JP3452476B2 - Flame retardant resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition, and in particular, a flame-retardant resin composition suitable as various extrusion-molded material materials such as electric wire insulating materials and sheath materials, and injection-molded material materials. Regarding

[0002]

2. Description of the Related Art Conventionally, flame-retardant cables have been used for flame prevention in wiring of various plants and buildings.
This flame-retardant cable is constructed by coating a conductor or an insulator with a flame-retardant resin composition, and various flame-retardant resin compositions have been developed. For example, halogen-containing polymers such as polyvinyl chloride, chloroprene rubber, and fluororesins are widely used as flame-retardant resin compositions. However, these halogen-containing polymers give flame retardancy to the cable by generating a hydrogen halide gas such as hydrogen chloride or hydrogen fluoride at the time of combustion to block the air, and have excellent flame retardancy. However, these gases are toxic and corrosive to metals.

Therefore, in recent years, in consideration of such industrial hygiene, a flame retardant composed of a polymer containing no halogen in the skeleton such as polyethylene and a metal hydroxide such as magnesium hydroxide or aluminum hydroxide, Further, a so-called non-halogen flame-retardant resin composition containing a flame-retardant aid such as a molybdenum compound such as calcium molybdate has become the mainstream. For example, JP-A-59-202243 discloses a flame-retardant polyolefin resin composition obtained by blending a polyolefin resin with a hydrous inorganic substance such as aluminum hydroxide, magnesium hydroxide or hydrotalcite and a molybdenum compound. Is disclosed. Further, in JP-A-2-150436, at least one powder selected from the group consisting of a mixed powder containing huntite and hydromagnesite in a thermoplastic resin, magnesium hydroxide and aluminum hydroxide, a silicone powder, and A flame-retardant resin composition containing at least one powder selected from the group consisting of zinc oxide, zinc borate and zinc carbonate as an essential component is disclosed.

[0004]

However, in the conventional non-halogen flame-retardant resin composition, it is difficult to obtain practical flame-retardant performance (for example, the flame-retardant performance defined in JIS K 7201). There is a problem in that a large amount of metal hydroxide, which is a flame retardant, must be blended, and as a result, the mechanical strength of the flame-retardant resin composition itself decreases. In particular, when used as an insulating material for electric wires, a sheath material, or a molded product material, in addition to flame retardancy, flexibility, tensile strength, elongation, etc. above a predetermined value are required.
The blending amount of the metal hydroxide is naturally limited, and it is difficult to obtain a satisfactory flame retarding performance even if a flame retardant aid composed of a molybdenum compound or silicone powder is added. Thus, there is no concern about industrial hygiene, and a flame-retardant resin composition excellent in both flame retardancy and mechanical strength has not yet been obtained.

The present invention has been made in view of the above circumstances, and provides a flame-retardant resin composition which has not only flame-retardant performance but also excellent mechanical strength and is safe from the viewpoint of industrial hygiene. The purpose is to

[0006]

To achieve the above object, according to the Invention The flame retardant resin composition of the present invention, the olefin resin, at least, a metal hydroxide compound represented by the following general formula (I) and characterized by being blended 及 beauty molybdate compound. Mg _{1-(X + Y)} Ma _X Mb _Y (OH) ₂ (I) where Ma and Mb are Mn ²⁺ , Fe ²⁺ , Co ²⁺ , N
A metal ion selected from the group consisting of i ²⁺ , Cu ²⁺ and Zn ²⁺ , which may be the same or different, and (X +
Y) is 0.005 <(X + Y) <0.7.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention will be described in detail below. The flame-retardant resin composition of the present invention uses an olefin resin as a base material. The olefin resin is not particularly limited, and known ones conventionally used in flame-retardant resin compositions can be used. For example, low density, medium density and high density polyethylene,
Poly α-olefins such as polypropylene and polybutene, copolymers of the above α-olefins, copolymers of α-olefins such as ethylene-ethyl acrylate copolymer (EEA) with other monomers, or ethylene-propylene. Examples thereof include multi-component copolymers such as diene elastomer. Further, these olefin resins may be crosslinked, or may be a polymer blend obtained by mixing two or more kinds. In the present invention, polyethylene and a polymer blend of polyethylene and EEA are particularly preferable.

The flame retardant resin composition of the present invention contains a metal hydroxide represented by the following general formula (I) and a molybdic acid compound as essential components. Mg _{1-(X + Y)} Ma _X Mb _Y (OH) ₂ (I) In the formula (I), Ma and Mb are Mn ²⁺ , Fe ²⁺ and Co.
It is a metal ion selected from the group of ²⁺ , Ni ²⁺ , Cu ²⁺ and Zn ²⁺ , and even if they are the same (that is, form a hydroxide of Mg and another metal), they are different. (Ie, form a hydroxide of Mg and two other metals). Further, the substitution amount of Mg by Ma and Mb (X + Y) is 0.005 <
It is preferable that (X + Y) <0.7, especially 0.0
It is preferable that 5 <(X + Y) <0.5. When the amount of substitution by Ma and Mb deviates from this range, the effect of the present invention that the flame retardancy and mechanical strength are excellent cannot be obtained. Moreover, this metal hydroxide can also be used in mixture of 2 or more types.

The metal hydroxide represented by the general formula (I) is a component which acts as a flame retardant, and the flame retarding performance increases as the blending amount increases, while the mechanical resistance of the flame retardant resin composition is increased. Reduce strength. Therefore, in order to achieve both flame retardancy and mechanical strength which is the object of the present invention, it must set the amount of the metal hydroxide properly, metal hydroxides olefin resin 30 to 100 parts by weight
Range of 120 parts by weight is preferred.

