得られたスラリーをろ過し、さらに15Lのイオン交換水で水洗した。その後、ウェットケーキを分取し、該ウェットケーキを3Lのイオン交換水に添加し、スラリー状になるまで混合した。別途、イオン交換水1Lに表面処理剤(花王株式会社製、商品名:ルナック S70 工業用ステアリン酸(カルシウム含有量測定下限値未満))7gを添加し、48%水酸化ナトリウム水溶液でpH10に調整した表面処理剤溶液を調製した。得られたスラリーを95℃に保持しながら、調製した表面処理剤溶液を添加し、48時間表面処理を行った。次いで、該スラリーから固体をろ別し、その後、ろ過ケーキを35℃、15Lのイオン交換水で水洗した。得られた水洗ケーキを100℃で24時間乾燥し、粉砕を行うことによって固形の生成物であるハイドロタルサイト類組成物(サンプルA)を得た。
3Lの反応容器にイオン交換水400mlを入れ、撹拌下において、塩化マグネシウム6水和物(富田製薬社製、カルシウム含有量:30ppm)と硫酸アルミニウム塩(純正化学社製、カルシウム含有量20ppm)との混合水溶液(Mg含有量33.0g/L、Al含有量17.0g/L)800mlと、苛性ソーダ(水酸化ナトリウム)(AGC旭硝子社製、カルシウム含有量20ppm)と炭酸ソーダ水溶液(水酸化ナトリウムに炭酸ガス(岩谷産業社製)を添加し、pH11にしたもの)との混合水溶液(NaOH含有量166.2g/L、Na2CO3含有量170g/L)800mlを同時に添加し10分間撹拌したものを、オートクレーブ内で180℃で4時間水熱合成を行った(圧力:1.0MPa)。得られたスラリーをろ過し、さらに15Lのイオン交換水(カルシウム含有量5ppm)で水洗した。その後、ウェットケーキを分取し、該ウェットケーキに3Lのイオン交換水を加え、スラリー状になるまで撹拌した。得られたスラリーを95℃に保持しながら、表面処理剤(花王株式会社製、商品名:ルナック S70 工業用ステアリン酸(カルシウム含有量測定下限値以下))5gを添加した。その後、48%水酸化ナトリウム水溶液をpH10になるよう添加した。調製した表面処理剤溶液を添加し、48時間表面処理を行った。次いで、該スラリーから固体をろ別し、その後、ろ過ケーキを35℃、10Lのイオン交換水で水洗した。得られた水洗ケーキを100℃で24時間乾燥し、粉砕を行うことによって、固形の生成物であるハイドロタルサイト類組成物(サンプルB)を得た。
実施例2で得られたハイドロタルサイト類組成物をオーブンを用いて250℃で3時間加熱処理し、ハイドロタルサイト類組成物(サンプルB-1)を得た。
メジアン径(d50)が7.0μmである水酸化アルミニウムを用いた以外は実施例1と同様にして、固形の生成物であるハイドロタルサイト類組成物(サンプルC)を得た。
カルシウム含有量が1500ppmである水酸化マグネシウム(商品名:MAGSTAR#4、タテホ化学工業社製)を用いたこと、イオン交換水に代えて工業用水を用いたこと、炭酸ナトリウムとして工業用炭酸ナトリウム(セントラル硝子株式会社製、商品名:ソーダ灰(重炭))を用いたこと以外は実施例3と同様にして、固形の生成物であるハイドロタルサイト類組成物(サンプルD)を得た。
カルシウム含有量が2000ppmである水酸化マグネシウム(商品名:MAGSTAR#20、タテホ化学工業社製)を用いたこと以外は比較例1と同様にして、固形の生成物であるハイドロタルサイト類組成物(サンプルE)を得た。
比較例2で得られたハイドロタルサイト類組成物をオーブンを用いて250℃で3時間加熱処理し、ハイドロタルサイト類組成物(サンプルE-1)を得た。
塩化マグネシウム6水和物(カルシウム含有量:30ppm)に代えて、硫酸マグネシウム7水和物(カルシウム含有量:2000ppm、工業用軽焼マグネシウム(タテホ化学工業社製)を硫酸でpH6に調整したもの)を用いたこと、水酸化ナトリウムと工業用炭酸ソーダの混合水溶液を用いたこと、イオン交換水に代えて工業用水を用いたこと以外は実施例2と同様にして、固形の生成物であるハイドロタルサイト類組成物(サンプルF)を得た。
得られたハイドロタルサイト類組成物5gおよびトルエン(和光純薬特級試薬)100mlをソックスレー抽出器にいれて、10時間加熱し、抽出作業を行った。得られた抽出液を100℃で2時間保持して恒量化し、重量を測定した100mlビーカーに入れ、プレート表面を120℃に設定したホットプレートを用いて蒸発乾固させ、乾固物(熱トルエン抽出物)を得た。次いで、重量を測定し、予め測定したビーカーの重量を引くことにより乾固物の重量を算出した。得られた乾固物の重量に対する最初にソックスレー抽出器に仕込んだハイドロタルサイトの重量の割合を算出し、熱トルエン抽出量とした。
2.熱トルエン抽出物のカルシウム含有量測定
上記熱トルエン抽出物、60%硝酸2ml、エーテル10ml、イオン交換水30mlを容器に入れて、プレート表面を120℃に設定したホットプレートを用いて加熱し、エーテルを除去した。次いで、得られた液を用いて、ICP-MS(セイコーインスツールメンツ株式会社製、製品名:ICP1700HVR)にて熱トルエン抽出物中のカルシウム含有量を測定した。最初に仕込んだハイドロタルサイト類組成物に対する割合を測定し、熱トルエンで抽出されるカルシウム量とした。
3.ハイドロタルサイト類組成物中のカルシウム含有量測定
