Classifications

• • 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
  • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
• • 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

• the present disclosure relates to a composite metal oxide powder, a rubber vulcanizing agent, a rubber composition, and a method for producing the composite metal oxide powder.
• a vulcanizing agent such as zinc oxide
• a vulcanization aid such as magnesium oxide
• composite metal oxides containing magnesium oxide and zinc oxide, and rubber compositions containing the composite metal oxides have been investigated.
• Patent Document 1 discloses the following composite metal oxide.
• Formula (1) Mg 1-x M 2+ x O (1)
• M2 + represents at least one divalent metal ion selected from the group consisting of Mn2 + , Fe2 + , Co2 + , Ni2 + , Cu2 + and Zn2 +
• x represents a number in the range of 0.001 ⁇ x ⁇ 0.5
• Mn2 + represents at least one divalent metal ion selected from the group consisting of Mn2 + , Fe2 + , Co2 + , Ni2 + , Cu2 + and Zn2 +
• x represents a number in the range of 0.001 ⁇ x ⁇ 0.5
• Patent Document 2 discloses the following composite metal oxide.
• Formula (1) Mg 1-x M 2+ x O (1) (wherein M2 + represents at least one divalent metal ion selected from the group consisting of Mn2 + , Fe2 + , Co2 + , Ni2 + , Cu2 + and Zn2 + , and x represents a number in the range of 0.001 ⁇ x ⁇ 0.5), and is a thermally conductive composite metal oxide which is a magnesium oxide-based solid solution having a BET specific surface area of 4 m2 /g or less.
• Patent Documents 1 and 2 do not disclose any structure of a composite metal oxide having a specific X-ray peak according to the present disclosure, the structure of which is defined by powder X-ray diffraction (XRD).
• An object of the present disclosure is to provide a composite metal oxide powder that is particularly useful as a vulcanizing agent for rubber.
• a composite metal oxide powder includes magnesium oxide and zinc oxide, and has a zinc oxide peak and a magnesium oxide peak in XRD, and the magnesium oxide peak value has a diffraction angle shift within ⁇ 0.05° compared to the peak value of magnesium oxide single crystal.
• the second disclosure relates to the first disclosure, wherein the composite metal oxide is represented by the following formula (1): Mg 1-x Zn x O Formula (1) It is expressed by: In formula (1), x satisfies 0.02 ⁇ x ⁇ 0.5.
• the powder has a t35 of 27 minutes or more and 38 minutes or less when 100 parts by mass of the chloroprene resin and 3 to 10 parts by mass of the powder are mixed and a Mooney scorch test is performed at 125°C in accordance with JIS K 6300-1:2013.
• the powder has a t10 of 3.1 minutes or more and 4.0 minutes or less when 100 parts by mass of the chloroprene resin and 3 to 10 parts by mass of the powder are mixed and a Mooney scorch test is performed at 153°C in accordance with JIS K 6300-1:2013.
• the present sixth disclosure is a vulcanizing agent for rubber, comprising the powder according to any one of the first to fifth disclosures.
• the seventh disclosure is a rubber composition comprising the rubber vulcanizing agent according to the sixth disclosure and a rubber raw material.
• the eighth disclosure relates to a method for producing a composite metal oxide powder.
• the manufacturing method includes a precipitation step, an aging step, a crushing step, and a calcination step.
• a water-soluble magnesium salt is mixed with an alkali to obtain a precipitate.
• the precipitate is mixed with a water-soluble zinc salt and aged to obtain a matured product.
• the crushing step the matured product is crushed.
• the calcination step the crushed matured product is calcined to obtain a composite metal oxide.
• the composite metal oxide powder disclosed herein is particularly useful as a vulcanizing agent for rubber.
• FIG. 1 shows the powder X-ray diffraction data of Powder No. 1.
• the composite metal oxide powder, rubber vulcanizing agent, rubber composition, and method for producing the composite metal oxide powder according to the present disclosure will be described in detail below.
• the composite metal oxide powder according to the present disclosure may be hereinafter referred to as the "powder according to the present disclosure.”
• the powder according to the present disclosure is a composite metal oxide powder, and contains magnesium oxide and zinc oxide.
• a composite metal oxide refers to a metal oxide that combines magnesium oxide and zinc oxide, in other words, the composite metal oxide does not include a mixture of magnesium oxide and zinc oxide.
• the powder according to the present disclosure has a zinc oxide peak and a magnesium oxide peak in powder X-ray diffraction (XRD).
• XRD powder X-ray diffraction
• the peak value in the (200) plane of the magnesium oxide is shifted in the diffraction angle (2 ⁇ ) within a range of ⁇ 0.05° compared to the peak value of magnesium oxide single crystal.
• CuK ⁇ radiation is used as the X-ray source, the peak value of the diffraction angle (2 ⁇ ) in the (200) plane of magnesium oxide single crystal appears at approximately 42.9°.
