JPH06157032A - Composite metal oxide, its production and its use - Google Patents

Abstract

PURPOSE:To produce the composite metal oxide exhibiting excellent characteristics as a thickening agent, a thermal stabilizer, etc., for resins, etc., by calcining a magnesium hydroxide solid solution of the formula at a prescribed temperature. CONSTITUTION:A magnesium hydroxide solid solution of formula: Mg1-xM<2+>x(OH2)2 (M<2+> is selected from Mn<2+>, Fe<2+>, Co<2+>, Ni<2+>, Cu<2+> and Zn<2+>; x is 0.001-0.5) is calcined at 400-1000 deg.C to produce a magnesium oxide solid solution of formula: Mg1-xM<2+>Ox. 0.001-20 pts.wt. of the composite metal oxide is compounded with 100 pts.wt. of a resin, etc., to provide a resin composition and/or a rubber composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel mixed metal oxide, a method for producing the same and use thereof. More specifically, a novel composite metal oxide capable of imparting thermal stability, weather resistance, vulcanizability, thickening property, etc. superior to magnesium oxide, a method for producing the same, and a heat stability obtained by blending the composite metal oxide. TECHNICAL FIELD The present invention relates to a resin and / or rubber composition having excellent properties, vulcanizability, thickening property, and the like.

[0002]

2. Description of the Related Art Magnesium oxide has been used in various fields because it is relatively inexpensive, relatively stable, relatively basic, and nontoxic. For example, it is present in acid acceptors during vulcanization of halogenated rubbers such as chloroprene and chlorosulfonated polyethylene, heat stabilizers and weather resistance improvers of polyvinyl chloride, thickeners of FRP, and resins such as ABS and EVA. It has also been used as a neutralizing agent for acidic substances generated during thermal decomposition, a ceramic raw material, an annealing separator for electromagnetic steel sheets, and the like.

However, magnesium oxide easily aggregates,
Poor dispersion in resin or rubber. Therefore, the original functions of neutralizing acid and halogen and thickening cannot be sufficiently exerted. In addition, the mechanical strength and appearance of resins and rubber are often impaired. In addition, it has a high hygroscopic property and is apt to cause various troubles. A novel method for producing highly dispersible magnesium oxide which hardly causes agglomeration has also been proposed (JP-A-2-14141).
No. 8). However, the reactivity with an acidic substance is not yet sufficiently satisfactory, and the disadvantages that unreacted magnesium oxide remains in the resin and that the hygroscopicity is large cannot be solved.

[0004]

DISCLOSURE OF THE INVENTION Magnesium oxide is
As an essential drawback, it is poor in water resistance and acid resistance and absorbs water in resin or rubber, so that the resin or rubber is often swollen and the original product characteristics are impaired. Further, when magnesium oxide is used in a resin or rubber container, when an acidic substance is added, magnesium oxide is gradually eluted into the acidic substance. For this reason, when a high level of water resistance is required, for example, toxic lead compounds are inevitably used in water packing, rubber used as lining material for reservoirs, PVC electric wires, window frames, pipes, etc. There is. Therefore, there has been a demand for a novel compound which can maintain the low toxicity which is the original advantage of magnesium oxide and can further enhance the reactivity with respect to an acid or a halogen, and can improve the hygroscopicity which is the inherent drawback of magnesium oxide.

[0005]

According to the present invention, a BET specific surface area of 5 to 300 m ² / g is given by the formula (1) Mg _1-x M ²⁺ _x O (1) (wherein M ²⁺ is Mn ^{2 +} , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu
²⁺ and Zn ^2+, which represents at least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , and x represents a number in the range of 0.001 <x <0.5), and a solid solution thereof, An acid-accepting agent (including a heat stabilizer and a thickening agent) for a resin and / or rubber, which contains as an active ingredient.
Further, in the present invention, the magnesium oxide solid solution is added to 0.001 to 2 parts by weight with respect to 100 parts by weight of resin and / or rubber.
A resin and / or rubber composition blended with 0 part by weight is provided. The present invention further provides a magnesium hydroxide-based solid solution of the formula (3) Mg _1-x M ²⁺ (OH) ₂ (3) (wherein M ²⁺ and x have the same meaning as in the formula (1)). Provided is a method for producing the above magnesium oxide-based solid solution, which comprises firing at about 400 to 1000 ° C.

The present inventor has conducted earnest research to overcome the drawbacks of magnesium oxide, such as poor water resistance and poor acid resistance. As a result, the poor water resistance of magnesium oxide
This is due to the physical properties peculiar to magnesium oxide, and as far as magnesium oxide is concerned, it has been thought that it would be difficult to remedy this drawback significantly, and further research was conducted.

As a result, the following formula (3) Mg _1-x M ²⁺ _x (OH) ₂ (3) previously invented by the present inventor (in the formula, M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu
²⁺ and Zn ²⁺ represents at least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , and x represents a number in the range of 0.001 <x <0.5), and a magnesium hydroxide solid solution of about 4
It has been discovered that a magnesium oxide-based solid solution is obtained by firing at 00 to 1000 ° C., and that this magnesium oxide-based solid solution exhibits superior water resistance and acid resistance to magnesium oxide. Further, they have also discovered an unexpected characteristic that this magnesium oxide-based solid solution has a higher reactivity with acids and halogens than magnesium oxide.

The powder X-ray diffraction pattern of the magnesium oxide type solid solution represented by the formula (1) of the present invention is substantially the same as that of magnesium oxide, and M ²⁺ O (M ²⁺ is M of the formula (1)).
²⁺ ) has the same meaning) and no diffraction pattern appears. Since M ²⁺ O is solid-dissolved in magnesium oxide, the diffraction angle slightly shifts depending on the amount of solid solution and the type of M ²⁺ dissolved. The larger the solid solution amount x of M ²⁺ O, the higher the water resistance and acid resistance, and the reactivity to acid and halogen,
The viscosity increase and the sinterability tend to be improved. But x
Is 0.5 or more, the reactivity becomes lower than that of magnesium oxide. Therefore, the range of x is preferably 0.0
1 ≦ x <0.5, more preferably 0.03 ≦ x <0.3
Is.

Among M ²⁺ of the formula (1), nickel has excellent water resistance and acid resistance. When M ²⁺ is zinc, the water resistance and acid resistance are not so much improved as that of nickel, but it shows superior whiteness and reactivity to acids and halogens than magnesium oxide, and as a heat stabilizer for resins, especially vinyl chloride. When used, it exhibits features such as remarkably suppressing reddish coloring of magnesium oxide. The magnesium oxide-based solid solution having the above characteristics is represented by the formula (2) Mg _1-x (Ni and / or Zn) _x O (2) (where x represents the same meaning as in the formula (1)).

The magnesium oxide-based solid solution of the present invention is preferably highly dispersible in resins and rubbers with almost no aggregation in order to maximize its ability. In order to exert such characteristics, the average secondary particle diameter is preferably 0.1 to 2 μm, particularly preferably 0.1 to 1.0 μm, and the BET specific surface area is 5 m ² / g or more, preferably 1
It is at 0m ² / g or more, and particularly preferably 20m ² / g~3
It is 00 m ² / g.

The magnesium oxide-based solid solution of the present invention can be used as it is, and higher fatty acids, metal salts of higher fatty acids, anionic surfactants, phosphoric acid esters, silane-based, titanate-based, aluminum-based coupling agents, You may use after surface-treating with surface-treating agents, such as ester of polyhydric alcohol and fatty acid.

Examples of the surface treatment agent preferably used are as follows. Higher fatty acids having 10 or more carbon atoms such as stearic acid, oleic acid, erucic acid, palmitic acid, lauric acid and behenic acid; salts of the higher fatty acids such as Mg, Ca, Zn, Al and Na; stearyl alcohol, oleyl Sulfate ester salts of higher alcohols such as alcohols; Sulfate ester salts of polyethylene glycol ethers; Amide bond sulfate ester salts, ester bond sulfate ester salts, ester bond sulfonates, amide bond sulfonates, ether bond sulfonates, ether bond alkyl allyls Anionic surfactants such as sulfonates, ester-bonded alkylallylsulfonates, amide-bonded alkylallylsulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc., or a mixture of both, Phosphates such as acid type or alkali metal salts or amine salts; vinylethoxysilane, vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxy Silane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-
Silane coupling agents such as mercaptopropyltrimethoxysilane; titanate coupling agents such as isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tridecylbenzenesulfonyl titanate; acetoalkoxyaluminum diisopropylate Aluminum-based coupling agents such as; esters of alcohols and fatty acids such as glycerin monostearate and glycerin monooleate.

The surface coating treatment of the magnesium oxide type solid solution of the formula (1) with the surface treating agent can be carried out by a method known per se. For example, the surface treatment agent may be added in the form of liquid, emulsion or solid with sufficient stirring of a magnesium oxide solid solution powder with a mixer such as a Henschel mixer, and the mixture may be sufficiently mixed with or without heating.
The addition amount of the surface treatment agent can be appropriately selected, but is usually about 0.1 to about 10 based on the weight of the magnesium oxide solid solution.
% By weight. After surface treatment, granulation, drying, crushing,
Means such as classification are appropriately selected and implemented to obtain the final product form.

The magnesium oxide-based solid solution of the present invention exhibits strong basicity like magnesium oxide, and therefore reacts well with acids and halogens to neutralize and inactivate them. Therefore, it reacts with monomers present in resins and rubbers, manufacturing processes, additives, catalysts such as Ziegler-Natta catalysts and Friedel-Crafts catalysts, halogens derived from post-halogenation, thermal decomposition, etc. Inactivate the
As a result, the heat resistance of resins and rubbers, weather resistance such as ultraviolet resistance, etc. are improved.

Specific examples of such fields of use include neutralization of catalyst residues remaining in a resin or rubber polymerized with a Ziegler-Natta catalyst such as polyethylene, polypropylene, 4-methylpentene-1, EPDM. , AB
Neutralization of acidic components in S, neutralization of Friedel-Crafts catalyst residues in polyacetal, neutralization of halogens liberated from organic halogen flame retardants, neutralization of acidic components in polyamide, heat of polyvinyl chloride Stabilizer (desorbed HCl
Neutralization), heat stabilizer for polyvinylidene chloride, heat stabilization by neutralization of acetic acid liberated from polyvinyl acetate and copolymers of ethylene and vinyl acetate and removal of acetic acid odor, heat stabilizer for polyphenylene sulfide ( Neutralization and inactivation of generated hydrogen sulfide), chloroprene rubber, halogenated butyl rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, acid acceptor for vulcanization of halogenated rubber such as chlorinated polyethylene, FRP Examples of the thickeners such as polyester and phenol resin used for the above.

The magnesium oxide type solid solution of the formula (1) used in the present invention is represented by the formula (3) Mg _1-x M ²⁺ _x (OH) ₂ (3) (wherein M ^{2 +} And x represent the same meaning as in the formula (1)), and the magnesium hydroxide solid solution represented by the formula (1) is about 400 to 1000.
It is produced by baking at 0.1 ° C. for about 0.1 to 10 hours in the atmosphere, atmosphere of nitrogen, helium, argon or the like or under vacuum.

