JP2826973B2 - Composite metal hydroxide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel composite metal hydroxide. More specifically, there is no foaming trouble of a molded article caused by decomposition of a flame retardant at a processing temperature with a resin and / or rubber, and excellent flame retardancy and acid resistance are imparted to the resin and / or rubber. Flame retardant containing a non-halogen composite metal hydroxide as an active ingredient,
And a novel composite metal hydroxide capable of providing a flame retardant resin and / or rubber composition containing the flame retardant.

[0002]

2. Description of the Related Art The demand for flame retardancy for resins and rubbers is increasing year by year and is becoming more severe. In order to meet such a requirement for flame retardancy, a flame retardant using an organic halide and antimony trioxide together has been proposed and implemented. However, this flame retardant partially decomposes during processing to generate halogen gas, which corrodes processing and molding machines, is toxic to workers, has a bad influence on heat resistance and weather resistance of resins and rubbers However, there is a problem that a large amount of smoke containing toxic gas is generated during combustion.

[0003] For this reason, there has been an increasing demand for non-halogen flame retardants which do not have the above-mentioned problems, and aluminum hydroxide, magnesium hydroxide and the like have attracted attention. However, aluminum hydroxide starts dehydration from about 190 ° C. and causes foaming troubles in the molded product.
It is necessary to keep the temperature below 0 ° C., which has a problem that the types of applicable resins and rubbers are limited. Magnesium hydroxide has a dehydration start temperature of about 340 ° C.
Therefore, it has an advantage that it can be applied to almost all resins and rubbers. Furthermore, the present inventors have developed a new method for synthesizing magnesium hydroxide that enables the production of well-developed crystals, so that it is possible to obtain good molded bodies and use them for communication cables, ships, and the like. It was started.

[0004]

However, it has been found that there is still a problem to be solved in the above magnesium hydroxide. First, a high level of flame retardancy cannot be achieved unless it is blended in a relatively large amount with resin and / or rubber. For example, when blended with polypropylene, in order to pass VO (highest flame retardancy level) with a thickness of 1/8 inch to 1/16 inch in UL-94 flame retardant standard, 100 parts by weight of resin About 150-250
It is necessary to mix parts by weight. A high content of magnesium hydroxide causes a problem of reducing the Izod impact strength, elongation, tensile strength and the like among the physical properties of the resin.

[0005] The second problem is poor acid resistance.
For example, if a communication cable, power cable, etc. made of polyethylene with magnesium hydroxide,
Magnesium hydroxide gradually dissolves and shifts to the surface of the molded body due to carbonic acid contained in water, and a phenomenon occurs in which magnesium carbonate precipitates and the surface is whitened. In the long term, there arises a problem that the flame retardancy is reduced by the amount of the magnesium hydroxide dissolved and disappeared, and the electric insulation is also reduced.

The present invention solves the above problems and provides a novel composite metal which can provide a flame retardant having excellent flame retardancy and acid resistance, and a flame retardant resin and / or rubber composition containing the flame retardant. The purpose is to provide hydroxide.

[0007]

The present invention has a BET specific surface area of 1 to ²⁰ m ² / g, preferably 3 to 15 m ² / g, and an average secondary particle diameter of 0. The following formula (1) Mg _1-x M ²⁺ (OH) ₂ (1) wherein M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , and Ni 2−4.0 μm, and preferably 0.4-2 μm.
²⁺ , at least one of divalent metal ions selected from the group consisting of Cu ²⁺ and Zn ²⁺ , wherein x is 0.00
5 <x <0.7, preferably a number in the range of 0.01 ≦ x ≦ 0.6).

[0008] The composite metal hydroxide of the present invention comprises a flame retardant for a resin and / or rubber containing the composite metal hydroxide as an active ingredient, and 20 to 100 parts by weight of the resin and / or rubber. It is useful for providing a flame-retardant resin and / or rubber composition containing 250 parts by weight.

The present inventor has been working on providing a flame retardant, a flame retardant resin and / or a rubber composition which can advantageously overcome a new problem in the use of magnesium hydroxide as a flame retardant. As a result, the above-mentioned problem is due to the physical properties inherent in magnesium hydroxide, and it has been considered that the essential solution of the above-mentioned problem is difficult as long as magnesium hydroxide is used.

That is, the present invention itself is considered to be substantially impossible to use as a flame retardant since Mn, Fe, Co, Ni have been considered to be substantially impossible to decompose and dehydrate at a lower temperature than aluminum hydroxide. A flame retardant which can solve the above problems by forming a hydroxide of at least one transition metal selected from, Cu and Zn with magnesium hydroxide, more specifically, by forming a solid solution of both. And a flame-retardant resin containing the flame retardant and / or
Alternatively, it was found that a rubber composition was obtained, and the composition was completed.

