JP3272110B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition. More specifically, M is added to resin and / or rubber.
The present invention relates to a resin and / or rubber composition excellent in flame retardancy, in which an organic acid salt of a metal such as n ²⁺ , Fe ²⁺ , and Co ²⁺ is compounded in combination with a metal hydroxide.

[0002]

2. Description of the Related Art The demand for flame retardant resins and rubbers has been increasing year by year. In addition, there is an increasing social demand that flame retardation be performed in a safe and non-toxic manner.
Even under such circumstances, most of the flame retardants are a combination of an organic halide and antimony trioxide. These flame retardants are partially decomposed during processing and molding to generate halogen gas, not only corrode equipment, but also toxic to workers. In addition, it produces large amounts of toxic gas and smoke when combusted, which has a serious impact on life. There is also a danger of corroding peripheral equipment and losing their functions. Further, when products using these flame retardants are burned, extremely toxic substances such as dioxin may be generated.

[0003] In recent years, metal hydroxides, especially magnesium hydroxide, have attracted attention as non-toxic and safe flame retardants. However, in order for the metal hydroxide to exhibit flame retardancy, it is necessary to incorporate a large amount of the metal hydroxide. Large amounts of compounding significantly impair some of the physical properties inherent in resins and rubbers. For this reason, the field of application of metal hydroxide does not expand, and it is stagnant.

[0004]

If an additive capable of remarkably improving the flame retardancy of a metal hydroxide can be developed, the above-mentioned problems of the metal hydroxide can be solved. Addition of a small amount that does not adversely affect the physical properties of resins and rubbers acts synergistically with metal hydroxides, and if a substance that can significantly improve flame retardancy can be developed, the amount of metal hydroxides can be significantly reduced it can. As a result, flame retardancy can be achieved without substantially impairing the inherent properties of the resin and rubber. An object of the present invention is to provide a harmless and safe flame-retardant resin composition by developing an additive that solves the above-mentioned problem of the metal hydroxide.

[0005]

SUMMARY OF THE INVENTION The present invention provides a resin and / or resin.
Or 100 parts by weight of rubber and (A) Formula (1) Mg _1-x M ²⁺ _x (OH) ₂ (1) wherein M ²⁺ is Ca ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Cu
^At least one of divalent metal ions consisting of ²⁺ and Zn ²⁺
Indicates species, x is a solid solution 2 0-200 parts by weight of the number of ranges of 0.005 <x <0.7], ( B) Mn 2+,
A flame retardant resin composition comprising 0.1 to 50 parts by weight of an organic acid salt of at least one metal selected from Fe ²⁺ , Co ²⁺ , Cu ²⁺ and Cr ³⁺ I will provide a.

The present inventors have sought to find a method that can advantageously solve the problem that the metal hydroxide cannot be flame-retardant unless it is filled with resin and / or rubber in a large amount, although it is safe. Was. As a result, they concluded that it would be difficult to overcome the above problems without changing the combustion mechanism of the resin and rubber. The conversion of the combustion mechanism refers to a so-called oxidation in which, in addition to the endothermic effect of the metal hydroxide, catalytically acts on the resin and / or the rubber, a dehydrogenation reaction and a subsequent oxidation reaction of this hydrogen produce H ₂ O. This is a conversion to a mechanism in which the dehydrogenation reaction is predominantly performed to carbonize resin or rubber to stop combustion. If this mechanism works, only the hydrogen of the resin or rubber, in other words, the hydrocarbon of the hydrocarbon, is burned (oxidized), and the remaining carbon is not burned. Therefore, the metal hydroxide only needs to offset the heat of combustion of hydrogen by its endothermic effect.

[0007] Based on the above idea, it exhibits an oxidative dehydrogenation catalytic action, and does not adversely affect the mechanical strength of the resin or rubber when added to the resin or rubber, and has excellent dispersion and compatibility with the resin or rubber. Compounds were searched. as a result,
They have discovered that an organic acid salt of a metal selected from Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Cu ²⁺ and Cr ³⁺ is a compound having the above-mentioned properties. By using these metal organic acid salts in combination with a small amount of the above-mentioned metal hydroxide solid solution , the flame retardancy is significantly improved, and as a result, the compounding amount of the metal hydroxide solid solution can be reduced. It became clear. This is the metal hydroxide in the resin or rubber
Thus, it is possible to prevent the physical properties inherent in resins and rubbers from lowering to an unacceptable level due to a large amount of solid solution . Further, it has become possible to provide a novel resin and / or rubber composition having a balance between workability and mechanical strength as well as flame retardancy.