得られたハイドロタルサイト類組成物0.2g、60%硝酸2ml、90%硫酸2mlを容器に入れ、プレート表面を120℃に設定したホットプレートで加熱し、水分を蒸発させた。その後、室温まで冷却し、60%硝酸2mlを加えた後、プレート表面を120℃に設定したホットプレートで加熱し、水分を蒸発させた。硝酸の添加および加熱の操作を5回繰り返し行った。次いで、水分を蒸発させた試料にイオン交換水を加え、メスフラスコを用いて、100mlの水溶液を調製した。次いで、得られた液を用いて、ICP-MS(セイコーインスツールメンツ株式会社製、製品名:ICP1700HVR)にてハイドロタルサイト類組成物中のカルシウム含有量を測定した。
4.粘度および分散性評価(100メッシュ金属網残さ)
500mlのガラスビーカーにジメチルアセトアミド(DMAC)300gを入れ、次いで得られたハイドロタルサイト類組成物50gを添加し、高速撹拌ディスパーにて3000rpmで3分間撹拌混合し、スラリーを得た。撹拌終了直後のスラリーの粘度をB型粘度計(東機産業株式会社製、製品名:TVB-10)にて測定した。その後、スラリーを2時間放置し、再度粘度を測定し、スラリーの状態を目視で観察した。均一で滑らかなスラリーであるものについては「良好」、視認できるほどの凝集物が存在し、一部分離しているものについては「不良」とした。
次いで、100メッシュ金属網に2時間放置後のスラリーを通過させた。網に残った残さを200mlのエタノールで洗浄した後、オーブンで100℃、12時間乾燥し、重量を測定した。添加したハイドロタルサイト類組成物50gの内、網を通過できなかった量(残さ量)を求めた。
Claims (6)
- ハイドロタルサイト類と有機化合物を含む表面処理剤とを含む組成物であって、
該ハイドロタルサイト類の少なくとも一部が前記表面処理剤で被覆された状態であり、
該組成物の熱トルエン処理により抽出される抽出物が該組成物の1重量%以下であり、かつ、該抽出物に含まれるカルシウムが該組成物の重量の500ppm以下である、ハイドロタルサイト類組成物。 - 前記抽出物に含まれるカルシウムが組成物の重量の200ppm以下である、請求項1に記載のハイドロタルサイト類組成物。
- 前記ハイドロタルサイト類が脱結晶水処理されたものである、請求項1または2に記載のハイドロタルサイト類組成物。
- 前記表面処理剤が高級脂肪酸、高級脂肪酸とカルシウム以外の金属との金属塩、アニオン界面活性剤、リン酸エステル、および、カップリング剤から選択される少なくとも1種である、請求項1から3のいずれかに記載のハイドロタルサイト類組成物。
- 請求項1から4のいずれかに記載のハイドロタルサイト類組成物を含む、添加剤。
- ウレタン系樹脂、アミド系溶媒、および、請求項5に記載の添加剤を含む、樹脂組成物。
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KR101040942B1 (ko) * | 2010-12-17 | 2011-06-16 | (주)세창 | 합성수지 안정제용 하이드로탈사이트 및 이를 포함하는 합성수지 조성물 |
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2017
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- 2018-03-01 WO PCT/JP2018/007776 patent/WO2018168496A1/ja active Application Filing
- 2018-03-01 KR KR1020197026001A patent/KR20190122701A/ko not_active Application Discontinuation
- 2018-03-01 CN CN201880018800.2A patent/CN110475750A/zh active Pending
- 2018-03-01 EP EP18766846.2A patent/EP3597599A4/en not_active Withdrawn
- 2018-03-14 TW TW107108622A patent/TW201840681A/zh unknown
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Also Published As
Publication number | Publication date |
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EP3597599A1 (en) | 2020-01-22 |
EP3597599A4 (en) | 2021-01-06 |
KR20190122701A (ko) | 2019-10-30 |
JP2018154526A (ja) | 2018-10-04 |
CN110475750A (zh) | 2019-11-19 |
US20200024147A1 (en) | 2020-01-23 |
TW201840681A (zh) | 2018-11-16 |
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