The completion of the present invention is based on the discovery of extremely surprising and remarkable characteristics in the course of research on the composite metal hydroxide of the present invention. First, the decomposition or dehydration temperature of the composite metal hydroxide becomes lower than that of magnesium hydroxide almost in proportion to the solid solution amount of the transition metal hydroxide. Is different depending on the type of the transition metal. Thus, as a flame retardant for resin and / or rubber, dehydration of magnesium hydroxide whose dehydration start temperature is slightly higher than about 190 ° C. of aluminum hydroxide and conversely higher than the ignition temperature of many resins and / or rubbers Starting temperature less than about 340 ° C.
Dehydration start temperature of about 200 to 340 ° C, 320 to 420 ° C
Thus, it has become possible to provide a composite metal hydroxide which is extremely useful as a flame retardant for a resin and / or a rubber which is dehydrated at an arbitrary temperature between the decomposition peak temperatures. It is presumed that the closer the combustion temperature (exothermic reaction) of the resin and / or rubber and the decomposition / dehydration temperature (endothermic reaction) of the metal hydroxide compounded therein, the higher the flame retardancy is obtained. . Secondly, it is presumed that some of the transition metals have an additional effect of promoting carbonization at the time of combustion of resin and / or rubber and increasing flame retardancy by their dehydrogenation catalytic action. . Third, although the degree of acid resistance varies depending on the type of transition metal, it has a characteristic of being significantly improved as compared with magnesium hydroxide. This characteristic is particularly remarkable in Ni.

The composite metal hydroxide of the formula (1) is expressed as Mg (O
H) ₂ and a solid solution of M ²⁺ (OH) ₂ . Therefore powder X
The line diffraction pattern is substantially the same as that of magnesium hydroxide, although the diffraction angle slightly varies depending on the ionic radius and amount of M ²⁺ . At the thermal decomposition temperature measured by differential thermal analysis (DTA), both hydroxides do not separate into two endothermic decomposition temperatures corresponding to their original decomposition temperatures, but one decomposition as one compound or crystal. Indicates temperature. The range of x in equation (1) is the type of M ²⁺ , that is, M
It is governed by the ionic radius of ²⁺ . The closer the ionic radius of M ²⁺ is to Mg ²⁺ , the larger the range of x because a solid solution can be formed in a wider range. When x is 0.005 or less,
Degradation temperature decreases less than magnesium hydroxide,
Conversely, if it is 0.7 or more, it approaches the decomposition temperature of aluminum hydroxide and foams. A more preferable range of x is 0.1.
01 ≦ x ≦ 0.6.

The composite metal hydroxide of the formula (1) has a crystallite size of 0.2 to 4 μm, particularly preferably 0.4 to 2 μm.
A substance having little or no secondary aggregation, that is, an average secondary particle diameter of 0.2 to 4 μm, and preferably 0.4 to 2 μm.
And a BET specific surface area of 1 to 20 g / m ² , preferably 3 to 15 g / m ² . The range of the above characteristic values of the composite metal hydroxide is suitable for various properties such as compatibility with resin and / or rubber, dispersibility, moldability or processability, appearance of molded article, mechanical strength and flame retardancy. This is a preferable range for maintaining the range.

In the composite metal hydroxide of the formula (1), M
^{2+, Mn 2+, Fe 2+, Co} 2+, Ni 2+, at least one divalent metal ion selected from the group consisting of Cu ²⁺ and Zn ^2+, M ²⁺ is more X represents the total of each of the divalent metal ions. Among the divalent metal ions, Ni ²⁺ and Zn ²⁺ are most preferably used. Ni ²⁺ has a particularly remarkable effect on improving acid resistance,
Zn ²⁺ is white and has the effect of lowering the decomposition temperature with the addition of a smaller amount.

Therefore, in the composite metal hydroxide of the formula (1),
Complex metal hydroxide of formula (2) Mg _1-x (Ni ²⁺ and / or Zn ²⁺ ) _x (OH) ₂ (2) wherein x has the same meaning as x in formula (1) Can be exemplified as a preferable example.

The composite metal hydroxide of the present invention can be used as a flame retardant as it is, and further includes, for example, higher fatty acids, anionic surfactants, phosphate esters, and coupling agents (silane, titanate, aluminum-based). ) And at least one surface treating agent selected from the group consisting of polyhydric alcohols and esters of fatty acids.

Preferred examples of the surface treating agent are as follows. Higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid and behenic acid; alkali metal salts of the higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl alcohol; polyethylene glycol ether Sulfate, amide bond sulfate, ester bond sulfate, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkylallyl sulfonate, ester bond alkylallyl sulfonate, amide Anionic surfactants such as a bonded alkylallyl sulfonate; orthophosphoric acid and mono- or diesters such as oleyl alcohol and stearyl alcohol or a mixture of both; Phosphoric acid esters such as emissions salt; vinyl triethoxysilane,
Vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltri Silane coupling agents such as methoxysilane and gamma-mercaptopropyltrimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate;
Titanate coupling agents such as isopropyltridecylbenzenesulfonyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; esters of fatty acids with polyhydric alcohols such as glycerin monostearate and glycerin monooleate.

The surface coating treatment of the composite metal hydroxide of the formula (1) with the surface treating agent can be carried out by a known wet or dry method. For example, as a wet method, the surface treating agent may be added in a liquid or emulsion state to the slurry of the composite metal hydroxide, and sufficiently mechanically mixed at a temperature up to about 100 ° C. As a dry method, the powder of the composite metal hydroxide is converted into a liquid, an emulsion, and a surface treatment agent under sufficient stirring by a mixer such as a Henschel mixer.
What is necessary is just to add in solid form, and to mix sufficiently under heating or non-heating. The addition amount of the surface treatment agent can be appropriately selected, but is preferably about 0.1 to about 10% by weight based on the weight of the composite metal hydroxide.
It is preferred that

After the surface treatment, if necessary, means such as washing, dehydration, granulation, drying, pulverization, classification and the like can be appropriately selected and carried out to obtain a final product form.

The composite metal hydroxide used in the present invention can be produced by various methods. For example, in an aqueous solution containing Mg ions and M ²⁺ ions, an alkali of approximately 1 equivalent or less, preferably 0.95 equivalents or less based on the total of Mg and M ²⁺ , preferably at about 40 ° C. or less is added. It can be produced by a coprecipitation method in which the precipitate is added under stirring. As another method, it can be produced by a method in which MgO and / or Mg (OH) ₂ and an aqueous solution containing M ²⁺ ions are mixed and reacted. As still another method, it can be produced by a sol-gel method by hydrolysis of an alcoholate of Mg and M ²⁺ .

The composite metal hydroxide produced by the above method is used in the presence of a reaction mother liquor or further with CaCl ₂ , CaBr ₂ , MgCl ₂ , to further grow crystals and further reduce secondary aggregation. MgBr ₂ , N
More preferably, a salt such as aCl or KCl is added as a crystal growth promoter, and the mixture is subjected to hydrothermal treatment using an autoclave at about 110 ° C. to 250 ° C. for about 1 hour or more.

Mg used for forming composite metal hydroxide
Examples of the ion supply material include, for example, alcoholates such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium acetate, magnesium ethoxide, magnesium propoxide, bittern, seawater, underground brine, and the like. Examples of M ²⁺ ion feedstocks include, for example, Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ and Zn
Chloride, bromide, iodide, fluoride, nitrate, formate, acetate, divalent metal ion selected from the group consisting of ²⁺
Examples include alcoholates such as propoxide, ethoxide, propoxide, and isopropoxide.

Examples of the alkali used to form the composite metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide (natural or synthetic), ammonia water, ammonia gas and the like.

The above raw materials are all preferably as pure as possible. In particular, the content of polyvalent metal ions such as sulfate ions, borate ions and silicate ions is preferably 100 ppm or less, particularly preferably 10 ppm or less, based on the total of MgO, M ²⁺ O and alkali solids.

Examples of the resin and rubber used in the present invention include, for example, polyethylene, a copolymer of ethylene and another α-olefin, a copolymer of ethylene and vinyl acetate, ethyl acrylate or methyl acrylate, Polypropylene, copolymer of propylene and other α-olefin, polybutene-1, polystyrene, styrene and acrylonitrile, copolymer of ethylene and propylene diene rubber or butadiene, vinyl acetate, polyacrylate, polymethacrylate, polyurethane, polyester , Polyether, thermoplastic resin such as polyamide, phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, thermosetting resin such as alkyd resin, EPD
Examples thereof include M, SBR, NBR, butyl rubber, isoprene rubber, chlorosulfonated polyethylene, and the like, but are not limited thereto.

In the present invention, the compounding amount of the composite metal hydroxide of the formula (1) with respect to the resin and / or rubber depends on the type of the resin and / or the rubber and the type of the composite metal hydroxide of the formula (1). About 20 parts of the complex metal hydroxide of the formula (1) with or without surface treatment with respect to 100 parts by weight of resin and / or rubber.
From about 250 parts by weight, preferably from about 30 to about 200 parts by weight. If the amount of the composite metal hydroxide of the formula (1) is less than the above range, the flame retardancy becomes insufficient. On the contrary, if the amount is too large, for example, the tensile strength, Izod impact strength and the like are reduced, or the acid resistance is reduced. Therefore, there is a possibility that disadvantages such as deterioration of the composition may occur.