• the peak value in the (220) plane may have a diffraction angle (2 ⁇ ) shift within a range of ⁇ 0.05° compared to the peak value of magnesium oxide single crystal.
• the peak value of the diffraction angle (2 ⁇ ) in the (220) plane of magnesium oxide single crystal appears at around 61.2°.
• the powder X-ray diffraction (XRD) can be performed using CuK ⁇ radiation as an X-ray source with a measurement range of 5 to 70°, a step width of 0.026°, and a measurement speed of 10 seconds/step.
• the CuK ⁇ radiation has a wavelength of 1.5418 ⁇ .
• An example of an apparatus for carrying out the above powder X-ray diffraction (XRD) is Empyrean-DY1356 manufactured by Malvern Panalytical.
• 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 amount of zinc oxide and magnesium oxide can be reduced compared to conventional systems that add zinc oxide and magnesium oxide. This can contribute to achieving the SDGs (Sustainable Development Goals) adopted at the United Nations Summit.
• the composite metal oxide is preferably represented by the following formula (1): Mg 1-x Zn x O Formula (1) It is expressed by: x preferably satisfies 0.02 ⁇ x, more preferably 0.05 ⁇ x, and further preferably 0.15 ⁇ x. Also, x preferably satisfies x ⁇ 0.5, more preferably x ⁇ 0.25, and further preferably x ⁇ 0.2. This makes it easier for zinc oxide to be exposed to the outside of magnesium oxide.
• the powder can be prepared by mixing 100 parts by mass of chloroprene resin with 3 to 10 parts by mass of the powder, and performing a Mooney scorch test at 125°C in accordance with JIS K 6300-1:2013, Unvulcanized rubber - Physical properties - Part 1: Determination of viscosity and scorch time using a Mooney viscometer.
• the test may be hereinafter referred to as the "125°C Mooney scorch test”.
• the powder has a t35 of preferably 27 minutes or more, more preferably 29 minutes or more, and even more preferably 31 minutes or more in the 125°C Mooney scorch test.
• the powder also has a t35 of preferably 38 minutes or less, more preferably 37 minutes or less, and even more preferably 36 minutes or less in the 125°C Mooney scorch test.
• t35 means the scorch time (minutes) at which the Mooney reading rises 35M above the minimum viscosity: Vm.
• Vm minimum viscosity
• the powder can be mixed with 100 parts by mass of chloroprene resin and 3 to 10 parts by mass of the powder, and subjected to a Mooney scorch test at 153°C in accordance with JIS K 6300-1:2013.
• the test may be hereinafter referred to as the "153°C Mooney scorch test.”
• the powder has a t10 of preferably 3.1 minutes or more, more preferably 3.3 minutes or more, and even more preferably 3.4 minutes or more.
• the powder has a t10 of preferably 4.2 minutes or less, more preferably 4.1 minutes or less, and even more preferably 4.0 minutes or less. This provides excellent curability for the rubber composition when the powder is used as a rubber vulcanizing agent.
• the "t10” refers to the scorch time (minutes) at which the Mooney reading rises by 10M from the minimum viscosity: Vm.
• the chloroprene resin has the same properties as in the 125°C Mooney scorch test.
• D50 means the 50% particle size based on volume, and can be measured by the laser diffraction method.
• An example of an instrument used in the laser diffraction method is the LMS-2000e laser diffraction scattering particle size distribution analyzer manufactured by Seishin Enterprises.
• the powder can have any BET specific surface area, and the preferred range may vary depending on the application.
• the powder when the powder is used as a rubber vulcanizing agent, the powder preferably has a BET specific surface area of 10 m2 /g or more, more preferably 15 m2 /g or more, and even more preferably 20 m2 /g or more.
• the powder when the powder is used as a rubber vulcanizing agent, the powder preferably has a BET specific surface area of 300 m2 /g or less, more preferably 280 m2 /g or less, and even more preferably 250 m2 /g or less.
• the BET specific surface area is measured, for example, by a high-speed specific surface area/pore distribution measuring device NOVA2000 manufactured by Yuasa Ionics Co., Ltd.
• the powder according to the present disclosure may not be surface-treated.
• the powder according to the present disclosure may be surface-treated with a surface treatment agent, for example, to improve dispersibility in the rubber raw material.
• a surface treatment agent include at least one of anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicone treatment agents, silicic acid, and water glass.
• Particularly preferred surface treatment agents are one or more selected from the group consisting of oleic acid, stearic acid, octanoic acid, and octylic acid.
• the amount of the surface treatment agent is 0.01 to 20% by mass, and preferably 0.1 to 15% by mass, based on the powder.