The organic acid of the metal organic acid salt used in the present invention includes carboxylic acid, sulfonic acid, sulfinic acid, phenol, enol, thiophenol, imide, oxime, aromatic sulfonamide, primary and secondary. Nitro compounds are exemplified. Among them, fatty acids having a relatively large number of carbon atoms are preferably used. Examples of such fatty acids include caproic acid, undecylic acid, lauric acid, stearic acid, oleic acid, sebacic acid and the like. Metals include Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Cu ²⁺ and Cr
³⁺ , and particularly preferred are Mn ²⁺ , Fe ²⁺ and Co
²⁺ . However, the valence of manganese, iron, and cobalt may include partially trivalent ones such as Mn ³⁺ , Fe ^3+, and Co ³⁺ . The amount of the metal organic acid salt is about 0.1 to 5 per 100 parts by weight of the resin and / or rubber.
0 parts by weight, preferably about 0.1 to 10 parts by weight.

[0009] metal hydroxide used in the present invention are developed Mg (OH) ₂ based solid solution of the present onset <br/> inventor. This solid solution has the formula (1) Mg _1-x M ²⁺ _x (OH) ₂ (1) wherein M ²⁺ is Ca ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Cu
^At least one of divalent metal ions consisting of ²⁺ and Zn ²⁺
And x represents a number in the range of 0.005 <x <0.7]. This metal hydroxide is required to have good dispersibility in resin and rubber. Physical properties to satisfy such requirements include a BET specific surface area of about 1
１５15 m ² / g, preferably about 4 to 10 m ² / g, and the average secondary particle diameter is about 0.4 to 2.0 μm, preferably about 0.5 to 1.0 μm. .

[0010] To increase the compatibility with the resin and rubber metal hydroxide Matako are higher fatty acids is a conventional means, anionic surfactants, phosphoric acid esters, silanes,
The metal hydroxide may be surface-treated with one or more surface treatment agents conventionally used when adding to resins or rubbers such as titanates and aluminum-based coupling agents and fatty acid esters of polyhydric alcohols. . Examples of the surface treatment agent preferably used are as follows. Stearic acid, erucic acid, palmitic acid,
Lauric acid, higher fatty acids having 10 or more carbon atoms such as behenic acid; the alkali metal salts of higher fatty acids; stearyl alcohol, sulfate ester salts of higher alcohols such as oleyl alcohol; sulfate of polyethylene glycol ether, amide bond sulfate Ester salt, ester-linked sulfate, ester-linked sulfonate, amide-linked sulfonate, ether-linked sulfonate, ether-linked alkylallyl sulfonate, ester-linked alkylallyl sulfonate, amide-linked alkylallyl sulfonate, etc. Anionic surfactants; orthophosphoric acid and mono- or diesters such as oleyl alcohol and stearyl alcohol or a mixture of both, and their acid forms or phosphoric esters such as alkali metal salts or amine salts; vinyl Tokishishiran, vinyl - tris (2
-Methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- Silane coupling agents such as mercaptopropyltrimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, isopropyl tridecylbenzenesulfonyl titanate; Titanate-based coupling agents; aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate; glycerin monostea Over DOO, esters of polyhydric alcohols and fatty acids such as glycerol monooleate. The amount of the metal hydroxide is about 2.0 to 200 parts by weight, preferably about 50 to 150 parts by weight, per 100 parts by weight of the resin and / or rubber.
Parts by weight.

The following are examples of the resin and rubber used in the present invention. Polyethylene, copolymers of ethylene and other α-olefins, ethylene and vinyl acetate,
Ethyl acrylate or methyl acrylate copolymer, polypropylene, copolymer of propylene with other α-olefin, polybutene-1,4-methylpentene
1, polystyrene, copolymer of styrene and acrylonitrile, copolymer of styrene and acrylonitrile and butadiene, copolymer of ethylene and propylene diene rubber or butadiene, polyvinyl acetate, polyacrylate, polymethacrylate, polyurethane, polyester Thermoplastic resins such as polyether, polyamide, polyvinyl chloride, chlorinated polyethylene, phenolic resins,
Thermosetting resins such as melamine resin, epoxy resin, unsaturated polyester resin, alkyd resin, EPDM, SB
Rubbers such as R, NBR, butyl rubber, isoprene rubber, and chlorosulfonated polyethylene can be exemplified, but not limited thereto.

