JPH0987437A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition satisfying low-bleeding tendency and low mold-corroding property and exhibiting excellent flame- retardant effect. SOLUTION: This resin composition contains 100 pts.wt. of a polyolefin, 1-30 pts.wt. of a mixture of tetrabromobisphenol A bis(2,3-dibromopropyl) ether and tetrabromobisphenol S bis(2,3-dibromopropyl) ether at a weight ratio of 0.5:9.5 to 3:7 and 0.1-3.0 pts.wt. of a fatty acid aluminum salt such as aluminum stearate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition which has little bleeding property and metal corrosion, exhibits a high flame-retardant effect, and has good workability.

[0002]

2. Description of the Related Art Conventionally, a resin composition containing various halides has been proposed as a method for flame-retarding a polyolefin. However, the flame-retardant has low bleeding property at the time of heat processing or use of a final molded product, and a molding die. There are only a few resin compositions that satisfy the low corrosion resistance and have an excellent flame retardant effect. For example, decabromodiphenyl ether has a low bleeding property, but since it has a low flame retardant effect, it requires a large amount of addition, resulting in the deterioration of the physical properties inherent to polyolefin. On the other hand, as a flame retardant capable of obtaining high flame retardance with a relatively small amount of addition, tetrabromobisphenol A bis (2,
Although 3-dibromopropyl) ether and bis (2,3-dibromopropyl) ether of tetrabromobisphenol S are known, the former has a high bleeding property and the latter has a drawback that it is easily deteriorated by heat during heat processing. are doing. Therefore, a method of improving the bleeding property by using the former and latter flame retardants in combination has been proposed (Japanese Patent Publication No. 62-49900).

However, the above composition has a drawback that the mold of the molding machine is easily corroded.

On the other hand, when etherified tetrabrominated bisphenol A is used as a flame retardant for polyolefin, the inclusion of metal soap suppresses decomposition of the flame retardant during molding and suppresses deterioration of the resin due to heat. It has been reported (JP-A-49-31749).

However, in this case as well, reduction in corrosiveness to the molding die has not been solved.

[0006]

As described above, few conventional flame-retardant compositions satisfy the low bleeding property and the low corrosiveness to the molding die, and exhibit an excellent flame-retardant effect.

Therefore, the development of a resin composition free from these problems has been an issue in polyolefins imparting flame retardancy.

[0008]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned problems, the present inventor has found that bis (2,3-dibromopropyl) ether of tetrabromobisphenol A and bis (2, The flame-retardant resin composition obtained by adding an aluminum salt of a fatty acid to a mixture containing 3-dibromopropyl) ether in a specific ratio satisfies low bleeding property and low corrosion resistance to a molding die, and The inventors have found that they exhibit an excellent flame retardant effect, and have completed the present invention.

That is, the present invention relates to (A) polyolefin 10
(B) tetrabromobisphenol A bis (2,3-dibromopropyl) ether and tetrabromobisphenol S bis (2,3-dibromopropyl) ether (B) in a weight ratio of 0.5: 9. A flame-retardant resin composition comprising 1 to 30 parts by weight of a mixture contained in a ratio of 5 to 3: 7 and 0.1 to 3.0 parts by weight of an aluminum salt of (C) fatty acid.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As the polyolefin used in the present invention, ethylene, propylene, butene-
1, homopolymers of α-olefins such as pentene-1, 4-methylpentene-1, and hexene-1, random copolymers of these α-olefins, block copolymers,
Examples thereof include copolymers such as graft copolymers, and mixtures of these homopolymers and copolymers. The above-mentioned copolymer may be copolymerized with a monomer other than α-olefin in an amount of 10 mol% or less, or modified with maleic anhydride or the like, as long as the properties of the copolymer are not impaired. It may be.

The bis (2,3-dibromopropyl) ether of tetrabromobisphenol A and the bis (2,3-dibromopropyl) ether of tetrabromobisphenol S used in the present invention have a weight ratio of 0.5: 9. 5-
It is used by mixing in a ratio of 3: 7. The blending amount of the above mixture is 1 to 3 with respect to 100 parts by weight of polyolefin.
It should be 0 parts by weight, preferably 3 to 20 parts by weight. If the compounding amount is less than the lower limit value, sufficient flame retardant effect cannot be obtained, and if the compounding amount is more than the upper limit value, not only moldability, impact resistance decrease and specific gravity increase but also stable. It is not preferable because the kneading work becomes difficult.