• Surface treatment with a surface treatment agent can be carried out, for example, by putting the powder into a Henshiel mixer, and while stirring the powder at high speed, dropping in the surface treatment agent either as is or diluted with a solvent, and mixing the powder and the surface treatment agent.
• the rubber vulcanizing agent according to the present disclosure includes the above powder.
• the zinc oxide is exposed on the outside of the magnesium oxide, and therefore when the powder is used as a rubber vulcanizing agent, the zinc oxide exposed on the outside of the magnesium oxide can promote initial vulcanization.
• the rubber composition according to the present disclosure includes the rubber vulcanizing agent and a rubber raw material.
• the rubber raw material include synthetic rubber raw materials.
• the synthetic rubber include acrylic rubber, ethylene propylene rubber (EPDM), butyl rubber, isoprene rubber, styrene butadiene rubber (SBR), nitrile rubber (NBR), and halogen-containing rubber.
• the halogen-containing rubber include at least one of chlorosulfonated polyethylene, fluororubber, brominated butyl rubber, and epichlorohydrin rubber.
• the ratio of the rubber raw material and the rubber vulcanizing agent may vary depending on the type of rubber to be formed. For example, 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass, of the rubber vulcanizing agent is added per 100 parts by mass of the rubber raw material.
• the rubber composition may further contain other additives in addition to the rubber vulcanizing agent.
• additives include antioxidants, UV absorbers, antistatic agents, pigments, lubricants, crosslinking agents, vinyl chloride heat stabilizers, foaming agents, plasticizers, and fillers.
• vinyl chloride heat stabilizers include at least one of organic acid salts of zinc, ⁇ -diketones, organotins, phosphites, and partial esters of polyhydric alcohols.
• the rubber vulcanizing agent according to the present disclosure is capable of vulcanizing raw rubber materials without the addition of other vulcanizing agents and/or vulcanization accelerators, but may further contain other vulcanizing agents and/or other vulcanization accelerators.
• the mixing of the rubber raw material and the rubber vulcanizing agent is not particularly limited as long as it is possible to mix them.
• the mixing can be carried out using, for example, at least one of a single screw extruder, a twin screw extruder, a roll, and a Banbury mixer.
• the rubber composition can be molded, for example, by at least one of injection molding, extrusion molding, blow molding, press molding, rotational molding, calendar molding, sheet forming molding, transfer molding, lamination molding, and vacuum molding.
• the powder according to the present disclosure has the same functions as conventional magnesium oxide, and is therefore useful in the above-mentioned rubber vulcanizing agent applications.
• the powder according to the present disclosure can be used in at least one of the applications in which 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 deodorant, a light resistance improver, and a resin hardener.
• the method for producing a composite metal oxide powder according to the present disclosure includes a precipitation step, an aging step, a grinding step, and a calcination step.
• a water-soluble magnesium salt is mixed with an alkali to obtain a precipitate.
• the precipitate contains magnesium hydroxide.
• the water-soluble magnesium salt include, but are not limited to, at least one of magnesium chloride, magnesium nitrate, magnesium acetate, and magnesium sulfate. From the viewpoint of suppressing aggregation of primary particles, the water-soluble magnesium salt is preferably magnesium chloride, magnesium nitrate, or magnesium acetate.
• the above alkali includes, for example, hydroxides of alkali metals and hydroxides of alkaline earth metals.
• the above alkali metal hydroxides include, for example, sodium hydroxide, potassium hydroxide, and lithium hydroxide.
• the above alkaline earth metal hydroxides include, for example, calcium hydroxide.
• the alkali can be added in an amount appropriate for forming magnesium hydroxide and zinc hydroxide from the water-soluble magnesium salt and the water-soluble zinc salt added in the aging step described below.
• the amount of alkali required theoretically for the water-soluble magnesium salt and the water-soluble zinc salt to completely form magnesium hydroxide and zinc hydroxide is taken as 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 alkali may be added in an amount of 100 mol % (1.0 equivalent) or less from the viewpoint of facilitating washing of at least one of the precipitate, the mixture, and the aged product.
• the precipitate is mixed with a water-soluble zinc salt and aged to obtain an aged product.
• the water-soluble zinc salt include zinc chloride and/or zinc nitrate.
• the ratio of the precipitate to the water-soluble zinc salt can be appropriately adjusted according to the preferred molar ratio of Mg and Zn in the composite metal oxide. For example, when the composite metal oxide has a chemical composition of Mg 1-x Zn x O, the precipitate can be mixed with the water-soluble zinc salt in such a ratio that the molar ratio of Mg:Zn is (1-x):x.
• the mixture may be washed, for example with deionized water, filtered, and resuspended, for example, in water and/or an organic solvent, if necessary, before maturation.
• a homogenizer may be used for the resuspension.
• the mixture is aged to form an aged product.
• the aging temperature 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, for example, using an autoclave.
• 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.
