WO2024241989A1 - 複合金属酸化物の粉体、ゴム用加硫剤、及びゴム組成物 - Google Patents

複合金属酸化物の粉体、ゴム用加硫剤、及びゴム組成物 Download PDF

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Publication number
WO2024241989A1
WO2024241989A1 PCT/JP2024/017975 JP2024017975W WO2024241989A1 WO 2024241989 A1 WO2024241989 A1 WO 2024241989A1 JP 2024017975 W JP2024017975 W JP 2024017975W WO 2024241989 A1 WO2024241989 A1 WO 2024241989A1
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Prior art keywords
powder
rubber
composite metal
oxide
metal oxide
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Ceased
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PCT/JP2024/017975
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English (en)
French (fr)
Japanese (ja)
Inventor
賢 細井
タン ティ ノック リュウ
大輔 工藤
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SETOLAS Holdings Inc
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SETOLAS Holdings Inc
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Priority to JP2025522345A priority Critical patent/JPWO2024241989A1/ja
Publication of WO2024241989A1 publication Critical patent/WO2024241989A1/ja
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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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • a vulcanizing agent such as zinc oxide
  • a vulcanization aid such as magnesium oxide
  • composite metal oxides containing magnesium oxide and zinc oxide have been investigated.
  • the third disclosure is a vulcanizing agent for rubber comprising the first disclosure or the second disclosure.
  • the fourth disclosure is a rubber composition comprising the rubber vulcanizing agent according to the third disclosure and a rubber raw material.
  • FIG. 1 shows powder X-ray diffraction data for Powder No. 1 and Powder No. 2.
  • FIG. 2 shows the results of the vulcanization test.
  • the peak value of the diffraction angle (2 ⁇ ) of zinc oxide may or may not be shifted from the peak value of the diffraction angle (2 ⁇ ) of zinc oxide single crystal.
  • the peak value of the diffraction angle (2 ⁇ ) of zinc oxide is preferably within a range of ⁇ 0.05° from the diffraction angle (2 ⁇ ) of zinc oxide single crystal.
  • the composite metal oxide is preferably represented by the following formula (2): 1-n(Mg 1-m Zn m O) ⁇ nZnO Formula (2) It is expressed by the formula: m preferably satisfies 0.05 ⁇ m, and more preferably 0.10 ⁇ m. Also, m preferably satisfies m ⁇ 0.45, and more preferably m ⁇ 0.35. Also, n preferably satisfies 0.05 ⁇ n, and more preferably 0.15 ⁇ n. Also, n preferably satisfies n ⁇ 0.45, and more preferably n ⁇ 0.40. This makes it easier for zinc oxide to be exposed to the outside of magnesium oxide and easier for zinc oxide to be dissolved in the interior of magnesium oxide.
  • Surface treatment with a surface treatment agent can be carried out by conventional means.
  • the powder is charged into a Henshiel mixer, and while stirring the powder at high speed, the surface treatment agent is dropped in either its original form or diluted with a solvent, and the powder and the surface treatment agent are mixed to perform the surface treatment.
  • the rubber raw material and the rubber vulcanizing agent may be mixed using any device capable of mixing them, including, for example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, and the like.
  • the rubber composition can be molded by known molding means such as injection molding, extrusion molding, blow molding, press molding, rotational molding, calendar molding, sheet forming molding, transfer molding, lamination molding, vacuum molding, and the like.
  • the powder disclosed herein has the same functions as conventional magnesium oxide solid solutions, and therefore can be used not only as a rubber vulcanizing agent as described above, but also in applications where magnesium oxide is used, such as an acid acceptor for resins, an acid acceptor for rubber, an acid neutralizer, a thickener for FRP, a heat stabilizer, a deodorizer, a light resistance improver, and a resin curing agent.
  • magnesium oxide such as an acid acceptor for resins, an acid acceptor for rubber, an acid neutralizer, a thickener for FRP, a heat stabilizer, a deodorizer, a light resistance improver, and a resin curing agent.
