JPH05163387A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. without detriment to the flame-retardant effect of red phosphorus while greatly reducing the fear of ignition due to friction or impact during mixing with a polyolefin resin by compounding the resin with a hydrated metal compd. and red phosphorus coated with a liq. chlorinated paraffin. CONSTITUTION:The title compsn. is prepd. by compounding 100 pts.wt. polyolefin resin with 1-200 pts.wt. hydrated metal compd. and 1-30 pts.wt. red phosphorus coated with a liq. chlorinated paraffin. The chlorinated paraffin having a degree of chlorination of 20-50% is pref.; the degree below 20% gives the paraffin an insufficient flame retardance and that higher than 50% results in such as high viscosity as to make the coating difficult. The paraffin is added to red phosphorus in an amt. just enough to coat the surface of red phosphorus, usually 1-20wt.% of it.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyolefin resin composition having improved flame retardancy.

[0002]

2. Description of the Related Art Polyolefin resin compositions used as insulation materials and sheath materials for electric wires and cables are required to be flame retardant. Techniques for this purpose include a method of blending a halogen flame retardant and a hydroxylation method. A method of blending a hydrated metal compound such as magnesium or aluminum hydroxide is known.

However, the one containing a halogen-based flame retardant has a problem that a large amount of smoke is generated during combustion and the generation of corrosive gas such as hydrogen halide. On the other hand, hydrated metal compounds such as magnesium hydroxide and aluminum hydroxide require a large amount of blending in order to impart sufficient flame retardancy, and therefore have a problem of significantly reducing the mechanical properties of the resin composition. ..

[0004]

Therefore, recently, attempts have been made to blend red phosphorus, which has a high flame retardant effect, alone or in combination with a hydrated metal compound. However, red phosphorus, which is untreated, easily ignites due to friction and impact, and poses a new problem that it is extremely dangerous when kneading with resin. Further, surface-treated red phosphorus is also commercially produced, but it is difficult to say that it is safe enough.

[0005]

[Means for Solving the Problems] Under these circumstances, the present inventors have found that in a polyolefin resin composition,
By coating red phosphorus, which is added for the purpose of improving flame retardancy, with chlorinated paraffin, the flame retardant effect of red phosphorus is not impaired, and ignition due to friction and impact during kneading with resin is significantly reduced. The present invention has been found out and the present invention has been completed.

That is, the present invention is based on 100 parts by weight of a polyolefin, 1 to 200 parts by weight of a hydrated metal compound and 1 to 30 parts by weight of red phosphorus coated with 1 to 20% by weight of liquid phosphorus chlorinated paraffin. The present invention relates to a flame-retardant resin composition containing

The present invention will be described in detail below.

As the olefin resin used in the present invention, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HD
PE), polypropylene, polybutene-1, polyisobutylene, poly-4-methyl-1-pentene, and other homopolymers of olefin monomers, and ethylene-acrylic acid (EA).
A), ethylene-ethyl acrylate (EEA), ethylene-methyl acrylate (EMA), ethylene-acrylamide (EAAM), ethylene-methacrylic acid (EMA)
A), ethylene-methyl methacrylate (EMMA), ethylene-glycidyl methacrylate, ethylene-maleic anhydride, ethylene-vinyl acetate (EVA), ethylene-
Mention may be made of binary copolymers such as propylene, ternary copolymers such as ethylene-propylene-butadiene (EPDM), copolymers containing olefin monomers such as ionomer resins, or mixtures of two or more thereof. You can

The hydrated metal compound used in the present invention is
Magnesium hydroxide and / or aluminum hydroxide, both of which can be used in combination. In this case, the average particle size of magnesium hydroxide or aluminum hydroxide is preferably about 1 μm in view of the dispersibility in the resin and the influence on the mechanical properties of the resin composition. preferable. The blending amount thereof varies depending on the desired degree of flame retardancy, but is usually 1 to 200 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the polyolefin resin, either alone or as a mixture of both. If it is less than 1 part by weight, it does not contribute to the improvement of flame retardancy.
If it is more than 00 parts by weight, the mechanical properties of the resin composition will be significantly reduced. In the resin composition of the present invention, since the flame retardancy is improved by blending red phosphorus described below, the blending amount of the hydrated metal compound may be relatively small as compared with the conventional one.
A sufficient flame retarding effect may be obtained with 50 to 100 parts by weight with respect to 00 parts by weight. In that case, since the blending amount is small, deterioration of mechanical properties of the resin composition can be suppressed.

The red phosphorus used in the present invention is 5 to 1 in view of the dispersibility in the resin and the influence on the mechanical properties of the resin composition.
About 0 μm is preferable. In addition, red phosphorus surface-treated with a phenol resin or the like can be used. The blending amount of the red phosphorus varies depending on the desired degree of flame retardancy, but a sufficient flame retarding effect can be obtained by blending 1 to 20 parts by weight with respect to 100 parts by weight of the polyolefin resin.

The liquid chlorinated paraffin used for coating red phosphorus in the present invention has a chlorination rate of 20 to 5.
About 0% is preferable. If it is 20% or less, there is a problem in the flame retardancy of paraffin, and if it is 50% or more, the viscosity is too high.
It is inconvenient to coat. The amount of red phosphorus to be added may be such that liquid chlorinated paraffin is coated on the surface of red phosphorus, and usually 1 to 20 parts by weight is preferable with respect to red phosphorus. As a method for coating liquid chlorinated paraffin on the surface of red phosphorus, sufficiently dry red phosphorus (moisture absorption rate of 0 to 0.1%) is sprayed and mixed with liquid chlorinated paraffin, or liquid chlorinated. If the paraffin has a high viscosity, there is a method in which it is dissolved in carbon tetrachloride, chloroform, etc., and the solution is sprayed onto red phosphorus and mixed. The red phosphorus coated with chlorinated paraffin has a significantly reduced ignition property due to friction and impact, and further has improved dispersibility in a resin and flame retardancy.