There are no particular restrictions on the method of mixing and kneading the resin and / or rubber with the composite metal hydroxide of the formula (1), and any mixing means capable of uniformly mixing both can be employed. For example, a single-screw or twin-screw extruder, a roll, a Banbury mixer and the like. There is no particular restriction on the molding method, and any known molding means can be arbitrarily employed according to the type of resin and / or rubber, the type of a desired molded product, and the like. For example, 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 flame-retardant resin and / or rubber composition of the present invention may optionally contain various additives in addition to the composite metal hydroxide of the formula (1). For example, it is a flame retardant aid containing at least one of carbon powder, ferrocene, anthracene, polyacetylene, red phosphorus, acrylic fiber, nickel oxide, and fibrous magnesium hydroxide. As the compounding amount of such a flame retardant aid, resin and / or rubber 10
About 0.01 to about 10 parts by weight per 0 parts by weight is preferably employed.

As other additives, lubricants such as zinc behenate, magnesium behenate, zinc stearate, calcium stearate, magnesium stearate, lead stearate, aluminum stearate and the like, as well as water resistance and acid resistance (whitening resistance) improvers. May be added as needed. As the compounding amount of such a lubricant, about 0.1 to about 10 parts by weight is preferably employed with respect to 100 parts by weight of the resin and / or rubber.

The flame-retardant resin composition of the present invention may contain other conventional additives in addition to the above components. Examples of such additives include antioxidants, ultraviolet inhibitors, antistatic agents, pigments, foaming agents, plasticizers, fillers, reinforcing agents, organic halogen flame retardants, and crosslinking agents.

Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 First-grade reagents, magnesium chloride and manganese chloride, were dissolved in deoxygenated deionized water to make 10 liters of a mixed solution of 2.0 mol / l and 0.2 mol / l, respectively, and the volume was 20 liters. The temperature was adjusted to 20 ° C. in a 1 liter stainless steel cylindrical reaction vessel. This solution was synthesized by a coprecipitation reaction of synthetic calcium hydroxide (Ca (OH) ₂ ) (reagent primary calcium chloride and sodium hydroxide) at 20 ° C. and 2.5 mol / l at a temperature of 2.5 ° C. while stirring with a chem stirrer under N ₂ gas atmosphere. ) Was added in about 2 minutes, corresponding to about 90% of the total equivalent weight of Mg and Mn, and stirring was continued for another 20 minutes to carry out the reaction. Immediately thereafter, the reaction was
It was placed in a 5-liter autoclave and subjected to hydrothermal treatment at 150 ° C. for 2 hours. Then dewater, wash with filter press,
After dehydration, it was vacuum dried. The dried product is pulverized, and the chemical analysis value, BET specific surface area, average secondary particle size, powder X-ray diffraction,
Differential thermal analysis (DTA) -thermogravimetric analysis (TGA) values were measured.

The BET specific surface area is determined by the N ₂ adsorption method, the sample powder is subjected to ultrasonic dispersion treatment in an aqueous solution of sodium hexametaphosphate having an average secondary particle diameter of 0.2%, and the DTA-TGA is treated in an N ₂ atmosphere by the microtrack method. Measured below. Table 1 shows the measurement results.

Example 2 In Example 1, reagent grade 2.0 was used as the mixed aqueous solution.
6 mol / l magnesium chloride and 0.16 mol / l
Reaction with 1 liter of ferrous chloride
The same operation as in Example 1 was performed except that the reaction was performed at 70 ° C. for 2 hours. Table 1 shows the measurement results of the obtained reactants.

Example 3 In Example 1, the reagent first-grade 2.1 was used as the mixed aqueous solution.
Synthetic slaked lime (synthesized in Example 1) was prepared using about 9 mol / l of magnesium chloride and 0.12 mol / l of cobaltous chloride, and the total equivalent weight of Mg ²⁺ and Co ²⁺ was about 9%.
8.0 liters equivalent to 0% was added, and the hydrothermal treatment was
The same operation as in Example 1 was performed except that the reaction was performed at 4 ° C. for 4 hours. Table 1 shows the measurement results of the obtained reactants.

Example 4 First-class reagent nickel chloride was dissolved in ion bitter (a by-product of NaCl in the ion-exchange membrane method and mainly containing MgCl ₂ , CaCl ₂ , and MgBr ₂ ). 10 liters of a mixed solution of 0.04 mol / l as liter and Ni was prepared, the temperature was adjusted to 25 ° C., and the mixture was placed in a 20 liter stainless steel cylindrical reaction tank. While stirring this solution, 2.5 mol / l of synthetic slaked lime (synthesized in Example 1) was added to 8.0 liter corresponding to about 93% of the total equivalent of Mg and Ni to about 25 liters.
After adjusting the temperature to 0 ° C, the mixture was added in about 3 minutes, and stirring was continued for 2 minutes.
The reaction was continued for 0 minutes. The reaction was placed in a 25 liter autoclave and hydrothermally treated at 180 ° C. for 3 hours. Then, after dehydration, washing and dehydration with a filter press, drying in an oven and pulverization were performed. Table 1 shows the measurement results of the obtained reactants.