  • the powder according to the present disclosure can be produced, for example, as follows. a coprecipitation step of mixing a water-soluble magnesium salt, a water-soluble zinc salt, and an alkali to obtain a coprecipitate containing magnesium hydroxide and zinc hydroxide; an aging step of aging the coprecipitate; a grinding step of pulverizing the aged coprecipitate; and a firing step of calcining the ground coprecipitate to form a powder of the composite metal oxide.
  • a water-soluble magnesium salt, a water-soluble zinc salt, and an alkali are mixed to obtain a coprecipitate containing magnesium hydroxide and zinc hydroxide.
  • the water-soluble magnesium salt include, but are not limited to, magnesium chloride, magnesium nitrate, magnesium acetate, magnesium sulfate, etc.
  • the water-soluble magnesium salt is preferably magnesium chloride, magnesium nitrate, or magnesium acetate.
  • the above-mentioned water-soluble zinc salts include zinc chloride, zinc nitrate, etc.
  • the above-mentioned alkalis include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., and hydroxides of alkaline earth metals such as calcium hydroxide.
  • the ratio of the water-soluble magnesium salt to the water-soluble zinc salt can be appropriately adjusted in accordance with the preferred molar ratio of Mg and Zn in the composite metal oxide.
  • the composite metal oxide has the formula Mg 1-x Zn x O
  • a water-soluble magnesium salt and a water-soluble zinc salt can be mixed in a ratio such that the molar ratio of Mg:Zn is (1 ⁇ x):x.
  • the above alkali can be added in an appropriate amount for the water-soluble magnesium salt and water-soluble zinc salt to form magnesium hydroxide and zinc hydroxide. If the amount of alkali calculated to be required for the water-soluble magnesium salt and water-soluble zinc salt to completely form magnesium hydroxide and zinc hydroxide is 100 mol % (1.0 equivalent), the alkali is preferably added in an amount of 80 mol % (0.8 equivalent) or more, more preferably 90 mol % (0.9 equivalent) or more, and even more preferably 95 mol % (0.95 equivalent) or more. The above alkali may be added in an amount of 100 mol % (1.0 equivalent) or less from the viewpoint of facilitating washing of the coprecipitate.
  • the coprecipitate can be washed with deionized water or the like, filtered, and then resuspended in water, an organic solvent, or the like, as necessary to remove impurities such as alkali metals and alkaline earth metals.
  • a homogenizer or the like can be used for the resuspension.
  • the coprecipitate is aged to form an aged coprecipitate.
  • the aging temperature in the aging step is preferably 40° C. or higher, more preferably 45° C. or higher, and even more preferably 48° C. or higher.
  • the aging temperature is preferably 200° C. or lower, more preferably less than 100° C., and even more preferably 95° C. or lower. This makes it easier to obtain the composite metal oxide powder.
  • the aging step can be carried out under high pressure using an autoclave or the like.
  • the aging temperature in the aging step is preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 3 hours or more, and is preferably 10 hours or less, more preferably 8 hours or less, and even more preferably 6 hours or less.
  • the coprecipitate after aging may be dehydrated (filtered), dried, etc., if necessary.
  • the aged coprecipitate is ground to form a ground coprecipitate.
  • the aged coprecipitate can be pulverized using a pulverizer known in the art, such as a jaw crusher, a gyratory crusher, a cone crusher, an impact crusher, a roll crusher, a cutter mill, a stamp mill, a ring mill, a roller mill, a jet mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, a ball mill, etc.
  • a pulverizer known in the art, such as a jaw crusher, a gyratory crusher, a cone crusher, an impact crusher, a roll crusher, a cutter mill, a stamp mill, a ring mill, a roller mill, a jet mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, a ball mill, etc.
  • the pulverized coprecipitate is calcined to obtain a composite metal oxide powder.
  • the calcination of the coprecipitate can be carried out by a method known in the art.
  • the calcination of the coprecipitate can be carried out at a temperature of preferably 300° C. or more, and more preferably 350° C. or more.
  • the calcination of the coprecipitate can be carried out at a temperature of preferably 600° C. or less, and more preferably 550° C. or less.
  • the calcination of the coprecipitate can be carried out for a time period of preferably 0.1 hours or more, more preferably 0.5 hours or more, and preferably 10 hours or less, and more preferably 6 hours or less.
  • the resuspended coprecipitate No. 1 was aged at 80°C for 4 hours, filtered, dried, ground in a ball mill, and then calcined at 450°C for 1 hour to obtain composite metal oxide powder No. 1.
  • the formula of composite metal oxide powder No. 1 was Mg0.8Zn0.2O .
  • the D50 and BET specific surface area of composite metal oxide powder No. 1 are shown in Table 1.
  • Powder X-ray diffraction (XRD) data of composite metal oxide powder No. 1 is shown in Figure 1 together with powder X-ray diffraction (XRD) data of magnesium oxide single crystal (Kyowa Chemical Industry Co., Ltd., Kyowamag 150).
  • Example 2 The mixed solution of magnesium chloride and zinc chloride was changed to have a magnesium concentration of 0.77 mol/L and a zinc concentration of 0.25 mol/L, and the aging and firing conditions were changed as shown in Table 1, but the same procedure as in Example 1 was used to obtain composite metal oxide powder No. 2.
  • the composition formula of composite metal oxide powder No. 2 was Mg0.75Zn0.25O .
  • the D50 and BET specific surface area of composite metal oxide powder No. 2 are shown in Table 1.
  • the powder X-ray diffraction (XRD) data of composite metal oxide powder No. 2 is shown in Figure 1 together with the powder X-ray diffraction (XRD) data of magnesium oxide single crystal (Kyowa Chemical Industry Co., Ltd., Kyowamag 150).
  • Composite metal oxide powder No. 3 was produced in accordance with Example 1 of Patent Document 1.
  • the specific production method is as follows. A reaction vessel was charged with 3.0 L of a mixed solution of magnesium chloride and zinc chloride (magnesium concentration: 0.96 mol/L, zinc concentration: 0.05 mol/L). While stirring the mixed solution, 2.0 mol/L of sodium hydroxide was charged into the reaction vessel in an amount of 0.95 equivalents of the total equivalent of magnesium and zinc, to obtain coprecipitate No. 3. Co-precipitate No. 3 was washed with deionized water, filtered, and then deionized water was added and resuspended using a homogenizer to obtain resuspended coprecipitate No. 3.
  • Example 3 100 parts by mass of chloroprene resin (PS-40A, manufactured by Denka Co., Ltd.), 0.5 parts by mass of stearic acid, 30 parts by mass of carbon black, and 4.0 parts by mass of Powder No. 1 were kneaded by a roll mill to form Rubber Composition No. 1. When rubber composition No. 1 was formed, most of the rubber composition No. 1 did not adhere to the roll.
  • PS-40A chloroprene resin
  • Rubber composition No. 1 was molded to a thickness of 2 mm, press-vulcanized at 153°C for 30 minutes, and then left to stand at room temperature for 24 hours to form sheet No. 1.
  • the properties of sheet No. 1 were measured according to JIS K6251, Vulcanized rubber and thermoplastic rubber - Determination of tensile properties. The results are shown in Table 2.
  • Tb means "tensile strength at break.”
  • Eb means “elongation at break.”
  • Se means "tensile stress at a given elongation.” For example, Se100 means tensile stress at 100% elongation.
  • the heat resistance of sheet No. 1 was measured according to JIS K6257:2017, Determination of heat aging properties of vulcanized and thermoplastic rubber. The heating conditions were 153°C and 0.5 hours. The results are shown in Table 2.
  • the Shore A hardness of Sheet No. 1 was measured according to JIS K6253-3:2012, Vulcanized rubber and thermoplastic rubber - Determination of hardness - Part 3: Durometer hardness. The results are shown in Table 2.
  • the compression set: CS (%) of sheet No. 1 was measured according to JIS K6262:2013, Vulcanized rubber and thermoplastic rubber - Determination of compression set at room temperature, high temperature and low temperature. The test temperature was 120°C and the test time was 72 hours. The results are shown in Table 2.