Other flame retardants can be used in combination with the resin composition of the present invention, and if necessary, various additives such as inorganic fillers, colorants, antioxidants, etc. can be added. Is possible.

[0013]

EXAMPLES The effects of the present invention will be clarified below with reference to specific examples, but the present invention is not limited to these examples.

Example 1 To 100 parts by weight of red phosphorus (manufactured by Kanto Chemical Co., Inc.), 10 parts by weight of liquid chlorinated paraffin (manufactured by Tosoh Corporation: A-400 (chlorination rate 40%)) was sprayed. , Chlorinated paraffin-coated red phosphorus was obtained.

The abrasion resistance and impact resistance of the red phosphorus coated with liquid chlorinated paraffin were examined by an impact ignition test. The test method is as follows: 1g of sample is placed in an iron mortar and the weight is 1.8kg.
The iron pestle of was dropped at different heights and the ignition point was examined. The results are shown in Table 1.

[0016]

[Table 1] From Table 1, it is clear that the red phosphorus coated with the liquid chlorinated paraffin has a significantly improved impact ignitability as compared with the untreated red phosphorus.

Examples 2 to 4 Liquid chlorinated paraffin-coated red phosphorus and magnesium hydroxide obtained in Example 1 were added to 100 parts by weight of an ethylene-vinyl acetate copolymer (Tosoh Corp .: Ultracene 630). Flame retardant resin compositions were prepared by blending the amounts shown in Table 2 respectively.

The obtained resin composition was prepared by a twin-screw extruder, and a test piece was prepared by injection molding. Mechanical properties were evaluated by tensile fracture strength and elongation according to JIS K 7113 test method. Also, the combustion test is J
It was evaluated by the oxygen index according to the IS K 7201 test method. The results are shown in Table 2.

Comparative Example 1 The mechanical properties and flame retardancy of the ethylene-vinyl acetate copolymer used in Example 2 were evaluated in the same manner as in Example 2. The results are shown in Table 2.

Comparative Example 2 Ethylene-vinyl acetate copolymer 100 used in Example 2
A resin composition was prepared by mixing 50 parts by weight of magnesium hydroxide with parts by weight. The mechanical properties and flame retardancy of the obtained resin composition were evaluated in the same manner as in Example 2. The results are shown in Table 2.

Comparative Example 3 A resin composition was prepared in the same manner as in Example 2 except that commercially available red phosphorus was used as the red phosphorus, and the mechanical properties and flame retardancy were evaluated in the same manner as in Example 2. The results are shown in Table 2.

[0022]

[Table 2] Examples 5 to 7 Low-density polyethylene (Tosoh Corp .: Petrosene 20)
3) 100 parts by weight of the liquid chlorinated paraffin-coated red phosphorus obtained in Example 1 and magnesium hydroxide were added to Table 3 respectively.
A flame-retardant resin composition was prepared by blending only the amount described in.

The obtained resin composition was evaluated in the same manner as in Example 2. The results are shown in Table 3.

Comparative Example 4 The mechanical properties and flame retardancy of the low density polyethylene used in Example 4 were evaluated in the same manner as in Example 2. The results are shown in Table 3.

Comparative Example 5 A resin composition was prepared and evaluated in the same manner as in Comparative Example 2 except that the low density polyethylene used in Example 4 was used as the polyolefin. The results are shown in Table 3.

Comparative Example 6 A resin composition was prepared and evaluated in the same manner as in Comparative Example 3 except that the low density polyethylene used in Example 4 was used as the polyolefin. The results are shown in Table 3.

[0027]

[Table 3] Examples 8-10 Polypropylene (manufactured by Tosoh Corporation: J7030B) 10
The liquid chlorinated paraffin-coated red phosphorus obtained in Example 1 and magnesium hydroxide were each mixed in an amount of 0 part by weight in the amounts shown in Table 4 to prepare a flame-retardant resin composition.

The resin composition thus obtained was evaluated in the same manner as in Example 2. The results are shown in Table 4.

Comparative Example 7 The mechanical properties and flame retardancy of the polypropylene used in Example 8 were evaluated in the same manner as in Example 2. The results are shown in Table 4.

Comparative Example 8 A resin composition was prepared and evaluated in the same manner as in Comparative Example 2 except that the polypropylene used in Example 8 was used as the polyolefin. The results are shown in Table 4.

Comparative Example 9 A resin composition was prepared and evaluated in the same manner as in Comparative Example 3 except that the polypropylene used in Example 8 was used as the polyolefin. The results are shown in Table 4.

[0032]

[Table 4]

[0033]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention exhibits excellent flame-retardant properties while maintaining mechanical properties, and also has good stability during kneading, which suppresses smoke emission during combustion. Has the effect of being

Claims (1)

[Claims] 1. A blend of 1 to 200 parts by weight of a hydrated metal compound and 1 to 30 parts by weight of red phosphorus coated with 1 to 20% by weight of red phosphorus on a liquid chlorinated paraffin basis, based on 100 parts by weight of polyolefin. A flame-retardant resin composition comprising: