JPH05209084A - Compound metal hydroxide and its use - Google Patents

Abstract

PURPOSE:To obtain a composition which gives a molding free from the trouble of bubbling due to the decomposition of a flame retardant and is improved in flame retardancy and acid resistance by incorporating a specified compound metal hydroxide into a resin and/or a rubber. CONSTITUTION:100 pts.wt. resin and/or rubber is mixed with 20-250 pts.wt. flame retardant comprising a compound metal hydroxide of the formula (wherein M <2+> represents at least one kind of divalent metal ion selected from Mu<2+>, Fc2+, Co2+, Ni<2+> Cu<2+> and Zn<2+>; and 0.001<=x<=0.005 or 0.7<=x<=0.9) having a BET specific surface of 1-20m<2>/g and a mean particle diameter (determined by the microtracking method) of 0.2-4.0mum, if necessary, having a surface treated with 0.1-10 pts.wt. of at least one surface treating agent selected from a higher fatty acid, an anionic surfactant, a phosphoric ester, a silane, titanate or aluminum coupling agent, and an ester of a polyhydric alcohol with a fatty acid; and if necessary, 0.01-10 pts.wt. of at least one additive selected from carbonaceous material powder, red phosphorus, acrylic fibers and nickel oxide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel composite metal hydroxide, and a resin and / or a resin capable of exhibiting excellent flame retardancy and acid resistance by compounding the composite metal hydroxide with a resin and / or rubber. Further, it relates to a flame retardant for rubber, and a flame retardant resin and / or a rubber composition containing the flame retardant. More specifically, there is no foaming trouble of the molded product caused by decomposition of the flame retardant at the processing temperature of the resins and / or rubbers, and excellent flame retardancy and acid resistance can be imparted to the resins and / or rubbers. The present invention relates to a flame retardant containing a non-halogen composite metal hydroxide as an active ingredient, and a flame retardant resin and / or a rubber composition containing the flame retardant.

[0002]

2. Description of the Related Art The requirements for flame retardancy of resins and rubbers have been increasing year by year and have become more severe. In order to meet such a demand for flame retardancy, conventionally, a flame retardant in which an organic halide and antimony trioxide are used in combination has been proposed and implemented. However, this flame retardant partly decomposes during processing to generate halogen gas, which corrodes the processing and molding machines, is toxic to workers, and adversely affects the heat resistance and weather resistance of resin and rubber. However, there is a problem that a large amount of smoke containing toxic gas is generated during combustion.

Therefore, the demand for non-halogen flame retardants that do not have the above problems has increased, and attention has been paid to aluminum hydroxide, magnesium hydroxide and the like. However, aluminum hydroxide starts to dehydrate at about 190 ° C and causes foaming troubles in the molded product, so the molding temperature is set to 190 ° C.
Since it is necessary to keep the temperature below 0 ° C, there is a problem that types of resins and rubbers that can be applied 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, since the present inventors have developed a new method for synthesizing magnesium hydroxide that enables the production of well-developed crystals, it becomes possible to obtain a good molded product, which is also used for communication cables, ships, etc. Came to be.

[0004]

However, it has become clear that the above magnesium hydroxide still has problems to be solved. The first is that a high level of flame retardancy cannot be exhibited unless a relatively large amount is blended with the resin and / or rubber. For example, when blended with polypropylene, in order to pass VO (highest flame retardant level) with a thickness of 1/8 inch to 1/16 inch in UL-94 flame retardancy standard 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, etc. among the original physical properties of the resin.

The second problem is poor acid resistance.
For example, if a communication cable, power cable, etc., in which polyethylene is mixed with magnesium hydroxide, is in contact with water for a long time,
Due to carbonic acid contained in water, magnesium hydroxide is gradually dissolved and transferred to the surface of the molded body, and magnesium carbonate is precipitated to cause a phenomenon that the surface is whitened. In the long term, there arises a problem that the flame retardancy is lowered and the electric insulation is lowered by the amount of magnesium hydroxide which is dissolved and disappeared.