The molybdic acid compound is a component that acts as a flame retardant aid, and is preferably added in an amount of 3 to 30 parts by weight based on 100 parts by weight of the olefin resin. A blending amount of less than 3 parts by weight does not sufficiently contribute to the improvement of the flame retardant performance, and a blending amount of more than 30 parts by weight lowers the mechanical strength of the flame retardant resin composition. More preferably, it is 10 to 30 parts by weight with respect to 100 parts by weight of the olefin resin. When the amount of the metal hydroxide compound is small, it is preferable to relatively increase the amount of the molybdic acid compound compound in order to improve the flame retardancy. Further, the molybdic acid compound is preferably a compound containing no halogen or phosphorus in its molecule from the viewpoint of preventing the generation of harmful gases, such as molybdenum trioxide, molybdenum (IV) hydroxide, molybdenum disulfide, molybdenum oxide. Acetylacetonate, ammonium molybdate, potassium molybdate, calcium molybdate, sodium molybdate, etc. can be used alone or in admixture of two or more. Particularly, calcium molybdate is preferable.

[0011]

[0012]

[0013]

The flame-retardant resin composition of the present invention comprises a conventional metal hydroxide as a flame-retardant agent and a molybdenum compound as a flame-retardant auxiliary agent (for example, JP-A-59-2022).
No. 43 publication can be referred to. ) Flame retardancy is expressed by the same action as, but metal hydroxide represented by the general formula (I), as compared with the conventional metal hydroxide is rich in pyrolytic, about 250 ° C. ~ early forms an insulating film at a low temperature of 350 ° C.. For this reason, small in amount conventionally least equivalent flame retardancy can be obtained than the conventional, it is possible to suppress a decrease in mechanical strength of the flame-retardant resin composition. Further, since it does not contain a source of harmful gas such as halogen, there is no concern about industrial hygiene.

The flame-retardant resin composition of the present invention may contain, if necessary, known antioxidants, crosslinking agents, crosslinking aids, fillers and the like in appropriate amounts.

[0016]

EXAMPLES The present invention will be described with reference to Examples and Comparative Examples below.
Further clarify. (Examples 1 to 7, Comparative Examples 1 and 2) As an olefin resin
, Low-density polyolefin (LDPE: Nippon Polyolefin)
"F-31" made by Iin, EEA (made by Nippon Polyolefin)
"A-1100") and Mg as the metal hydroxide
_0.95Ni²⁺ _0.05(OH)₂ , Mg_0.95Co²⁺ _{0. 05}(O
H)₂ , Mg_0.95Zn²⁺ _0.05(OH)₂ , Mg_0.5
Ni²⁺ _0.01Co²⁺ _0.49(OH)₂ And Mg (OH)₂ 
(Kyowa Chemical Industry "Kisuma 5B")
Calcium Denate (Sherwin Williams "K
EMGARD911A ") and the ratios shown in Table 1
(Unit: parts by weight) to prepare a flame-retardant resin composition.
It was In addition, C was used as an antioxidant in all flame-retardant resin compositions.
A single "IRGANOX 1010" made by IBAGEIGY
It is compounded in parts.

[0017]

[Table 1]

Then, a copper wire was coated with each flame-retardant resin composition to prepare a test electric wire, which was subjected to a flame-retardant test and a strength test (tensile strength and elongation). Flame retardant test is JIS K 72
The oxygen index is shown in Table 1. The target value is 30 or more. Also, the tensile strength and elongation are JIS
The measurement values are shown in Table 1 according to K 6760.
It was shown to. The target value of tensile strength is 16 (MPa) or more, and the target value of elongation is 150 (%) or more. Table 1
As is clear from the above, the flame-retardant resin compositions of Examples 1 to 7 according to the present invention have achieved the target values of each test, and are found to have excellent flame retardancy and mechanical strength. On the other hand, although the flame-retardant resin composition of Comparative Example 1 achieved the target value of mechanical strength, it was inferior in flame-retardant performance, and the flame-retardant resin composition of Comparative Example 2 had a flame-retardant performance. Although the target value was achieved, the mechanical strength was inferior, and the superiority of the flame-retardant resin composition of the present invention was confirmed.

[0019]

[0020]

[0021]

[0022]

As described above, the flame-retardant resin composition of the present invention is excellent not only in flame-retardant performance but also in mechanical strength, and there is no concern from the viewpoint of industrial hygiene. It is suitable as various extruded molded article materials and injection molded article materials for which flame retardant performance is desired, such as wiring for buildings and buildings.

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Claims (4)

(57) [Claims] To 1. A olefin resin, at least flame-retardant resin, characterized in that by blending a metal hydroxide Mono及 beauty molybdate <br/> compound represented by the following general formula (I) Composition. Mg _{1-(X + Y)} Ma _X Mb _Y (OH) ₂ (I) where Ma and Mb are Mn ²⁺ , Fe ²⁺ , Co ²⁺ , N
A metal ion selected from the group consisting of i ²⁺ , Cu ²⁺ and Zn ²⁺ , which may be the same or different, and (X +
Y) is 0.005 <(X + Y) <0.7. 2. The metal hydroxide of 30 to 120 parts by weight and the molybdic acid compound of 3 to 30 parts by weight are mixed with 100 parts by weight of the olefin resin. The flame-retardant resin composition described. 3. The flame-retardant resin composition according to claim 1, wherein the molybdic acid compound contains no halogen or phosphorus in the molecule. 4. The olefin resin is polyethylene,
Or polyethylene and ethylene-ethyl acrylate
The flame retardant resin composition according to any one of claims 1-3, characterized in Oh Rukoto a polymer blend of a copolymer.