• the aging temperature is preferably 10 hours or less, more preferably 8 hours or less, and even more preferably 6 hours or less.
• the aged product can be dehydrated, filtered, and/or dried as necessary.
• the aged product is ground to form a ground aged product.
• the aged product can be crushed using a crusher known in the art, such as at least one of 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, and a ball mill.
• a crusher known in the art, such as at least one of 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, and a ball mill.
• the pulverized aged product is calcined to obtain a composite metal oxide powder.
• Calcination of the aged product can be carried out by a method known in the art. Calcination of the aged product can be carried out at a temperature of preferably 300°C or higher, and more preferably 350°C or higher. Calcination of the coprecipitate can be carried out at a temperature of preferably 600°C or lower, and more preferably 550°C or lower. 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.
• Example 1 0.84 L of magnesium chloride solution with a magnesium concentration of 1.0 mol/L was added to the reaction vessel. While stirring the magnesium chloride solution, sodium hydroxide with a sodium concentration of 2.0 mol/L was added to the reaction vessel so that the amount was 0.95 equivalents of magnesium, and precipitate No. 1 was obtained. Precipitate No. 1 was washed with deionized water, filtered, and then 2.97 L of deionized water was added and resuspended using a homogenizer to obtain resuspended precipitate solution No. 1.
• the resuspended precipitate solution No. 1 was added to the container and stirred while maintaining the temperature at 30°C. 0.16 L of zinc chloride solution with a zinc concentration of 1.0 mol/L was added dropwise to the container over 30 minutes to obtain mixture No. 1.
• Mixture No. 1 was aged at 80°C for 4 hours, filtered, dried, and pulverized in a ball mill, and then calcined at 400°C for 1 hour to obtain composite metal oxide powder No. 1.
• the chemical composition of the composite metal oxide powder No. 1 was Mg0.8Zn0.2O .
• the D50 of the composite metal oxide powder No. 1 was 24.35 ⁇ m.
• the BET specific surface area of the composite metal oxide powder No. 1 was 128 m2 /g.
• the powder X-ray diffraction (XRD) data of the composite metal oxide powder No. 1 is shown in FIG. 1 together with the powder X-ray diffraction (XRD) data of a commercial product containing a magnesium oxide single crystal.
• the commercial product was Kyowamag 150 manufactured by Kyowa Chemical Industry Co., Ltd. In FIG. 1, the peak corresponding to the (200) plane appears at about 42.9°, and the peak corresponding to the (220) plane appears at about 61.2°.
• Powder No. 2 was formed by mixing zinc oxide (Zinc Oxide Type 2, manufactured by Seido Chemical Industry Co., Ltd.) and magnesium oxide (Kyowamag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) in a mass ratio of zinc oxide:magnesium oxide of 1:4.
• Composite metal oxide powder No. 5 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. 1. Co-precipitate No. 1 was washed with deionized water, filtered, and then deionized water was added and resuspended using a homogenizer to obtain resuspended coprecipitate No. 1.
• the resuspended coprecipitate No. 1 was aged at 175°C for 12 hours using an autoclave, filtered, dried, ground in a ball mill, and then calcined at 450°C for 1 hour to obtain composite metal oxide powder No. 5.
• the chemical composition of composite metal oxide powder No. 5 was Mg0.95Zn0.05O .
• the D50 of composite metal oxide powder No. 5 was 0.90 ⁇ m .
• the BET specific surface area of composite metal oxide powder No. 5 was 142 m2 /g.
• Example 2 100 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.
• Rubber composition No. 1 As the storage stability of rubber composition No. 1, Vm, t5 and t35 were measured according to the 125° C. Mooney scorch test described in this specification. The results are shown in Table 2. Rubber composition No. 1 was molded to a thickness of 2 mm, press-vulcanized at 153°C for 30 minutes, and then allowed 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 120°C for 72 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 2, except that the amount of powder No. 1 was as shown in Table 2. Their properties are shown in Table 2.
• Rubber compositions No. 4 to No. 6 and sheets No. 4 to No. 6 were formed according to Example 2, except that powder No. 1 was replaced with powders No. 2 to 4 in the amounts shown in Table 2. Their properties are shown in Table 2.
• Rubber Composition No. 7 and Sheet No. 7 were made according to Example 2, except that Powder No. 1 was replaced with Powder No. 5 in the amounts shown in Table 2. Their properties are shown in Table 2.
• Rubber composition No. 8 was obtained by kneading 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, 5 parts by mass of zinc oxide (zinc oxide type 2, manufactured by Seido Chemical Industry Co., Ltd.), and 4 parts by mass of magnesium oxide (Kyowamag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) using a roll mill.
• Sheet No. 8 was formed from rubber composition No. 8 in the same manner as in Example 2. The properties of rubber composition No. 8 and sheet No. 8 are shown in Table 2.

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