An object of the present invention is to solve the above-mentioned problems and to 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 present invention provides a novel composite metal hydroxide, a flame retardant containing the composite metal hydroxide as an active ingredient, and a flame retardant resin and / or rubber composition containing the flame retardant. For the purpose of provision.

[0008]

The present invention provides the following formula (1) Mg _1-x M ²⁺ _x (OH) ₂ (1) (wherein M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu
^At least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , where x is 0.001 ≦ x ≦ 0.00
5 or a number in the range of 0.7 ≦ x ≦ 0.9), and a flame retardant for resin and / or rubber containing the composite metal hydroxide as an active ingredient.

The present invention further provides a flame-retardant resin and / or rubber composition containing 20 to 250 parts by weight of the above flame retardant with respect to 100 parts by weight of the resin and / or rubber.

The inventor of the present invention has conducted research to provide 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 problem was caused by the physical properties peculiar to magnesium hydroxide, and as far as magnesium hydroxide was used, it was thought that the essential solution of the above problem was difficult, and further research was conducted.

As a result, the present inventor has previously found that the following formula (3) Mg _1-x M ²⁺ _x (OH) ₂ (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, and x represents a number in the range of 0.005 <x <0.7). It was found that a flame retardant and a flame retardant resin and / or a rubber composition containing the flame retardant capable of solving the above-mentioned problems are obtained (Japanese Patent Application No. 3-36816).

As a result of further research by the inventor, even in a range exceeding the range of x defined by the equation (3),
It was discovered that it is effective as a flame retardant. x is 0.
When it is 005 or less, the characteristic that the decomposition temperature is lower than that of magnesium hydroxide which is a characteristic of the composite metal hydroxide of the present invention becomes poor, and the flame retardancy is hardly improved as compared with magnesium hydroxide. I thought in the previous invention.
However, in reality, x is 0.1 due to the carbonization action of M ²⁺ .
It was discovered that even at 005 or less, the flame retardancy is superior to that of magnesium hydroxide.

Further, if x is 0.7 or more, it is considered that there is a risk of foaming at a processing temperature of about 200 ° C. or above, approaching the decomposition temperature of aluminum hydroxide. However, as a result of further research, the temperature of 200 ° C is about 10 ° C higher than the decomposition temperature of aluminum hydroxide, and
As the crystal grows larger, the decomposition temperature increases and
It has been found that the workability is also improved, and as a result, the foamability is improved. As a result, in the formula (1), x has a heat resistance equal to or higher than aluminum hydroxide up to about 0.9,
It was also found to exhibit foaming resistance.

Therefore, in the present invention, the region represented by M ²⁺ in the formula (1) having a small amount of transition metal, that is, the range of x is 0.001.
Even in the case of ≤x≤0.005, the flame retardancy is superior to that of magnesium hydroxide. Particularly in nickel, the carbonization catalyst promoting action is remarkable. When forming a solid solution with magnesium hydroxide in the total composition such as nickel or cobalt, water often used as a flame retardant even in a region with a large x, that is, 0.7 ≦ x ≦ 0.9. While maintaining heat resistance and foaming resistance equal to or higher than that of aluminum oxide, the endothermic dehydration decomposition temperature of the flame retardant of the formula (1) is brought close to the exothermic decomposition temperature of the resin or rubber to efficiently perform the resin or rubber. Has the effect of suppressing the ignition of. Furthermore, M in equation (1)
^It exhibits excellent flame retardancy due to the action of ²⁺ to promote the carbonization catalyst of resin or rubber. Among M ²⁺ , nickel and cobalt, in particular, remarkably improve the acid resistance, which is a drawback of magnesium hydroxide, and as a result, the water resistance and electric insulation are remarkably improved.

The composite metal hydroxide of the formula (1) has a crystallite size of 0.2 to 4 μm, preferably 0.4 to 2 μm, particularly preferably 0.6 to 1 μm, and has secondary aggregation. With little or no particles, that is, an average secondary particle diameter of 0.2 to
4 μm, preferably 0.4 to 2 μm, particularly preferably 0.1 μm.
6 to 1 μm and BET specific surface area of 1 to ²⁰ m ^2.
/ G, preferably 3 to 15 m ² / g, particularly preferably 5
It is preferably from 10 m ² / g.

The range of the above characteristic values of the composite metal hydroxide is
It is a preferable range for maintaining various properties such as compatibility with resin and / or rubber, dispersibility, moldability or processability, appearance of a molded product, mechanical strength and flame retardancy within a suitable range.

In the composite metal hydroxide of the formula (1), M
²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ and Z
When at least one divalent metal ion selected from the group consisting of n ²⁺ and M ²⁺ consists of a plurality of divalent metal ions, x represents the sum of each. Among the above divalent metal ions, Co ²⁺ , Ni ²⁺ and Zn ²⁺ are most preferably used. Co ²⁺ and Ni ²⁺ form a solid solution in the entire range of x, and among them, Ni ²⁺ has a particularly remarkable effect in improving acid resistance, and also has an excellent effect in catalyzing the carbonization of resin or rubber. Indicates. Zn ²⁺ has the effect of improving the whiteness and lowering the decomposition temperature with the addition of a smaller amount.

Therefore, in the composite metal hydroxide of formula (1),
Compound metal hydroxide of formula (2) Mg _1-x (Ni ²⁺ and / or Zn ²⁺ ) _x (OH) ₂ (2) (wherein x represents the same meaning as x in formula (1)) The thing can be illustrated as a preferable example.

The complex metal hydroxide of the present invention can be used as it is as a flame retardant, and further, for example, higher fatty acid, anionic surfactant, phosphate ester, coupling agent (silane type, titanate type, aluminum type). ) And a polyhydric alcohol and an ester of a fatty acid, and may be surface-treated with at least one surface-treating agent selected from the group consisting of esters.

The following are examples of those preferably used as the surface treatment agent. 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 above higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl call; polyethylene glycol ether Sulfate ester salt, amide bond sulfate ester salt, ester bond sulfate ester salt, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkyl allyl sulfonate, ester bond alkyl allyl sulfonate, amide Anionic surfactants such as bound alkylallyl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc., or a mixture of both, and their acid forms or alkali metal salts or salts thereof. 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; isopropyltriisostearoyl 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 polyhydric alcohols and fatty acids such as glycerin monostearate and glycerin monooleate.

The surface coating treatment of the composite metal hydroxide of the formula (1) with the surface treatment agent can be carried out by a wet or dry method known per se. For example, as a wet method, the surface treatment agent may be added to the slurry of the composite metal hydroxide in the form of a liquid or an emulsion, and mechanically sufficiently mixed at a temperature of up to about 100 ° C. As the dry method, the powder of the composite metal hydroxide is mixed with a mixer such as a Henschel mixer to sufficiently stir the surface treatment agent in a liquid form, an emulsion form,
It may be added in a solid state and mixed sufficiently with or without heating. The addition amount of the surface treatment agent can be appropriately selected, but is about 0.1 to about 10% by weight based on the weight of the composite metal hydroxide.
Is preferred.

After the surface treatment, if necessary, for example, washing, dehydration, granulation, drying, pulverization, classification, etc. are 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, about 1 equivalent or less, preferably 0.95 equivalents or less of alkali is preferably added at about 40 ° C. or less with respect to the total of Mg and M ^2+. It can be produced by a coprecipitation method in which the mixture is added with stirring to cause precipitation. As another method, it can be produced by mixing MgO and / or Mg (OH) ₂ and an aqueous solution containing M ²⁺ ions and reacting them. As another method, a sol-gel method by hydrolysis of Mg and M ²⁺ alcoholate can be used.