The mixing and kneading of the resin and / or rubber with the metal organic acid salt and the metal hydroxide are not particularly limited, and any 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 limitation on the molding method, and any known molding means can be appropriately used according to the type of resin and / or rubber, the type of a desired molded product, and the like.
For example, injection 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 contain other conventional additives. Examples of such additives include, for example, antioxidants, ultraviolet inhibitors, antistatic agents, pigments, foaming agents, plasticizers, fillers, reinforcing agents, crosslinking agents, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. The sodium salt ratio Comparative Examples 1-5 organic acid, this with chloride equimolar metal reacted under stirring in a water medium, the resulting precipitate filtered, washed with water and dried in vacuo, The organic acid salts of metals shown in Table 1 were obtained. The organic acid salt of the metal shown in Table 1 and a BET specific surface area of 6 m ² / g, a microtrack method (laser diffraction method)
Mg (OH) ₂ having an average secondary particle system of 0.74 μm and a surface treatment with 1% by weight of oleic acid,
Impact-resistant polypropylene (copolymer with ethylene) 10
0 parts by weight and 0.2 parts by weight of antioxidant (0.1 parts by weight of Irganox 1010, 0.1 parts by weight of Weston 626). Table 1 shows the types and amounts of metal organic acid salts and metal hydroxides.

After mixing, using a single screw extruder, about 230 ℃
The mixture was melt-kneaded with water, cooled with water, and then pelletized. The pellet was vacuum-dried at 120 ° C. for 2 hours, and then injection-molded at about 230 ° C. using an injection molding machine to prepare a test piece. For this test piece, the flammability was measured according to the UL-94 method, the tensile strength and elongation were measured according to JIS K-7113, and the notched Izod impact strength was measured according to JIS K-7110. Table 2 shows the measurement results.

Example 1 In Comparative Example 1, BET was used instead of Mg (OH) _2.
Specific surface area is 8 m ² / g, average secondary particle diameter is 0.62 μm
And a solid solution Mg _0.7 Ni _0.3 (OH) ₂ surface-treated with 1% by weight of oleic acid, and Mn decanoate as a metal organic acid salt, and the mixing amounts thereof are shown in Table 1. A test piece was prepared in the same manner as in Comparative Example 1. The physical properties of this test piece were measured in the same manner as in Comparative Example 1. Table 2 shows the measurement results.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

According to the present invention , a compound represented by the formula
(1) A harmless and safe flame-retardant resin that does not impair the intrinsic properties of the resin and / or rubber by drastically reducing the amount of Mg _1-x M ²⁺ _x (OH) ₂ A composition is provided.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08K 5:09) C08K 5:09) (56) References JP-A-3-41132 (JP, A) JP-A-1-307107 (JP, A) JP-A-53-12943 (JP, A) JP-A-4-359941 (JP, A) JP-A-6-256582 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (3)

(57) [Claims] 1. 100 parts by weight of resin and / or rubber and (A) Formula (1) Mg _1-x M ²⁺ _x (OH) ₂ (1) wherein M ²⁺ is Ca ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Cu
^At least one of divalent metal ions consisting of ²⁺ and Zn ²⁺
Indicates species, x is a solid solution 2 0-200 parts by weight of the number of ranges of 0.005 <x <0.7], ( B) Mn 2+,
A flame retardant resin composition comprising 0.1 to 50 parts by weight of an organic acid salt of at least one metal selected from Fe ²⁺ , Co ²⁺ , Cu ²⁺ and Cr ³⁺ . 2. The flame-retardant material according to claim 1, wherein the metal organic acid salt is an organic acid salt of at least one metal selected from Mn ²⁺ , Fe ²⁺ and Co ^2+. Resin composition. (3)Mg of the formula (1) _1-x M ²⁺ _x (OH)
_Two Has a BET specific surface area of 1 to 10 m^Two/ G, average secondary particles
A diameter is 0.5-2.0 micrometers.
2. The flame-retardant resin composition according to 1.