WO2023135927A1 - 亜鉛含有ハイドロタルサイト - Google Patents

亜鉛含有ハイドロタルサイト Download PDF

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WO2023135927A1
WO2023135927A1 PCT/JP2022/042554 JP2022042554W WO2023135927A1 WO 2023135927 A1 WO2023135927 A1 WO 2023135927A1 JP 2022042554 W JP2022042554 W JP 2022042554W WO 2023135927 A1 WO2023135927 A1 WO 2023135927A1
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Prior art keywords
hydrotalcite
resin
zinc
present
resins
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PCT/JP2022/042554
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English (en)
French (fr)
Japanese (ja)
Inventor
賢 細井
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SETOLAS Holdings Inc
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SETOLAS Holdings Inc
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Priority to US18/279,373 priority Critical patent/US20240182319A1/en
Priority to EP22920447.4A priority patent/EP4464667A4/en
Priority to CN202280010100.5A priority patent/CN116848065A/zh
Priority to KR1020247000320A priority patent/KR102916273B1/ko
Priority to JP2023530309A priority patent/JP7614350B2/ja
Publication of WO2023135927A1 publication Critical patent/WO2023135927A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing zinc, with or without oxygen or hydrogen, and containing two or more other elements
    • 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, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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
    • 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
    • C08K2003/267—Magnesium carbonate
    • 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

Definitions

  • the present invention relates to hydrotalcite added to resins such as chlorine-containing resins.
  • Hydrotalcite is known as a compound added to resins, such as a heat stabilizer for chlorine-containing resins (for example, vinyl chloride resins) and a deoxidizing agent for olefin resins.
  • Hydrotalcite has the drawback that foaming occurs in the resin molding due to inter-layer water and water of crystallization due to heat during processing and use of the resin.
  • Such drawbacks can be improved by calcining hydrotalcite at 200° C. to 300° C. to remove the decrystallized water. thermal stability is not obtained.
  • the hydrotalcite described in Patent Documents 1 and 2 is used in combination with magnesium oxide or magnesium hydroxide for improvement.
  • the present invention can suppress foaming and exhibit excellent thermal stability without using additives when added to resins such as chlorine-containing resins, and also suppresses coloring of resins.
  • An object of the present invention is to provide a hydrotalcite capable of
  • conventional hydrotalcite can be obtained by strongly sintering zinc (Zn)-containing hydrotalcite under specific temperature conditions of 400°C to 850°C.
  • Zn zinc
  • a hydrotalcite having a high specific surface area not found in sites can be obtained, and when this hydrotalcite is added to a resin such as a chlorine-containing resin, foaming can be suppressed and good thermal stability can be exhibited. It was found that the coloration of the resin can also be suppressed.
  • the present invention has been completed based on such findings, and includes the following aspects.
  • One aspect (aspect 1) of the present invention is hydrotalcite represented by the following formula (1) and having a specific surface area of 120 m 2 /g to 250 m 2 /g according to the BET method.
  • M 2+ x Zn y M 3+ z O x+y+(3/2)z (1) (wherein M 2+ represents at least one divalent metal ion, M 3+ represents at least one trivalent metal ion, x, y and z are 0 ⁇ x ⁇ 0.5, 0 ⁇ represents a number that satisfies y ⁇ 0.2 and 0 ⁇ z ⁇ 0.4.)
  • the hydrotalcite of this aspect 1 is represented by the above formula (1) and has a specific surface area of 120 m 2 /g to 250 m 2 /g by the BET method, that is, a strong It is a calcined zinc-containing hydrotalcite.
  • the interlayer water and carbonate ions (interlayer anions) existing between the layers of the layered structure are removed by strong sintering, so foaming due to these can be made difficult to occur.
  • the desorption of the inter-layer water existing between the layers of the layered structure lowers the ion-exchange capacity, and untrapped chloride ions (Cl ⁇ ) are likely to occur.
  • thermal stability is reduced by hydrogen chloride (HCl) gas caused by Release of the water present greatly increases the specific surface area from 120 m 2 /g to 250 m 2 /g, thus increasing the portion that can react with the acid (i.e., Cl ⁇ ) and neutralizing with the acid. Reaction easily occurs (that is, it has a high acid-accepting capacity), and excellent thermal stability can be exhibited.