The composite metal hydroxide produced by the above method further grows crystals and further reduces secondary agglomeration, so that the reaction mother liquor is allowed to coexist, or CaCl ₂ , CaBr ₂ , MgCl ₂ , MgBr ₂ , N
It is more preferable to add a salt such as aCl or KCl as a crystal growth promoter and perform hydrothermal treatment at about 110 ° C. to 250 ° C. for about 1 hour or longer using an autoclave.

Mg used to form complex metal hydroxides
Examples of the ion feed material include alcoholates such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium acetate, magnesium ethoxide, and magnesium propoxide, bittern, seawater, and underground brine. Examples of M ²⁺ ion feed materials include, for example, Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ and Zn.
Chloride, bromide, iodide, fluoride, nitrate, formate, acetate of divalent metal ion selected from the group consisting of ²⁺
Examples thereof include alcoholates such as propioxide, ethoxide, propoxide and isopropoxide.

Examples of the alkali used for forming the composite metal hydroxide include sodium hydroxide, potassium hydroxide, calcium hydroxide (natural product or synthetic product), aqueous ammonia, ammonia gas and the like.

It is preferable that all the above raw materials have higher purity. In particular, the content concentration 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 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-olefin, polybutene-1, polystyrene, styrene and acrylonitrile, copolymer of ethylene and propylene diene rubber or butadiene, vinyl acetate, polyacrylate, polymethacrylate, polyurethane, polyester , Thermoplastic resins such as polyether, polyamide, thermosetting resins such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, alkyd resin, EPD
Examples thereof include M, SBR, NBR, butyl rubber, isoprene rubber, and chlorosulfonated polyethylene, 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 the rubber is the kind of the resin and / or the rubber, the kind of the composite metal hydroxide of the formula (1), etc. The amount of the compound (1) mixed metal hydroxide is about 20 parts surface-treated or untreated with respect to 100 parts by weight of the resin and / or rubber.
To about 250 parts by weight, preferably about 30 to about 200 parts by weight. If the compounded amount of the composite metal hydroxide of the formula (1) is less than the above range, the flame retardancy becomes insufficient, and conversely, if it is too large, for example, the tensile strength, Izod impact strength, etc. are lowered or the acid resistance is lowered. Since there is a risk of deteriorating the composition and other disadvantages, it is preferable to properly select and mix the above-mentioned compounding amount range.

There is no particular restriction 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 the two can be adopted. 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 per se can be adopted depending on the type of resin and / or 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 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 flame retardant aid, resin and / or rubber 10
About 0.01 to about 10 parts by weight is preferably employed with respect to 0 parts by weight.

Further, as other additives, zinc behenate, magnesium behenate, zinc stearate, calcium stearate, magnesium stearate, lead stearate, aluminum stearate and the like as a lubricant and water resistance, acid resistance (whitening resistance) improver May be added if necessary. The amount of such a lubricant blended is preferably about 0.1 to about 10 parts by weight per 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, UV inhibitors, antistatic agents, pigments, foaming agents, plasticizers, fillers, reinforcing agents, organic halogen flame retardants, crosslinking agents and the like. Also, in magnesium hydroxide, the complex metal hydroxide of the formula (1), x
It is also possible to add a non-halogen inorganic flame retardant such as a composite metal hydroxide or aluminum hydroxide having a ratio of 0.005 <x <0.7.

The present invention will be described in more detail based on the following examples. Example 1 Ionic bitter soup (MgCl ₂ = 2.9 mol / liter, CaC
10 liters (l ₂ = 0.8 mol / liter) were placed in a 30 liter stainless steel tank equipped with a stirrer, 0.13 mol of nickel nitrate was added and dissolved, and the temperature was raised to 20 ° C. While stirring this solution with a chemi-stirrer, 2.0 mol / liter of synthetic slaked lime (Ca (OH) ₂ ) at 20 ° C. (synthesized by coprecipitation reaction of reagent-grade calcium chloride and sodium hydroxide) was mixed with Mg. 13.1 liter, which corresponds to about 90% of the total equivalent of Ni, is added in about 2 minutes, and stirring is further performed for 20 minutes.
The reaction was continued for a minute. The reaction was allowed to settle and the precipitate was concentrated to remove the mother liquor to 18 liters, which was brought to a volume of 25
It was put in a liter autoclave and hydrothermally treated at 160 ° C. for 3 hours. A part of the treated product was filtered under reduced pressure, washed with water, dehydrated and then dried.