Example 5 In Example 4, the mixed aqueous solution was adjusted to have a Mg concentration of 1.87 mol / L and a Ni concentration of 0.14 mol / L, and the synthetic slaked lime (synthesized in Example 1) was used. The same operation as in Example 4 was performed except that 1 liter was added. Table 1 shows the measurement results of the obtained reactants.

Example 6 In Example 4, the mixed aqueous solution was prepared by adjusting the Mg concentration of the mixed aqueous solution to 1.13 mol / L and the Ni concentration to 0.48 mol / L, and synthesizing slaked lime (synthesized in Example 1) to 6.0. The same operation as in Example 4 was performed except that 1 liter was added. Table 1 shows the measurement results of the obtained reactants.

Example 7 In Example 4, the mixed aqueous lime (synthesized in Example 1) was prepared in the same manner as in Example 4 except that the mixed solution had an Mg concentration of 0.80 mol / L and a Ni concentration of 0.93 mol / L. The same operation as in Example 4 was performed except that 1 liter was added. Table 1 shows the measurement results of the obtained reactants.

Example 8 The procedure of Example 4 was repeated except that the Mg concentration of the mixed aqueous solution was 2.1 mol / l and the concentration of cupric chloride of the first class of reagent was 0.04 mol / l instead of Ni. Example 4
The same operation was performed. Table 1 shows the measurement results of the obtained reactants.

Example 9 The same procedure as in Example 4 was carried out except that the aqueous Mg concentration of the mixed aqueous solution was 2.13 mol / l, the concentration of the first grade zinc nitrate was 0.02 mol / l instead of Ni, and the hydrothermal treatment was 12 mol / l.
The same operation as in Example 4 was performed except that the temperature was changed to 0 ° C. for 4 hours.
Table 1 shows the measurement results of the obtained reactants.

Example 10 In Example 4, the Mg concentration of the mixed aqueous solution was set to 2.01 mol / L, the concentration of zinc nitrate of the first grade of the reagent was set to 0.14 mol / L instead of Ni, and natural magnesium was used instead of synthetic slaked lime. Example 4 except that 7.3 liters of 2.5 mol / liter slaked lime obtained by calcining and hydrating limestone were used.
The same operation was performed. Table 1 shows the measurement results of the obtained reactants.

Example 11 600 liters of filtered and decarbonated seawater (15 ° C., M
(concentration: 0.052 mol / l) was placed in a reaction vessel having a capacity of 1000 liters, and nickel chloride and zinc nitrate (first grade reagent) were added thereto with stirring, and the concentrations of both were 9.7 × 10 ^-4.
It was adjusted to mol / liter. Next, after adjusting the temperature to 20 ° C., a synthetic slaked lime (20 mol / liter) having a concentration of 2.5 mol / liter corresponding to about 90% of the total equivalent of Mg, Ni and Zn was prepared.
C) 11.7 liters was added in about 1 minute and stirring continued for another 20 minutes. The cake was dehydrated with a filter press, and the resulting cake was added to a reagent-grade calcium chloride aqueous solution having a concentration of 2.0 mol / l, dispersed using a stirrer, and then placed in a 25-liter autoclave. Hydrothermal treatment for hours. Thereafter, dehydration, washing and dehydration were performed with a filter press, followed by drying and pulverization. Table 1 shows the measurement results of the obtained reactants.

Comparative Example 1 In Example 4, an aqueous solution containing 0.6 mol / l of Mg and 1.12 mol / l of Ni was used as the mixed aqueous solution, and 6.4 liter of synthetic slaked lime was added. Except having made it react, it operated similarly to Example 4. Table 1 shows the measurement results of the obtained reactants.

Comparative Example 2 A reaction was carried out in the same manner as in Example 4 except that an aqueous solution containing 1.9 mol / l of Mg and 0.24 mol / l of first-grade zinc nitrate as a mixed aqueous solution was used. Was operated in the same manner as in Example 4. Table 1 shows the measurement results of the obtained reactants.

Comparative Examples 3 to 10 Mn (OH) ₂ (Comparative Example 3) and Fe synthesized by a coprecipitation method of a chloride aqueous solution and sodium hydroxide in a nitrogen atmosphere.
(OH) ₂ (Comparative Example 4), first-grade reagent Co (OH) ₂ (Comparative Example 5), Ni (OH) ₂ (Comparative Example 6), Cu (OH) ₂
(Comparative Example 7), Zn (OH) ₂ (Comparative Example 8) synthesized by a coprecipitation method of an aqueous chloride solution and sodium hydroxide, and Al (OH) ₃ (Comparative Example 9) as a commercial product, Mg (OH) ₂ It measured similarly using (Comparative Example 10). Table 1 shows the measurement results.

[0046] Table 1 Example Chemical composition BET specific surface area Average secondary particle diameter ^{(m 2 / g) (μm} ) Example _{1 Mg 0.90 Mn 0.10 (OH)} 2 15 0.56 2 Mg 0.92 Fe 0.08 (OH) 2 10 _{0.64 3 Mg 0. 94 Co 0.06} (OH) 2 5 0.94 4 Mg 0.98 Ni 0.02 (OH) 2 6 0.81 5 Mg 0.86 Ni 0.14 (OH) 2 4 1.40 6 Mg 0.68 Ni 0.32 ( _{OH) 2 5 0.90 7 Mg 0.42} Ni 0.58 (OH) 2 6 0.86 8 Mg 0.98 Cu 0.02 (OH) 2 12 0.45 9 Mg 0.99 Zn 0.01 (OH) 2 7 0.79 10 Mg 0.93 Zn _{0.07 (OH) 2 19 0.41 11} Mg 0.96 Ni 0.02 Zn 0.02 (OH) 2 9 0.71 Comparative example _{1 Mg 0.30 Ni 0.70 (OH)} 2 11 0.51 2 Mg 0.88 Zn 0.12-y (OH) 2 _{-2y + yZnO 13 0.35 3 Mn (} OH) 2 synthetic - - 4 Fe ( H) ₂ synthetic - - 5 Co (OH) ₂ reagent - - 6 Ni (OH) ₂ reagent - - 7 Cu (OH) ₂ reagent - - 8 Zn (OH) ₂ synthetic - - 9 Al (OH) ₃ Commercial product--10 Mg (OH) ₂ Commercial product--

Table 1 (continued) Example X-ray powder diffraction Dehydration start temperature Dehydration peak temperature Pattern (° C.) (° C.) Example 1 A 275 390 2 A 212 350 3 A 244 380 4 A 304 400 5 A 295 402 6 A 253 360 7 A 245 350 8 A 308 399 9 A 300 415 10 A 210 37311 A 265 380 Comparative Example 1 A 200 330 2 B 250 333, 383 3-120 180 4-150 2005 5-150 240 6-170 310 7-40 160 8-50 50 220 9-190 320 10-340 430 Notes; B: shows a diffraction pattern similar to Mg (OH) ₂ and B: shows a diffraction pattern similar to Mg (OH) ₂ and ZnO.

Examples 12 to 18 Each of the composite metal hydroxide powders obtained in Examples 1, 3, 4, 5, 8, 9 and 11 was suspended in water and dispersed well with stirring. After the temperature was raised to 70 ° C., a previously dissolved aqueous solution of sodium oleate (about 70 ° C.) was added to the composite metal hydroxide in an amount of 1.5% by weight as oleic acid. Then, it was dehydrated, washed with water, granulated and dried.

0.2 parts by weight of an antioxidant (0.1 part by weight of Irganox 1 per 100 parts by weight of impact-resistant polypropylene)
010 and 0.1 part by weight of Weston 626) and the compounding amount of hydroxide shown in Table 2 were uniformly mixed, and then melt-kneaded at about 230 ° C. using a twin-screw extruder to obtain composite pellets. The pellets were dried at 120 ° C. for 2 hours using a vacuum dryer, and then injection molded at about 230 ° C. using an injection molding machine to prepare test pieces. Table 2 shows the evaluation results of the injection moldability, flammability, and mechanical strength.

Comparative Examples 11 to 15 Test pieces were prepared in the same manner as in Example 12 except that the metal hydroxide shown in Table 2 was used as the flame retardant instead of the composite metal hydroxide of the present invention. Was prepared, and injection moldability and the like were evaluated. Table 2 shows the evaluation results.

Example 19 The composite metal hydroxide powder obtained in Example 4 was heated at about 80 ° C.
After stirring in warm water, sodium salt of stearyl phosphate (a mixture of monoester and diester) was added to the hydroxide at a concentration of 3.0% by weight with stirring, and the surface was treated with sufficient stirring. Then, it was dehydrated, washed with water, granulated and dried.
A test piece was prepared in the same manner as in Example 12 except that this product and carbon black were used as the flame retardant in the amounts shown in Table 2, and the injection moldability and the like were evaluated. Table 2 shows the evaluation results.

Example 20 The composite metal hydroxide powder obtained in Example 9 was heated at about 80 ° C.
After dispersion in warm water, 1.0 part by weight of lauric acid was added to the hydroxide with stirring, and the mixture was further sufficiently stirred to perform surface treatment. Then, it was dehydrated, washed with water, granulated and dried. A test piece was prepared in the same manner as in Example 12 except that this material and acrylic fiber (diameter 0.5 denier) were used as flame retardants in the amounts shown in Table 2, and the injection moldability and the like were evaluated. Table 2 shows the evaluation results.

[0053] Table 2 Example type flame retardant amount of the resin type flame retardant Example 12 Polypropylene _{Mg 0.90 Mn 0.10 (OH) 2} 190 13 Polypropylene _{Mg 0.94 Co 0.06 (OH) 2} 180 14 Polypropylene Mg _0.98 Ni _0.02 (OH) ₂ 170 15 polypropylene Mg _0.86 Ni _0.14 (OH) ₂ 175 16 polypropylene Mg _0.98 Mn _0.02 (OH) ₂ 190 17 polypropylene Mg _0.99 Zn _0.01 (OH) ₂ 190 18 polypropylene Mg _0.96 Ni _0.02 Zn _0.02 (OH) ₂ 160 Comparative Example 11 Polypropylene Mg (OH) ₂ (Comparative Example 10) 190 12 Polypropylene Al (OH) ₃ (Comparative Example 9) 190 13 Polypropylene Ni (OH) ₂ (Comparative Example 6) 190 14 Polypropylene Mg _0.30 Ni _0.70 (OH) ₂ 190 15 Polypropylene _{Mg 0.88 Zn 0.12 (OH) 2-2y} + yZnO 190 Example 19 Polypropylene _{Mg 0.98 Ni 0.02 (OH) 2} 150 Carbon black 2.5 20 Polypropylene _{Mg 0.99 Zn 0.01 (OH) 2} 170 acrylic fibers 2.5 Note: The flame retardant The amount is based on 100 parts by weight of the resin.

Table 2 (continued) Example Injection Moldability Flammability Tensile Break Izod Molded product appearance Strength Impact strength Example 12 AV-0 187 5.9 13 AV-0 195 9.3 14 AV-0 210 12.9 15 AV-0 194 19.6 16 A V-0 185 5.9 17 A V-0 189 6.1 18 18 A V-0 218 14.2 Comparative Example 11 A V-2 172 4.6 12 D Non-standard --- 13 D Non-standard --- 14 B V-2 180 5.2 15 A V-2 170 4.0 Example 19 A V-0 223 19.8 20 A V-0 230 18.5 Note: A shows good injection moldability and molded article appearance.
B indicates injection moldability, somewhat poor, and a flash pattern on the appearance of the molded product, D indicates strong foaming and is impossible to mold, and flammability indicates a test result of 1/16 inch thickness according to UL-94 standard. The unit of tensile breaking strength is kg · f /
cm ² , and the unit of the Izod impact strength (with notch) is kg · cm / cm.

Example 21, Comparative Example 16 The composite metal hydroxide obtained in Example 10 and commercially available magnesium hydroxide were added to very low density linear polyethylene (VLLDPE), respectively, with vinyl-tris (2-methoxy-
After surface treatment with 1% by weight of ethoxy) silane, they were mixed in the amounts shown in Table 3 (Example 21, Comparative Example 16). Then, the mixture was melt-kneaded at 200 ° C by a twin-screw extruder to prepare pellets, dried in vacuum at 100 ° C for 2 hours, and injection-molded at 200 ° C. Table 3 shows the evaluation results of the injection moldability and the like.

Example 22, Comparative Example 17 The composite metal hydroxide obtained in Example 11 and commercially available magnesium hydroxide were each subjected to a surface treatment with 1% by weight of γ-aminopropyltrimethoxysilane, and the results are shown in Table 3. The mixture was mixed in the compounding amount, and then melt-kneaded at about 230 ° C. using a twin-screw extruder to form a pellet. After vacuum drying the obtained pellets, they were molded at 230 ° C. using an injection molding machine to obtain test pieces. Table 3 shows the evaluation results of the injection moldability and the like.

Example 23, Comparative Example 18 The composite metal hydroxide obtained in Example 11 and commercially available magnesium hydroxide were added to 100 parts by weight of ethylene propylene diene rubber (EDPM), respectively, to obtain isopropyl triisostearoyl titanate 1 After surface treatment in weight%, at the compounding amount shown in Table 3, and the following other additives: zinc oxide 5 parts by weight Accelerator TT (tetramethyluram disulfide) 1.5 parts by weight Sulfur 0.5 parts by weight Stearic acid 1 2.0 parts by weight in the above amount, and then mixed with an open roll.
The mixture was melt-kneaded at 50 ° C. The obtained kneaded material was vulcanized at 160 ° C. for 30 minutes by a press molding machine to form a sheet,
A test piece was made from this sheet. Table 3 shows the evaluation results.

[0058] Table 3 Example Type flame retardant amount of the resin type flame retardant Example _{21 VLLDPE Mg 0.93 Zn 0.07 (OH} ) 2 120 Comparative Example 16 VLLDPE Mg (OH) ₂ 120 Example 22 Nylon 6 Mg _0.96 Zn _0.02 Ni _0.02 (OH) ₂ 50 Comparative Example 17 Nylon 6 Mg (OH) ₂ 50 Example 23 EDPM Mg _0.98 Ni _0.02 (OH) ₂ 120 Comparative Example 18 EDPM Mg (OH) ₂ 120 Note: The amount of the flame retardant is resin 100 The parts by weight of the flame retardant relative to parts by weight are shown.