The magnesium hydroxide-based solid solution of the formula (3) can be produced by various methods. For example, Mg ion and M ²⁺
Coprecipitation in which an aqueous solution containing ions is added with an alkali of about 1 equivalent or less, preferably 0.95 equivalent or less with ^respect to the total equivalent of Mg and M ²⁺ , with stirring, preferably at about 40 ° C. or less, with stirring. Manufactured by law. As another method, it can also be produced by a method of mixing magnesium oxide and / or magnesium hydroxide with an aqueous solution containing M ²⁺ and reacting them. Yet another method is magnesium and M ²⁺
It is also produced by the sol-gel method by hydrolysis of the alcoholate. The reaction product may be further heated and pressurized at about 100 to 250 ° C. in the presence or absence of mother liquor or calcium chloride or sodium chloride in an autoclave in order to improve crystal growth and dispersion.

Examples of the resins and rubbers used in the present invention include polyethylene, copolymers of ethylene with other α-olefins, copolymers of ethylene with vinyl acetate, ethyl acrylate or methyl acrylate, Polypropylene, copolymer of propylene and other α-olefins, polybutene-1,4-methylpentene-1, polystyrene, styrene and acrylonitrile, copolymer of ethylene and propylene diene rubber or butadiene, polyvinyl acetate, polyvinyl Thermoplastic resins such as alcohol, polyacrylate, polymethacrylate, polyurethane, polyester, polyether, polyamide, ABS, polycarbonate, polyphenylene sulfide,
Thermosetting resin such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, alkyd resin, E
PDM, SBR, NBR, butyl rubber, chloroprene rubber, isoprene rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluororubber, chlorinated butyl rubber, brominated butyl rubber, epichlorohydrin rubber, chlorinated polyethylene and the like are exemplified.

In the present invention, the compounding amount of the magnesium oxide type solid solution of the formula (1) with respect to the resin and / or the rubber is appropriately changed depending on the kind of the resin or the rubber and the kind of the halogen and the acid contained therein. Approximately 0.0 of the magnesium oxide solid solution of the formula (1) surface treated or not treated with 100 parts by weight of resin and / or rubber.
01 to about 20 parts by weight, preferably about 0.01 to about 10 parts by weight is blended.

There are no particular restrictions on the method of mixing and kneading the resin and / or rubber with the magnesium oxide-based solid solution of the formula (1), as long as they can be uniformly mixed.
For example, they are mixed and kneaded by a single-screw or twin-screw extruder, a roll, a Banbury mixer, or the like. There is no particular restriction on the molding method, and any known molding means can be arbitrarily adopted depending on the types of resin and rubber, the type of desired molded product, and the like.
For example, injection molding, extrusion molding, blow molding, press molding,
Rotational molding, calendar molding, sheet forming molding,
Examples include transfer molding, laminated molding, and vacuum molding.

The heat conductive resin and / or rubber composition of the present invention may contain other conventional additives in addition to the above components. Examples of such additives include antioxidants, ultraviolet absorbers, vulcanizing agents, vulcanization accelerators, antistatic agents,
Pigment, lubricant, cross-linking agent, organic salt of zinc, β-diketone, organotin, phosphite, vinyl ester heat stabilizer such as partial ester of polyhydric alcohol, foaming agent, plasticizer, filler Etc. are illustrated.

The composite metal oxide of the present invention is a resin and / or
Alternatively, it may be blended with rubbers to react with acidic substances and / or halogens contained in them rapidly and for a long time to improve thermal stability, to act on vulcanization of halogen-containing rubbers, and to It acts to form a pregel, extends the thermal stability and weather resistance of PVC, etc., and removes the odor of resin and rubber. Acid acceptors for resins and / or rubber, vulcanization It is useful as an agent, a thickener, a heat stabilizer, a deodorant, and a weather resistance improver.

The present invention will be described in more detail based on the following examples. In the following examples, parts mean parts by weight unless otherwise specified. Examples 1 and 2 Mixed aqueous solution of magnesium chloride and zinc nitrate (Mg ²⁺ =
1.9 mol / l, Zn ²⁺ = 0.035 mol / l, 20 ° C.) 5 liters were placed in a stainless steel round reaction tank of about 10 liters, and stirred with a chemistirrer.
Mol / l calcium hydroxide (20 ° C) 4.3
5 liters (corresponding to about 0.9 equivalent of the total equivalent of Mg and Zn) were added and reacted. The slurry containing the obtained white precipitate was put into an autoclave together with the reaction mother liquor, and heated and pressurized at 110 ° C. for 2 hours. The total, dehydration, washing with water, drying and crushing were carried out. The chemical composition of this product is Mg _0.98 Zn
_The powder X-ray diffraction pattern of _0.02 (OH) ₂ is Mg
The diffraction pattern was similar to that of (OH) ₂ .

This composite metal hydroxide was heated in an atmosphere of silicon using a silicon knit furnace at 500 ° C. for 5 minutes (Example 1), 7
Firing was performed at 50 ° C. for 30 minutes (Example 2). Chemical composition, powder X-ray diffraction, BET of the obtained composite metal oxide
The specific surface area and the average secondary particle diameter were measured. The results are shown in Table 1.

Including the following examples, the chemical composition was determined by the chelate titration method, and the BET specific surface area was determined by the nitrogen adsorption method on average of 2
The secondary particle diameter was measured by a Microtrac particle size analyzer after the sample was added to alcohol and sufficiently dispersed by ultrasonic waves.

Examples 3, 4 Mixed aqueous solution of magnesium chloride and nickel chloride (Mg ²⁺
= 1.73 mol / l, Ni ²⁺ = 0.27 mol / l, 15 ° C.) 5 liters were placed in a stainless steel round reaction tank of about 10 liters, and stirred with a chemister stirrer,
2. Add 2 mol / l calcium hydroxide (15 ° C) 4.
5 liters (corresponding to about 0.9 equivalent of the total equivalent of Mg and Zn) were added and reacted. The slurry containing the obtained white precipitate was put into an autoclave together with the reaction mother liquor, and heated and pressurized at 120 ° C. for 1 hour. The total, dehydration, washing with water, drying and crushing were carried out. The chemical composition of this product is Mg _0.85 Ni
_{It was 0.15} (OH) ₂ . Powder X-ray diffraction pattern is Mg
The diffraction pattern was similar to that of (OH) ₂ .

This composite metal hydroxide was heated in an air atmosphere using a silicon knit furnace at 500 ° C. for 5 minutes (Example 3), 7
Firing was performed at 50 ° C. for 30 minutes (Example 4). Chemical composition, powder X-ray diffraction, BET of the obtained composite metal oxide
The specific surface area and the average secondary particle diameter were measured. The results are shown in Table 1.

Example 5 150 liters of seawater filtered with sand and decarbonated (Mg ²⁺ =
(0.052 mol / liter, 12 ° C.) was placed in a reaction tank having a capacity of 200 liters, and 0.15 mol of cupric chloride was added and dissolved while stirring with a stirrer. 7.02 liters (corresponding to 0.88 equivalents of the total equivalents of Mg and Ca, 15 ° C.) of 1 mol / liter of calcium hydroxide was added and reacted.
After filtration and dehydration, the mixture was emulsified in a 2 mol / liter calcium chloride aqueous solution and heated at 100 ° C. for 1 hour. Then dehydration,
Washed with water, dried and crushed. The chemical composition of this product is Mg _0.96 C
It was u _0.04 (OH) ₂ . Powder X-ray diffraction pattern is M
It showed a pattern similar to g (OH) ₂ .

This composite metal hydroxide was fired in air at 750 ° C. for 30 minutes using a silicon knit furnace. The test results of this oxide are shown in Table 1.

Example 6 Magnesium nitrate and cobalt chloride were dissolved in deionized water which had been deoxidized by blowing nitrogen gas after boiling,
6 liters of a mixed aqueous solution of ²⁺ = 1.0 mol / liter and Co ²⁺ = 0.20 mol / liter was placed in a reaction tank having a volume of 10 liters while stirring and 4 mol / liter in a nitrogen gas atmosphere.
3 liters of sodium hydroxide (20 ° C.) was added and reacted. The reaction product was heated with a mother liquor in a nitrogen gas atmosphere at 98 ° C. for 3 hours, then filtered, washed with water, dried and pulverized.
The chemical composition of this product was Mg _0.80 Co _0.20 (OH) ₂ . The powder X-ray diffraction pattern showed the same pattern as Mg (OH) ₂ .

This composite metal hydroxide was fired at 450 ° C. for 5 minutes in a nitrogen atmosphere using a silicon knit furnace. The test results of this oxide are shown in Table 1.

Examples 7 and 8 4 liters (15 ° C.) of a mixed aqueous solution prepared by dissolving magnesium chloride and manganese chloride (Example 7) or ferrous sulfate (Example 8) in deionized water that had been deoxygenated had a volume of 10 It was placed in a liter reaction tank, and 4 liters of 2 mol / liter sodium hydroxide deoxidized while stirring was added and reacted. The obtained reaction product was placed in an autoclave together with the mother liquor, and heated and pressurized at 140 ° C. for 2 hours, filtered, washed with water, dried and pulverized. All the above operations were carried out under a nitrogen gas atmosphere. The chemical composition of this product is Mg _0.90 Mn _0.10 (OH)
₂ (Example 7) and Mg _0.90 Fe _0.10 (OH) ₂ (Example 8). These powder X-ray diffraction patterns are Mg
A pattern similar to that of (OH) ₂ was shown. These composite metal hydroxides were placed in a silicon atmosphere in a nitrogen atmosphere at 8
It was baked at 00 ° C. for 30 minutes. The test results are shown in Table 1.

Comparative Examples 1 and 2 Table 1 shows the test results of two types of commercially available high activity magnesium oxide and medium activity magnesium oxide.

Comparative Example 3 In Example 1, Mg ²⁺ = 1.1 mol / liter, Z
n ²⁺ = 0.3 mol / liter mixed aqueous solution (10 ° C.) 6
Liter and 2 mol / liter calcium hydroxide (1
Hydroxide was produced in the same manner as in Example 1 except that 3 liters (0 ° C.) were reacted. The powder X-ray diffraction pattern of the obtained hydroxide is similar to that of magnesium hydroxide: Mg _1-x Zn _x (OH) ₂ and (0.3-x) Zn (OH) 2.
The pattern of the mixture with _1.6 Cl _0.4 was shown. Zn / Mg
The molar ratio of was 0.30. Table 1 shows the test results of the product obtained by firing the product at 500 ° C. for 5 minutes.

Comparative Example 4 In Example 3, Mg ²⁺ = 0.54 as a mixed aqueous solution.
A hydroxide was obtained in the same manner as in Example 3 except that mol / liter and Ni ²⁺ = 1.26 mol / liter were used.
The chemical composition of this product was Mg _0.30 Ni _0.70 (OH) ₂ . The powder X-ray diffraction pattern was similar to that of Mg (OH) ₂ . This composite hydroxide is heated at 500 ° C in a nitrogen atmosphere at 5 ° C.
Bake for minutes. The oxide test results are shown in Table 1.

Table 1 Example Powder X-ray diffraction BET specific surface area Average secondary particle size (M ² / g) (μm) Example 1 Same as MgO 181 0.22 2 Same as MgO 42 0.27 3 Same as MgO 220 0.31 4 Same as MgO 40 0.33 5 Same as MgO 44 44. 30 6 Same as MgO 212 0.72 7 Same as MgO 34 0.63 8 Same as MgO 32 0.48 Comparative Example 1 Same as MgO 148 5.52 2 Same as MgO 32 4.16 3 MgO and ZnO 126 1. 73 4 Same as MgO 141 0.46