  • HCl hydrogen chloride
  • the hydrotalcite of Embodiment 1 contains zinc (Zn), if metal ions other than Zn (for example, Mg 2+ etc.) Even if a complex is formed, due to the existence of a similarly formed metal complex between the zinc ion (Zn 2+ ) and the double bond portion in the resin molecule, the coordination colors of each complex are in a complementary color relationship and mutually Since the coordination colors of are canceled each other, coloring of the resin can be suppressed as a result.
  • the hydrotalcite of Embodiment 1 containing such Zn has zinc oxide (ZnO) formed on the surface by strong sintering, and the ZnO is generated by a neutralization reaction compared to MgO and the like.
  • the hydrotalcite of this aspect 1 can suppress foaming and exhibit excellent thermal stability without using additives when added to a resin such as a chlorine-containing resin. Coloring of the resin can also be suppressed.
  • the hydrotalcite of aspect 1 is characterized in that the specific surface area is 150 m 2 /g to 200 m 2 /g.
  • hydrotalcite of aspect 2 Since the hydrotalcite of aspect 2 has a specific surface area within the above specific range, it can more reliably exhibit the effects of aspect 1 above.
  • the hydrotalcite of aspect 1 or 2 is characterized in that M 2+ is Mg 2+ and M 3+ is Al 3+ in the formula (1).
  • hydrotalcite of aspect 3 has the above-mentioned specific composition, it can more reliably exhibit the effects of aspect 1 above.
  • the hydrotalcite according to any one of aspects 1 to 3 is characterized in that the weight loss rate upon ignition at 500°C is 10% or less.
  • the hydrotalcite of this aspect 4 has a weight loss rate of 10% or less at the time of ignition, and most of this is due to a decrease in adhered moisture, so it is possible to more reliably suppress the occurrence of foaming.
  • FIG. 1 is a schematic diagram for explaining the structural change due to firing of hydrotalcite.
  • FIG. 2 is a graph showing the results of X-ray diffraction (XRD) measurement of Examples of the present invention and Comparative Examples.
  • FIG. 3 is a table showing the results of the static thermal stability test of Examples of the present invention and Comparative Examples.
  • hydrotalcite of the present invention will be described in detail below.
  • the hydrotalcite of the present invention is obtained by strongly sintering an unsintered zinc-containing hydrotalcite under a specific temperature condition of 400° C. to 850° C., represented by the following formula (1) and a ratio by the BET method. It is a strongly sintered zinc-containing hydrotalcite having a surface area of 120 m 2 /g to 250 m 2 /g.
  • M 2+ x Zn y M 3+ z O x+y+(3/2)z (1) (wherein M 2+ represents at least one divalent metal ion, M 3+ represents at least one trivalent metal ion, x, y and z are 0 ⁇ x ⁇ 0.5, 0 ⁇ represents a number that satisfies y ⁇ 0.2 and 0 ⁇ z ⁇ 0.4.)
  • the inter-layer water and carbonate ions existing between the layers of the hydrotalcite layered structure before firing are removed by strong firing. Even if it is used as such, foaming due to interlayer water and carbonate ions is less likely to occur.
  • the thermal stability of the hydrotalcite of the present invention decreases due to hydrogen chloride (HCl) gas, as shown in FIG. ), the specific surface area is greatly increased to 120 m 2 /g to 250 m 2 /g by releasing the water present in the basic layers and between the layers of the layered structure, so that it reacts with the acid (i.e. Cl ⁇ ).
  • the portion that can be used increases, and the neutralization reaction with acid easily occurs (that is, it has a high acid-accepting capacity), and excellent thermal stability can be exhibited.
  • FIG. 1 is a schematic diagram for explaining the structural change due to firing of hydrotalcite.
  • (a) shows the layered structure of uncalcined zinc-free hydrotalcite
  • (b) shows the uncalcined zinc-free hydrotalcite at 200 to 300°C.
  • the layered structure of the calcined zinc-free hydrotalcite obtained by calcining under temperature conditions (i.e., conventional calcination temperature conditions)
  • (c) shows the uncalcined zinc-free hydrotalcite.
  • (d) shows unsintered zinc-containing hydrotalcite at 400° C. to 850° C.
  • FIG. 1 shows a layered structure of strongly sintered zinc-containing hydrotalcite (that is, the hydrotalcite of the present invention) obtained by strong sintering at a temperature of 850°C.
  • the symbol BL represents the base layer of hydrotalcite
  • the symbol ML represents the intermediate layer of hydrotalcite.
  • the hydrotalcite of the present invention contains zinc (Zn), if metal ions other than Zn (for example, Mg 2+ ) form the double bond portion in the resin molecule and the metal complex as described above, Even if they are formed, the presence of similarly formed metal complexes of zinc ions (Zn 2+ ) and double bond moieties in the resin molecules causes the coordination colors of each complex to become complementary colors. Since the coordination colors cancel each other out, the coloring of the resin can be suppressed as a result.
  • Zn zinc ions other than Zn
  • the hydrotalcite of the present invention can suppress foaming and exhibit excellent thermal stability without using additives when added to a resin such as a chlorine-containing resin. Coloring of the resin can also be suppressed.
  • the types of metals M 2+ (divalent metal ion) and M 3+ (trivalent metal ion) in formula (1) are not particularly limited, and are included in hydrotalcite. Any available metal can be employed. Among them, in the hydrotalcite of the present invention, M 2+ in the formula (1) is preferably magnesium ion (Mg 2+ ) and M 3+ is preferably aluminum ion (Al 3+ ). If the hydrotalcite has such a specific composition, the above effects can be exhibited more reliably.
  • the hydrotalcite of the present invention must have a BET specific surface area of 120 m 2 /g to 250 m 2 /g, preferably 150 m 2 / g to 200 m 2 /g. When the specific surface area by the BET method is within such a specific range, the above effects can be exhibited more reliably.
  • the hydrotalcite of the present invention having such a specific specific surface area (that is, a BET specific surface area of 120 m 2 /g to 250 m 2 /g) and represented by the above formula (1) is as described above. It can be obtained by strongly sintering unsintered zinc-containing hydrotalcite under specific temperature conditions of 400°C to 850°C.
  • the uncalcined hydrotalcite that can be used for producing the hydrotalcite of the present invention is not particularly limited as long as it contains zinc, and any known zinc-containing hydrotalcite can be used.
  • the zinc-containing hydrotalcite is calcined at a temperature below 400°C, it becomes difficult to obtain an oxide having high acid reactivity, and if it is calcined at a temperature above 850°C, the layered structure of the hydrotalcite cannot be maintained. , tends to have a spinel structure, and as a result, the thermal stability tends to decrease.
  • the preferred firing temperature range is 450°C to 800°C.
  • Hydrotalcite which is strongly calcined under such specific temperature conditions, can be analyzed by X-ray diffraction (XRD) and thermogravimetric differential thermal analysis (TG-DTA) in addition to the specific surface area by the BET method described above.
  • XRD X-ray diffraction
  • TG-DTA thermogravimetric differential thermal analysis
  • XRD can confirm the presence or absence of oxides and spinel structures formed by firing
  • TG-DTA can detect interlayer water and interlayer anions contained in hydrotalcite, The presence or absence of a group (OH group) can be confirmed.
  • the calcination time for producing the hydrotalcite of the present invention is not particularly limited as long as the calcination time is such that the peak of the oxide can be confirmed by XRD.
  • the firing time may be, for example, 30 minutes or longer, preferably 1 hour or longer, and more preferably 2 hours or longer, depending on the firing temperature.
  • the hydrotalcite of the present invention preferably has a weight loss rate of 10% or less upon ignition at 500°C.
  • water adhering to the particle surface is removed in a drying process at about 120 ° C., but in a normal calcining process (i.e., calcining process at 200 ° C. to 300 ° C.), inter-layer water and inter-layer anions , OH groups contained in the basic layer of hydrotalcite are difficult to remove, so the weight loss rate during ignition at 500 ° C. tends to be high (for example, 20% or more), resulting in inter-layer water etc. Foaming is likely to occur.
  • the hydrotalcite of the present invention is easily removed by strong sintering, such as interlayer water, interlayer anions, OH groups, etc., so that the weight loss rate at the time of ignition at 500 ° C. tends to be low, and as a result, the interlayer water The resulting foaming is less likely to occur.
  • the weight reduction rate during ignition is 10% or less, most of the reduction is due to the reduction of adhering moisture, so there is an advantage that the occurrence of foaming can be suppressed more reliably.
  • the weight loss rate during ignition is preferably 5% or less, more preferably 3% or less. Also, the lower limit of the weight loss rate during ignition is not particularly limited, but is, for example, 0.5%.
  • the hydrotalcite of the present invention may be subjected to a surface treatment for improving the dispersibility in the resin.
  • the surface treatment agent that can be used for this surface treatment is not particularly limited, but examples include anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, and aluminum cups. Ring agents, silicone treatment agents, silicic acid, water glass, and the like.
  • Particularly preferred surface treating agents include at least one surface treating agent selected from the group consisting of oleic acid, stearic acid, octanoic acid and octylic acid.
  • the amount of the surface treatment agent is not particularly limited, it is, for example, 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the mass of hydrotalcite.
  • the hydrotalcite of the present invention can be used in the same manner as conventional hydrotalcite. It can be used as an additive component blended with the resin.
  • the resin composition of the present invention comprises an arbitrary resin and strongly sintered zinc-containing hydrotalcite represented by the above formula (1) and having a BET specific surface area of 120 m 2 /g to 250 m 2 /g. It is a resin composition comprising: Since the resin composition of the present invention contains strongly sintered zinc-containing hydrotalcite, it is excellent in productivity and thermal stability, and can be used for the production of molded articles in which the occurrence of foaming and coloring is suppressed. .
  • any resin can be adopted according to various uses, and examples thereof include thermoplastic resins such as chlorine-containing resins and thermosetting resins. In addition, these resins can be used individually or in combination of 2 or more types.
  • the chlorine-containing resin which is an example of the thermoplastic resin that can be used in the resin composition of the present invention, is not particularly limited, but examples include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride- Vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride- Styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, chloride Vinyl-vinylidene chloride-vinyl acetate terpolymer, vinyl chlor
  • vinyl chloride resins such as chloroprene rubber, chlorinated butyl rubber, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, and epichlorohydrin rubber; These chlorine-containing resins can be used alone or in combination of two or more.
  • these chlorine-containing resins are other thermoplastic resins that do not contain chlorine, such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth ) It can be used in combination with acrylate copolymers, polyesters, etc., for example, it can be used in the form of a mixture of a chlorine-containing resin and another chlorine-free thermoplastic resin, a block copolymer or a graft copolymer. can be done.
  • thermoplastic resins other than chlorine-containing resins that can be used in the resin composition of the present invention are not particularly limited, but examples include olefin resins, polystyrene, copolymers of ethylene and vinyl acetate, and ethylene and acrylic acid.
  • copolymer with ether copolymer of ethylene and methyl acrylate, copolymer of ethylene and vinyl acetate, copolymer of ethylene and acrylic ether, copolymer of ethylene and methyl acrylate, Polypropylene, copolymers of propylene and other ⁇ -olefins, polybutene-1, poly4-methylpentene-1, polystyrene, copolymers of styrene and acrylonitrile, copolymers of ethylene and propylene diene rubber, ethylene and butadiene copolymer, polyvinyl acetate, polylactic acid, polyvinyl alcohol, polyacrylate, polymethacrylate, polyurethane, polyester, polyether, polyamide, ABS, polycarbonate, polyphenylene sulfide, synthetic rubber, and the like.
  • the olefin resin is not particularly limited, but examples include polyethylene, copolymers of ethylene and other ⁇ -olefins, polypropylene, copolymers of propylene and other ⁇ -olefins.
  • Olefin-based resins such as coalescence, polybutene-1, poly-4-methylpentene-1, and the like, and synthetic rubbers are not particularly limited, but examples include ethylene propylene diene rubber (EPDM), styrene butadiene rubber (SBR ), acrylonitrile butadiene rubber (NBR), butyl rubber, isoprene rubber, silicone rubber, fluororubber, brominated butyl rubber, epichlorohydrin rubber, and the like. These thermoplastic resins can be used alone or in combination of two or more.
  • EPDM ethylene propylene diene rubber
  • SBR styrene butadiene rubber
  • NBR acrylonitrile butadiene rubber
  • butyl rubber butyl rubber
  • isoprene rubber silicone rubber
  • fluororubber brominated butyl rubber
  • epichlorohydrin rubber epichlorohydrin rubber
  • thermosetting resin that can be used in the resin composition of the present invention is not particularly limited, but examples include phenol resins, melamine resins, epoxy resins, unsaturated polyester resins, and alkyd resins. These thermosetting resins can be used alone or in combination of two or more.
  • the resin composition of the present invention preferably contains a chlorine-containing resin.
  • Chlorine-containing resins are particularly susceptible to problems such as foaming, reduced thermal stability, and coloration as described above. Even if the resin composition contains a chlorine-containing resin, it effectively exhibits the above-mentioned effects, that is, excellent productivity and thermal stability, and can suppress the occurrence of foaming and coloring. can do.
  • the content of the strongly sintered zinc-containing hydrotalcite is not particularly limited as long as it does not inhibit the effects of the present invention. part to 250 parts by mass, preferably 1 part to 200 parts by mass.
  • the resin composition of the present invention may contain additives other than the strongly sintered zinc-containing hydrotalcite within a range that does not impair the effects of the present invention.
  • additives include, but are not limited to, antioxidants, reinforcing agents such as talc, ultraviolet absorbers, lubricants, matting agents such as fine silica, pigments such as carbon black, Fire retardants, flame retardants such as phosphate ester flame retardants, flame retardant aids such as zinc stannate, alkali metal stannate, and carbon powder, and fillers such as calcium carbonate.
  • antioxidants such as talc, ultraviolet absorbers, lubricants, matting agents such as fine silica, pigments such as carbon black, Fire retardants, flame retardants such as phosphate ester flame retardants, flame retardant aids such as zinc stannate, alkali metal stannate, and carbon powder, and fillers such as calcium carbonate.
  • reinforcing agents such as talc
  • ultraviolet absorbers such as ultraviolet absorb
  • the resin composition of the present invention can be obtained by mixing or kneading at least the above resin and strongly sintered zinc-containing hydrotalcite.
  • the means for mixing or kneading the resin and the strongly sintered zinc-containing hydrotalcite is not particularly limited, and examples thereof include a single-screw or twin-screw extruder, rolls, and a Banbury mixer.
  • the resin composition of the present invention can be produced into a desired molded article by any known molding means.
  • the molding means for manufacturing the molded body is not particularly limited, and any molding means can be adopted according to the type of the resin, the molded body, and the like. Examples of such molding means include, but are not limited to, injection molding, extrusion molding, blow molding, press molding, rotational molding, calender molding, sheet forming molding, transfer molding, laminate molding, and vacuum molding.
  • the molded article formed from the resin composition of the present invention includes any resin and strongly sintered zinc represented by the above formula (1) and having a BET specific surface area of 120 m 2 /g to 250 m 2 /g. Since it is formed from a resin composition containing the contained hydrotalcite, it is used as a resin product that has excellent productivity and thermal stability, suppresses the occurrence of foaming and coloring, and has excellent appearance and various physical properties. be able to.
  • Example 1 (Production of MgAlZn-type hydrotalcite fired at 450°C)
  • Raw materials 1.5 mol / L magnesium chloride and 0.50 mol / L aluminum chloride acid mixture (A), 5.7 mol / L zinc chloride aqueous solution (B), 3.3 N caustic soda and 0
  • the reaction product thus obtained was subjected to solid-liquid separation using a Nutsche, and the obtained solid was washed with ion-exchanged water and dried at 105° C. for 24 hours. Further, the obtained dried product was pulverized with a hammer mill and then sieved with a 150 micron filter to obtain a powder. Next, the obtained powder was placed in a crucible, and the crucible was placed in a firing furnace preliminarily heated to 450° C. and fired at the same temperature for 2 hours in the atmosphere. The content was taken out from the crucible after sintering, and a powder of MgAlZn-type hydrotalcite sintered at 450° C. of Example 1 was obtained.
  • Example 2 (Production of MgAlZn-type hydrotalcite fired at 600°C) Powder of MgAlZn-type hydrotalcite fired at 600°C of Example 2 was obtained in the same manner as in Example 1 except that the firing temperature was changed to 600°C.
  • Example 3 (Production of MgAlZn-type hydrotalcite fired at 800°C) Powder of MgAlZn-type hydrotalcite fired at 800°C of Example 3 was obtained in the same manner as in Example 1 except that the firing temperature was changed to 800°C.