The dried product was pulverized and subjected to chemical analysis, BET specific surface area measurement, average secondary particle size measurement, powder X-ray diffraction, differential thermal analysis (DTA) -thermogravimetric analysis (TGA).
The BET specific surface area was measured by a nitrogen adsorption method, and the average secondary particle diameter was measured by a microtrack method after ultrasonically dispersing the sample powder in a 0.2% sodium hexametaphosphate aqueous solution. Then, the DTA-TGA was measured in a nitrogen atmosphere. .. The chemical composition of the obtained dried product was Mg _0.996 Ni _0.004 (OH) ₂
Met. The measurement results are shown in Table 1.

Example 2 In Example 1, 0.05 was added to 10 liters of ionic bitter juice.
A dried product was obtained in the same manner as in Example 1 except that a solution in which mol of nickel chloride was dissolved was used. The chemical composition of the obtained dried product was Mg _0.998 Ni _0.002 (OH) ₂ .
The measurement results are shown in Table 1.

Example 3 A dried product was obtained in the same manner as in Example 1 except that a solution of 0.1 mol of cobalt chloride in 10 liters of ionic bitter juice was used. The chemical composition of the obtained dried product was Mg _0.996 Co _0.004 (OH) ₂ . The measurement results are shown in Table 1.

Example 4 In Example 1, 10 liters of ionic bitter juice was added to 0.05.
A dried product was obtained in the same manner as in Example 1 except that a solution in which mol of nickel chloride and 0.05 mol of zinc nitrate were dissolved was used. The chemical composition of the obtained dried product is Mg _0.996 Ni
_{It was 0.002} Zn _0.002 (OH) ₂ . The measurement results are shown in Table 1.

Example 5 10 liters of a mixed aqueous solution of 0.72 mol / liter magnesium chloride and 1.5 mol / liter nickel chloride was temperature-controlled at 15 ° C. and placed in a stainless steel cylindrical reaction tank having a capacity of 20 liters. I put it in. While stirring this solution, 2.5 mol / liter of synthetic slaked lime (8.0 liter, which corresponds to about 90% of the total equivalent of Mg and Ni) was adjusted to about 15 ° C., and then added in about 3 minutes. Stirring was continued for 20 minutes to react. 1 as a crystal growth aid in the reaction solution
After adding 6 mol of calcium chloride and dissolving, the volume is 25
It was put in a liter autoclave and hydrothermally treated at 180 ° C. for 3 hours. After that, it was filtered under reduced pressure and washed with water, and then a part thereof was collected, dried and pulverized. The chemical composition of the obtained pulverized product is M
It was _{g 0.25 Ni 0.75 (OH) 2} . The measurement results are shown in Table 1.

Example 6 In Example 5, 0.47 mol / liter of magnesium chloride and 1.74 were used instead of 10 liter of the mixed aqueous solution.
A pulverized product was obtained in the same manner as in Example 5 except that a mixed aqueous solution of mol / liter of nickel chloride and 0.02 mol / liter of zinc nitrate was used. The chemical composition of the obtained pulverized product was Mg _0.12 Ni _0.87 Zn _0.01 (OH) ₂ .
The measurement results are shown in Table 1.

Comparative Examples 1-2 Commercially available aluminum hydroxide (Comparative Example 1, Al (O
H) ₃ ), magnesium hydroxide (Comparative Example 2, Mg (O
H) ₂ ) was used to perform the same measurement as in Example 1.
The measurement results are shown in Table 1.

Table 1 Example BET average secondary powder X-ray dehydration start dehydration peak (M ² / g) particle diameter diffraction pattern Temperature Temperature Example 1 6 0.82 A 339 429 Example 2 6 0.86 A 340 430 Example 3 7 0.7 A 339 428 Example 4 8 0.66 A 335 428 Example 5 7 0.76 A 235 338 Example 6 14 0.51 A 222 324 Comparative Example 1 10 1.28-190 320 320 Comparative Example 2 6 0.87 Mg (OH) ₂ 340 430 Note: unit; The average secondary particle diameter (μm), dehydration start temperature and peak temperature (° C.) A; A diffraction pattern similar to Mg (OH) ₂ is shown.

Examples 7 to 12 The water-washed reaction products obtained in Examples 1 to 6 were emulsified in water, the temperature was adjusted to about 70 ° C., and then the previously-dissolved aqueous sodium oleate solution was used. (About 70 ° C.) was added to the reaction product as oleic acid in an amount of 1.5% by weight,
Further, the surface treatment was carried out with sufficient stirring. Dewater the surface-treated product,
It was washed with water, granulated and dried.

0.2 parts by weight of antioxidant (0.1 parts by weight of Irganox) per 100 parts by weight of high impact polypropylene.
1010 and 0.1 part by weight of Weston 626) and the metal hydroxide in the compounding parts shown in Table 2 were uniformly mixed and then melt-kneaded at about 220 ° C. using a twin-screw extruder to obtain composite pellets. .. After vacuum drying the pellets at 120 ° C. for 2 hours,
A test piece was prepared by injection molding at about 220 ° C. using an injection molding machine. Table 2 shows the evaluation results of injection moldability, flammability, and mechanical strength.

Comparative Examples 3 to 4 Test pieces were prepared in the same manner as in Example 7 except that the metal hydroxide shown in Table 2 was used in place of the composite metal hydroxide of the present invention. And evaluated. The evaluation results are shown in Table 2.

Table 2 Example Resin Flame Retardant Injection Moldability Combustibility Tensile Izod Example Type Mixing amount Appearance of molded product Breaking strength Impact strength 7 PP 1 190 AV-0 186 6.1 8 PP 2 190 AV-0 189 6.5 9 PP 3 190 A V-0 187 5.8 10 PP 4 190 A V-0 185 5 .5 11 PP 5 190 A V-0 192 5.0 12 PP 6 1 A V-0 191 6.0 1 179 Comparative Example 3 PP 1 190 D Non-standard − − 4 PP 2 190 A V-2 172 4 4. 6

Note: PP indicates polypropylene. Types of flame retardants; the numbers in the examples indicate the flame retardants of Examples 1 to 6, and the numbers in the comparative examples indicate the flame retardants of Comparative Examples 1 and 2, respectively. The blending amount is parts by weight based on 100 parts by weight of the resin. Injection moldability and appearance of molded product: A: Both injection moldability and appearance of molded product are good, B: Injection moldability is somewhat poor, flash pattern is on the appearance of molded product, D: Foam is strongly unmoldable, flammability is UL-94. measured at 1/16 inch thickness by standard, unit: tensile breaking strength ^{(kg · f / cm 2)} , Izod impact strength (kg · cm / cm).

Examples 12 to 13 and Comparative Example 5 100 parts by weight of ethylene propylene diene rubber (DPDM) were washed with water and washed with the composite metal hydroxide of the present invention obtained in Examples 1 and 5. After the emulsification, 1% by weight of isopropyltriisostearoyl titanate was added to perform surface treatment. The commercially available magnesium hydroxide of Comparative Example 2 was also surface-treated in the same manner as above. These are added in the amounts shown in Table 3, and the following other additives: zinc oxide 5 parts by weight vulcanization accelerator (tetramethylthiuram disulfide) 1.5 parts by weight sulfur 0.5 parts by weight stearic acid 1.0 parts by weight. After mixing with the above blending amount, 1 using an open roll
Melt kneading was carried out at 50 ° C. The obtained kneaded product is vulcanized by a press molding machine at 160 ° C. for 30 minutes to form a sheet,
A test piece was created from this sheet. The evaluation results are shown in Table 3.