Example 9 (Acid acceptor for chloroprene rubber) Magnesium oxide compounds shown in Table 2 were blended as an acid acceptor with chloroprene rubber as follows. Chloroprene rubber (Showa Denko DuPont Co., Ltd., Neoprene GS) 100 parts Acid acceptor 4 parts Zinc oxide (Shodo Chemical Co., Ltd., Zinc Hua No. 1) 5 parts Stearic acid (Wako Pure Chemical Industries, Ltd., Reagent grade 1) 1 part Carbon black (Tokai Electrode Co., Ltd., Seast S) 30 parts After uniformly mixing the above components using an open roll,
A Mooney scorch test was conducted, and physical properties were measured by press vulcanization at 153 ° C. for 30 minutes. The test results are shown in Table 2.

The magnesium oxide-based solid solution of the present invention exhibited significantly improved storage stability (mooney scorch property) and improved rubber physical properties after vulcanization, as compared with magnesium oxide. In particular, water resistance, compression set, and modulus were improved.

Table 2 Types of magnesium oxide compounds Examples Comparative Example 1 3 6 1 3 4 Storage stability Original minimum viscosity Vm (Moonie) 30.4 30.9 29.9 29.0 29.2 29.5 T ₅ 34.8 35.7 34.0 31.2 30.7 26.2 T ₃₅ 62.0 65.7 61.8 50.5 48.0 36.5 Physical properties of vulcanized rubber 100% modulus 30 32 30 27 26 24 300% modulus 125 130 114 109 102 95 Tensile strength 215 220 219 207 199 190 Elongation (%) 520 518 522 540 558 565 Hardness 66 67 67 65 64 62 Compression set (%) 54.6 53.2 54.5 56.3 57.0 57.9 Water resistance 9.5 6.2 5.3 10.6 10.4 4.5 Note: Storage stability; Mooney scorch, 125 ° C Compression set; 100 ° C, after 22 hours Water resistance; 7 at 70 ° C Volume increase rate (%) after immersion for a day. Unit: modulus (kgf / cm ² ), tensile strength (kg
f / cm ² )

Example 10 (Use of Polyester Resin as Thickening Agent) In order to investigate the performance of the polyester resin as a thickening agent for SMC (sheet molding compound), unsaturated polyester resin (Nippon Shokubai Co., Ltd., Epolak) was used. N-2
1) 100 parts, calcium carbonate (Nitto Koka Co., Ltd., NS
-100), 1.0 part of the magnesium oxide-based thickener was mixed with a homogenizer for 2 minutes and then placed in an oven at 30 ° C.
The change in viscosity with time was measured using a Brookfield viscometer. The test results are shown in FIG. 1, symbol 1 shows the case where the composite metal oxide of Example 2 was added, and symbol 2 shows the case where the composite metal oxide of Example 4 was added. Reference numeral 3 shows the case where the commercially available magnesium oxide used in Comparative Example 2 was added. An ideal thickener is one that has a low initial viscosity, then shows a sharp S-shaped thickening, and has a high final viscosity. From FIG. 1, it can be seen that the magnesium oxide-based solid solution of the present invention is a thickener that is closer to the ideal than the commercially available magnesium oxide.

Example 11 (Suppression of acetic acid generation from EVA and suppression of acetic acid odor) EVA (manufactured by Mitsui DuPont Co., Ltd., ELVALOY 74)
1) 0.5 part of a magnesium oxide compound was mixed with 100 parts and kneaded at about 140 ° C. using an open roll to prepare a sample. 1.0 g of this sample was placed under a nitrogen gas flow to obtain D
Using a TA device, the temperature was raised to 200 ° C. and maintained for 60 minutes, the acetic acid generated by thermal decomposition was absorbed in deionized water, and the amount of acetic acid was quantified by neutralization titration with sodium hydroxide. The test results are shown in Table 3.