  • Rubber compositions No. 2 and No. 3, and sheets No. 2 and No. 3 were formed according to Example 3, except that the amount of powder No. 1 was as shown in Table 2. Their properties are shown in Table 2. When rubber compositions No. 2 and No. 3 were kneaded, they did not generally adhere to the roll.
  • Rubber compositions No. 4 to No. 6 and sheets No. 4 to No. 6 were formed according to Example 3, except that Powder No. 1 was replaced with Powder No. 2 in the amounts shown in Table 2. Their properties are shown in Table 2. When rubber compositions No. 4 to No. 6 were kneaded, they were not generally attached to the roll.
  • Rubber Composition No. 7 and Sheet No. 7 were made according to Example 3, except that Powder No. 1 was replaced with Powder No. 3 in the amounts shown in Table 2. Their properties are shown in Table 2.
  • Sheet No. 8 was formed from rubber composition No. 8 in the same manner as in Example 3. The properties of rubber composition No. 8 and sheet No. 8 are shown in Table 2.
  • Example 9 and Comparative Example 4 Each of rubber composition No. 2 and rubber composition No. 8 was subjected to a vulcanization test in accordance with JIS K6300-2:2001, "Unvulcanized rubber-Physical properties-Part 2: Determination of vulcanization properties using a stretching vulcanization tester.” The results are shown in FIG.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2024/017975 2023-05-25 2024-05-15 複合金属酸化物の粉体、ゴム用加硫剤、及びゴム組成物 Ceased WO2024241989A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157032A (ja) * 1992-03-30 1994-06-03 Kaisui Kagaku Kenkyusho:Kk 複合金属酸化物、その製造方法およびその使用
WO2014002574A1 (ja) * 2012-06-29 2014-01-03 トヨタ自動車株式会社 半導体膜の製造方法
CN113511668A (zh) * 2021-05-25 2021-10-19 扬州工业职业技术学院 一种空心六方体状Zn-Mg氧化物及其在协同双氧水降解罗丹明B中的应用
WO2023135927A1 (ja) * 2022-01-14 2023-07-20 セトラスホールディングス株式会社 亜鉛含有ハイドロタルサイト

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157032A (ja) * 1992-03-30 1994-06-03 Kaisui Kagaku Kenkyusho:Kk 複合金属酸化物、その製造方法およびその使用
WO2014002574A1 (ja) * 2012-06-29 2014-01-03 トヨタ自動車株式会社 半導体膜の製造方法
CN113511668A (zh) * 2021-05-25 2021-10-19 扬州工业职业技术学院 一种空心六方体状Zn-Mg氧化物及其在协同双氧水降解罗丹明B中的应用
WO2023135927A1 (ja) * 2022-01-14 2023-07-20 セトラスホールディングス株式会社 亜鉛含有ハイドロタルサイト

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DHANANJAYA N., AMBUJAKSHI N.P., RAVIKUMAR C.R., NAVEEN KUMAR A.: "Comparative study on photocatalytic degradation and sensor properties of Chonemorpha fragrans leaf extract assisted MgxZn1−xO (0 ≤ x ≤ 1) nanoparticles", INORGANIC CHEMISTRY COMMUNICATIONS, vol. 144, 1 October 2022 (2022-10-01), NL , pages 109827 - 109827-13, XP093243708, ISSN: 1387-7003, DOI: 10.1016/j.inoche.2022.109827 *
YATHISHA R.O.; ARTHOBA NAYAKA Y.; PURUSHOTHAMA H.T.; MANJUNATHA P.; BASAVARAJAPPA K.V.; VINAY M.M.: "Investigation the influence of Zn2+ doping on the photovoltaic properties (DSSCs) of MgO nanoparticles", JOURNAL OF MOLECULAR STRUCTURE, vol. 1217, 8 May 2020 (2020-05-08), NL , XP086190979, ISSN: 0022-2860, DOI: 10.1016/j.molstruc.2020.128407 *

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