Table 3 Flame Retardant Molded Product Combustibility Tensile Fracture Type Compounding Content Appearance Strength Elongation Example 12 1 120 Good V-0 105 446 Example 13 5 2 Ratio 2 118 Good V-0 111 434 Comparative Example 5 Ratio 2 120 Good Nonstandard 84 410 Note: Types of flame retardants; 1 and 5 are respectively The flame retardants of Examples 1 and 5 and the ratio 2 indicate the flame retardant of Comparative Example 2. Unit: tensile breaking strength (kg · f / cm ² ), tensile breaking elongation (%)

[0050]

According to the present invention, there are provided a flame retardant having excellent flame retardancy and acid resistance, and a flame retardant resin and / or rubber composition containing the flame retardant. Further, according to the present invention, a novel composite metal hydroxide, a flame retardant containing the composite metal hydroxide as an active ingredient, and a flame retardant resin and / or rubber composition containing the flame retardant are provided. To be done.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C01G 53/00 A 8516-4G C08K 9/04 KCP 7167-4J C08L 101/00

Claims (8)

[Claims] 1. The following formula (1) Mg _1-x M ²⁺ _x (OH) ₂ (1) with respect to 100 parts by weight of resin and / or rubber (wherein M ²⁺ is Mn ²⁺ and Fe ^{2 +} , Co ²⁺ , Ni ²⁺ , Cu
^At least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , where x is 0.001 ≦ x ≦ 0.00
5 or 0.7 ≦ x ≦ 0.9), which is a flame-retardant resin and / or rubber composition containing 20 to 250 parts by weight of a composite metal hydroxide. 2. A composite metal hydroxide of formula (1) has the following formula (2): Mg _1-x (Ni ²⁺ and / or Zn ²⁺ ) _x (OH) ₂ (2) The flame-retardant resin and / or rubber composition according to claim 1, which is a composite metal hydroxide represented by the formula (1). 3. The complex metal hydroxide of formula (1) comprises a higher fatty acid, an anionic surfactant, a phosphoric ester, a silane, a titanate and an aluminum coupling agent,
The flame-retardant 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 esters of polyhydric alcohols and fatty acids. 4. The composite metal hydroxide of the formula (1) has a BET specific surface area of 1 to ²⁰ m ² / g and an average secondary particle diameter measured by the Microtrac method of 0.2 to 4.0 μm. The flame-retardant resin and / or rubber composition according to claim 1, which comprises: 5. The composition according to claim 1, further comprising at least one selected from the group consisting of carbon powder, red phosphorus, acrylic fibers and nickel oxide.
The flame-retardant resin and / or rubber composition described. 6. The composition according to claim 1, wherein the total amount of the composite metal hydroxide according to claim 1 and another metal hydroxide is 2%.
The flame-retardant resin and / or rubber composition according to claim 1, which comprises 0 to 250 parts by weight. 7. The following formula (1) Mg _1-x M ²⁺ _x (OH) ₂ (1) (wherein M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu
^At least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , where x is 0.001 ≦ x ≦ 0.00
5 or a resin having a composite metal hydroxide of 0.7 ≦ x ≦ 0.9) as an active ingredient, and / or
Or flame retardant for rubber. 8. The following formula (1) Mg _1-x M ²⁺ _x (OH) ₂ (1) (wherein M ²⁺ is Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu
^At least one divalent metal ion selected from the group consisting of ²⁺ and Zn ²⁺ , where x is 0.001 ≦ x ≦ 0.00
5 or a composite metal hydroxide having a number in the range of 0.7 ≦ x ≦ 0.9).