Table 3 MgO compound acetic acid generation amount (mg / g-sample) Sample of Example 1 2.1 Sample of Comparative Example 1 3.4 Blank 5.8

Example 12 Polyvinyl chloride having the following composition Polyvinyl chloride (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 700) 100 parts Zinc stearate (manufactured by Shodo Chemical Co., Ltd.) 0.5 parts Magnesium oxide compound 1. 0 part was kneaded at 170 ° C. using an open roll. Using a part of this sheet as a sample, the heat stabilization time was measured at 180 ° C. by the Congo red method (JIS K6723-1969). The test results are shown in Table 4.

[0044] 4.9 Table Table 4 MgO-based heat stabilizer thermal stabilization time _{(min) Mg 0.98 Zn 0.02 O 18.7 Mg} 0.76 Cu 0.04 O 20.6 Mg 0.85 Ni 0.15 O 19.4 MgO 12.1 no addition From 4, it can be seen that the magnesium oxide-based solid solution of the present invention exhibits excellent thermal stability as compared with magnesium oxide.

[0045]

According to the present invention, acid, which maintains low toxicity,
Provided is a novel magnesium oxide-based solid solution having excellent reactivity with halogen and improved hygroscopicity. The magnesium oxide-based solid solution exhibits excellent properties as an acid acceptor for resins and / or rubbers, a thickener, a heat stabilizer, a deodorant, and a weather resistance improver. Further, according to the present invention, there is provided a resin and / or rubber composition containing the above magnesium oxide-based solid solution.

[Brief description of drawings]

FIG. 1 is a graph showing the thickening effect of the magnesium oxide-based solid solution of the present invention.

[Explanation of symbols]

 1 Composite metal oxide of Example 2 2 Composite metal oxide of Example 4 3 Commercially available magnesium oxide of Comparative Example 2

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Claims (8)

[Claims] 1. 100 parts by weight of resin and 0.001-20
Parts by weight of formula (1) Mg _1-x M ²⁺ _x O (1) (wherein M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu
²⁺ and Zn ²⁺ represents at least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , and x represents a number in the range of 0.001 <x <0.5). A resin and / or rubber composition comprising an oxide. 2. The complex metal oxide of the formula (1) has the formula (2) Mg _1-x (Ni ²⁺ and / or Zn ²⁺ ) _x O (2) (where x is the formula (1)). A resin and / or rubber composition according to claim 1, which is a mixed metal oxide having the same meaning as in (1) above. . 3. The complex metal oxide of the formula (1) comprises higher fatty acids, phosphoric acid esters, silanes, titanates and aluminum-based coupling agents, and esters of polyhydric alcohols and fatty acids and metal salts of higher fatty acids. The resin and / or rubber composition according to claim 1, which is surface-treated with at least one surface-treating agent selected from the group consisting of: 4. The rubber is at least one rubber selected from chloroprene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, chlorinated or brominated butyl rubber, chlorinated polyethylene rubber and fluororubber, and the composite metal oxide is The resin and / or rubber composition according to claim 1, which is an acid acceptor or a vulcanizing agent for the rubber. 5. The resin according to claim 1, wherein the resin is at least one resin selected from unsaturated polyester resin, vinyl resin and phenol resin, and the composite metal oxide is a thickener for the resin. / Or a rubber composition. 6. A formula (1) Mg _1-x M ²⁺ _x O (1) having a BET specific surface area of 5 to 300 m ² / g (wherein M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co) ²⁺ , Ni ²⁺ , Cu
²⁺ and Zn ²⁺ represents at least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , and x represents a number in the range of 0.001 <x <0.5). Oxide. 7. The composite metal oxide according to claim 6, which has an average secondary particle diameter of 0.1 to 2.0 μm measured by the Microtrac method. 8. A magnesium hydroxide-based solid solution of the formula (3) Mg _1-x M ²⁺ _x (OH) ₂ (3) is added at about 400 to 1000 ° C.
The method for producing a composite metal oxide according to claim 6, which comprises firing at.