  • Comparative example 1 Production of unfired MgAl-type hydrotalcite
  • 160 mL of 1.5 mol/L aqueous magnesium chloride solution While stirring predetermined ion-exchanged water in a 1 L volume reaction vessel, 160 mL of 1.5 mol/L aqueous magnesium chloride solution, 120 mL of 1 mol/L aqueous aluminum chloride solution, and 90 mL of 8 mol/L aqueous sodium hydroxide solution were added to the water. and a mixed solution of 60 mL of a 1 mol/L sodium carbonate aqueous solution were simultaneously added and reacted to obtain a reactant. The pH during the reaction was 9.5.
  • the reaction product thus obtained was subjected to solid-liquid separation using a Nutsche, and the obtained solid was washed with ion-exchanged water, and ion-exchanged water was added again to obtain a re-emulsified slurry. Further, the obtained re-emulsified slurry was hydrothermally treated at 170° C. for 13 hours and cooled. After that, the obtained slurry was heated to 80° C., an aqueous solution (80° C.) of 0.55 g of sodium stearate was gradually added to the slurry under stirring, and this state was maintained for 30 minutes.
  • Comparative example 2 (Production of MgAl-type hydrotalcite calcined at 250°C)
  • the unfired MgAl-type hydrotalcite powder of Comparative Example 1 was placed in a stainless steel tray, and the tray was placed in a blower constant temperature thermostat (DKN602 type, manufactured by Yamato Scientific Co., Ltd.) preliminarily heated to 250 ° C. and placed in the atmosphere. was fired at the same temperature for 2 hours. The content was taken out from the tray after sintering, and powder of MgAl type hydrotalcite sintered at 250° C. of Comparative Example 2 was obtained.
  • DKN602 type blower constant temperature thermostat
  • Comparative example 3 (Production of MgAl-type hydrotalcite calcined at 600°C) While stirring predetermined ion-exchanged water in a 1 L volume reaction vessel, 160 mL of 1.5 mol/L aqueous magnesium chloride solution, 120 mL of 1 mol/L aqueous aluminum chloride solution, and 90 mL of 8 mol/L aqueous sodium hydroxide solution were added to the water. and a mixed solution of 60 mL of a 1 mol/L sodium carbonate aqueous solution were simultaneously added and reacted to obtain a reactant. The pH during the reaction was 9.5.
  • the reaction product thus obtained was subjected to solid-liquid separation using a Nutsche, and the obtained solid was washed with ion-exchanged water and dried at 105° C. for 18 hours. Further, the obtained dried product was pulverized with a hammer mill and then sieved with a 150 micron filter to obtain a powder. Next, the obtained powder was placed in a crucible, and the crucible was placed in a firing furnace preliminarily heated to 600° C. and fired at the same temperature for 2 hours in the atmosphere. The content was taken out from the crucible after firing, and a powder of MgAl type hydrotalcite fired at 600° C. of Comparative Example 3 was obtained.
  • the reaction product thus obtained was subjected to solid-liquid separation using a Nutsche, and the obtained solid was washed with ion-exchanged water, and ion-exchanged water was added again to obtain a re-emulsified slurry. Further, the obtained re-emulsified slurry was hydrothermally treated at 160° C. for 14 hours and cooled. After that, the obtained slurry was heated to 80° C., an aqueous solution (80° C.) of 0.55 g of sodium stearate was gradually added to the slurry under stirring, and this state was maintained for 30 minutes.
  • Comparative example 5 (Production of MgAlZn-type hydrotalcite fired at 250°C)
  • the unfired MgAlZn-type hydrotalcite powder of Comparative Example 4 was placed in a stainless steel tray, and the tray was placed in a blower constant temperature thermostat (DKN602 type, manufactured by Yamato Scientific Co., Ltd.) preliminarily heated to 250 ° C. and placed in the atmosphere. was fired at the same temperature for 2 hours. The content was taken out from the tray after sintering, and powder of MgAlZn-type hydrotalcite sintered at 250° C. of Comparative Example 5 was obtained.
  • DKN602 type manufactured by Yamato Scientific Co., Ltd.
  • Comparative example 6 (Production of MgAlZn-type hydrotalcite fired at 350°C) Powder of MgAlZn-type hydrotalcite fired at 350°C of Comparative Example 6 was obtained in the same manner as in Comparative Example 5 except that the firing temperature was changed to 350°C.