Table 3 (continued) Example Injection Moldability Flammability Tensile Break Tensile Break Molded product appearance Elongation at strength (%) Example 24 A V-0 151 800 Comparative Example 16 A Nonstandard 128 730 Example 22 A V-0 850 8 Comparative Example 17 A V-2 831 2 Example 23 -V-0 106 440 Comparative Example 18-Out of specification 84 410 Note: A indicates good injection moldability and good molded product appearance. Flammability is measured at 1/8 inch thickness according to UL-94 standard. Tensile rupture strength. Is in kg · f / c
m ² .

Example 24, Comparative Example 19 [Acid Resistance Test] 100 mg of the flame retardant powder shown in Table 4 was
30 ml of deionized water is charged and kept at 35 ° C.
And the volume stirred with a magnetic stirrer 50
Placed in a beaker of 1 ml and stirred uniformly for 1 minute. Then, the pH was maintained at 4.0 using a pH stat device, and the pH was adjusted to 0.1.
The time until 5.15 ml of N-HCl was consumed was measured. Table 4 shows the measurement results. The longer the time, the better the acid resistance.

[Carbon-Resistant Water Resistance] The flame retardants shown in Table 4 were each subjected to a surface treatment with 3% by weight of sodium stearate with respect to the flame retardants by a wet method.
After mixing 130 parts by weight of the flame retardant with respect to 0 parts by weight, melt-kneading at 240 ° C. using a twin-screw extruder, and vacuum drying,
13 × 127 × 3.2m using an injection molding machine at 240 ° C
m test pieces were prepared. 50 pieces of this test piece
It was impregnated with 0 ml of deionized water, the temperature was kept at 20 ° C., and CO ₂ gas was blown at a rate of about 500 ml / min.
The surface appearance of the test piece was visually evaluated in five stages. Table 4 shows the evaluation results.

Table 4 Examples Types of Flame Retardants pH Stat Test (min ) Example 24-1 Mg _0.90 Mn _0.10 (OH) ₂ 2.0 24-2 Mg _0.94 Co _0.06 (OH) ₂ 1.6 24-3 Mg _0.98 Ni _0.02 (OH) ₂ 5.4 24-4 Mg _0.86 Ni _0.14 (OH) ₂ 44.2 24-5 Mg _0.68 Ni _0.32 (OH) ₂ 102.4 Comparative Example 19 Mg (OH) ₂ 0.9

[0063] Note: The evaluation of the resistance to carbonated water is as follows: 5: No whitening, 4: Slightly whitening, 3: Whitening, 2:
Violent whitening 1: Violent whitening over the entire surface.

[0064]

According to the present invention, a novel composite metal hydroxide is provided. Furthermore, according to the present invention, a flame retardant for a resin and / or rubber capable of exhibiting excellent flame retardancy and acid resistance by blending the composite metal hydroxide with a resin and / or rubber, and the flame retardant A novel composite metal hydroxide useful for providing a flame retardant resin and / or rubber composition having excellent flame retardancy and acid resistance. Further, according to the present invention, there is provided a flame retardant capable of exhibiting excellent flame retardancy and acid resistance without causing trouble of foaming of a molded article due to decomposition of the flame retardant at a processing temperature of resin and rubber, and the flame retardant. A novel composite metal hydroxide useful for providing a flame-retardant resin and / or rubber composition containing the same is provided. According to the present invention, a flame retardant containing, as an active ingredient, a composite metal hydroxide capable of maintaining a decomposition / dehydration temperature close to the combustion temperature of resins or rubbers by arbitrarily adjusting the dehydration start temperature; A novel composite metal hydroxide useful for providing a flame retardant resin and / or rubber composition containing a flame retardant is provided. ADVANTAGE OF THE INVENTION According to this invention, the flame retardant which can obtain desired flame retardance with a comparatively small compounding amount, and the flame retardant resin which contains the said flame retardant and which was excellent in mechanical properties, such as Izod impact strength, and / or A novel composite metal hydroxide useful for providing a rubber composition is provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 21/00 C08L 21/00 101/00 101/00

Claims (2)

(57) [Claims] 1. Mg _1-x M having a BET specific surface area of 1 to 20 m ² / g and an average secondary particle diameter of 0.2 to 4.0 μm measured by a microtrack method. ²⁺ _x (OH) ₂ (1) (where M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni
²⁺ represents at least one divalent metal ion selected from the group consisting of Cu ²⁺ and Zn ²⁺ , and x represents 0.00
5 <x <0.7). 2. The composite metal hydroxide of the formula (1) is represented by the following formula (2): Mg _1-x (Ni ²⁺ and / or Zn ²⁺ ) _x (OH) ₂ (2) 2. The composite metal hydroxide according to claim 1, wherein the composite metal hydroxide has the same meaning as in (1).