  • Comparative example 7 (Production of MgAlZn-type hydrotalcite fired at 900°C) Powder of MgAlZn-type hydrotalcite fired at 900°C of Comparative Example 7 was obtained in the same manner as in Example 1 except that the firing temperature was changed to 900°C.
  • Comparative example 8 (Production of MgAlZn-type hydrotalcite fired at 1000°C) A 1000°C sintered MgAlZn-type hydrotalcite powder of Comparative Example 8 was obtained in the same manner as in Example 1 except that the sintering temperature was changed to 1000°C.
  • the specific surface area by the BET method was measured using "BELsorp-mini" manufactured by Microtrack Bell Co., Ltd. Specifically, it was measured by a constant volume gas adsorption method using nitrogen gas, and the specific surface area (m 2 /g) was obtained by analysis by the BET multipoint method.
  • Weight reduction rate at the time of ignition at 500 ° C. Also, the weight loss rate at the time of ignition at 500° C. was measured according to the following procedure. (1) Put the sample in a stainless steel vat and dry it at 120° C. for 2 hours. (2) Place 1 g of the dried sample in a crucible. (3) Place the crucible in a firing furnace and fire at 500° C. for 1 hour. (4) After firing, take out the crucible, weigh the sample (g), and calculate the weight reduction rate (%).
  • Vinyl chloride resin manufactured by Shin-Etsu Chemical Co., Ltd., grade name: TK-1300
  • plasticizer manufactured by Daihachi Chemical Co., Ltd., grade name: DINP (diisononyl phthalate)
  • calcium carbonate manufactured by Shiraishi Calcium Co., Ltd., grade name: Whiten SB
  • Henschel mixer manufactured by Nippon Coke Kogyo Co., Ltd.
  • the density (g/cm 3 ) of the molded article to be tested was measured using an electronic density meter SD120L (manufactured by Alpha Mirage Co., Ltd.), and this was defined as the pre-foaming density. Then, using a press molding machine (manufactured by Shindo Kinzoku Kogyosho Co., Ltd.), the compact to be tested was subjected to sheet molding under the conditions of 230° C., 1 MPa, and 5 minutes to obtain a sheet. The density (g/cm 3 ) of the thus obtained sheet was measured using an electronic density meter SD120L (manufactured by Alpha Mirage Co., Ltd.), and this was taken as the post-foaming density.
  • the strongly sintered zinc-containing hydrotalcite of the present invention is non-toxic and highly safe, it can be used, for example, as a stabilizer for resin compositions or moldings in the fields of medicine and food packaging.
  • foaming is suppressed even at high processing temperatures and it has excellent thermal stability and colorability, it can be used in soft to hard materials such as building materials, interior and exterior materials for automobiles, home appliances, food packaging materials, and insulating materials. It can be used in a wide range of plastic fields using chlorine-containing resins.
  • plastics such as chlorinated PVC (CPVC) with high processing temperatures and polyolefin resins (non-chlorine containing resins) such as agricultural films.
  • CPVC chlorinated PVC
  • non-chlorine containing resins non-chlorine containing resins

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  • Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
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US18/279,373 US20240182319A1 (en) 2022-01-14 2022-11-16 Zinc-containing hydrotalcite
EP22920447.4A EP4464667A4 (en) 2022-01-14 2022-11-16 HYDROTALCITE CONTAINING ZINC
CN202280010100.5A CN116848065A (zh) 2022-01-14 2022-11-16 含锌水滑石
KR1020247000320A KR102916273B1 (ko) 2022-01-14 2022-11-16 아연 함유 하이드로탈사이트
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WO2024252951A1 (ja) * 2023-06-07 2024-12-12 セトラスホールディングス株式会社 複合金属酸化物の粉体、ゴム用加硫剤、ゴム組成物、及び複合金属酸化物の粉体の製造方法

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WO2024252951A1 (ja) * 2023-06-07 2024-12-12 セトラスホールディングス株式会社 複合金属酸化物の粉体、ゴム用加硫剤、ゴム組成物、及び複合金属酸化物の粉体の製造方法

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JP7614350B2 (ja) 2025-01-15
CN116848065A (zh) 2023-10-03
US20240182319A1 (en) 2024-06-06
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