As the aluminum salt of a fatty acid used in the present invention, an aluminum salt of a fatty acid having 12 to 20 carbon atoms is preferable, and aluminum stearate, aluminum laurate and the like are preferably used.

The blending amount of the aluminum salt of the fatty acid is 0.1 to 3.0 with respect to 100 parts by weight of the polyolefin.
It must be 0.1 part by weight, preferably 0.1 part by weight. If the compounding amount is less than the lower limit value, sufficient low corrosion resistance cannot be obtained, and if it is more than the upper limit value,
Not only is the flame retardance reduced, but stable kneading work becomes difficult, which is not preferable.

The flame-retardant composition according to the present invention exhibits a sufficient flame-retardant effect only by the combination of the above-mentioned flame-retardants, but the amount of addition can be reduced by using antimony trioxide together. . Such antimony trioxide is
Any commonly available product can be used without any limitation. Further, the amount of antimony trioxide mixed is the same as that of the flame retardant
It is preferably 20 to 200 parts by weight with respect to 00 parts by weight. If the compounding amount of antimony trioxide is less than 20 parts by weight, a sufficient synergistic effect cannot be obtained,
If the amount is more than the amount by weight, no synergistic effect is observed, and the specific gravity increases and the impact resistance decreases, which is not preferable.

The flame-retardant resin composition of the present invention contains, in addition to the above-mentioned components, conventionally known antioxidants (phenolic compounds, phosphorus-based compounds, if necessary) within a range that does not impair the effects of the present invention. Sulfur compounds, etc.), weathering agents (benzophenone, salicylate, benzotriazole, hindered amine, etc.), metal deactivators, colorants, antistatic agents (anionic, cationic, nonionic, amphoteric), It may contain a nucleating agent (metal salt-based, sorbitol-based, etc.), a filler (talc, calcium carbonate, barium sulfate, glass fiber, mica, etc.) and an anti-blooming agent.

The mixing order and mixing method of the respective components for preparing the flame-retardant resin composition of the present invention are not particularly limited, and generally, a tumbler type blender, a V type blender, a Henschel mixer, a ribbon mixer and the like are used in a conventional method. Done by.

[0017]

EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention satisfies the requirements of low bleeding property and low corrosiveness to a molding die, and exhibits an excellent flame retardant effect.

[0018]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below, but the present invention is not limited to these examples. The symbols shown in Examples and Comparative Examples are as follows.

1. Polyolefin A: Ethylene-propylene block copolymer (Tokuyama Polypro PN670G, manufactured by Tokuyama) B: Propylene homopolymer (Tokuyama Polypro PN150)
G, made by Tokuyama) 2. Flame retardant C: Tetrabromobisphenol A bis (2,3-dibromopropyl) ether D: Tetrabromobisphenol S bis (2,3-dibromopropyl) ether 3. 3. Flame retardant aid E: Antimony trioxide Aluminum salt of fatty acid F: Aluminum stearate G: Aluminum laurate H: Calcium stearate Examples and Comparative Examples The preparation and test methods of the flame-retardant resin composition were carried out as follows, and the results are shown in Table 1.

(1) Premixing With respect to 100 parts by weight of polypropylene, the flame retardant and tetrakis [methylene-3- (3,5-di-t] in the recipe of Table 1 are added.
-Butyl-4-hydroxyphenyl) propionate]
Methane (Irganox 101, manufactured by Japan Ciba Geigy)
0) 0.1 part by weight, tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba-Geigy Japan, Irgafos 168: 0.1 part by weight, dilaurylthiodipropionate (manufactured by Sumitomo Chemical Co., Ltd.) , Sumilizer-TPL-
R): 0.2 parts by weight were compounded and premixed with a Henschel mixer.

(2) Pelletization The above mixture was pelletized using a vented 50 mmφ extruder.

(3) Preparation of test piece A test piece (length: 5 inches, width: 1/2 inch, thickness: 1/8 inch) was prepared from the above pellets using a 2oz injection molding machine.

(4) Effect test (a) Combustion test Using the test piece prepared by the method of (3), the flammability was judged by a vertical combustion test in accordance with UL94 standard.

(A) Bleed property acceleration test After heating the test piece prepared by the method of (3) at 80 ° C. for 1 hour, the bleeding state was evaluated in three stages.

○: No bleeding △: Slight bleeding ×: Bleeding (c) Metal corrosiveness test Pellets prepared by the method (2) were heated and melted at 210 ° C., and then S55C steel material (Cr plating) was melted and pelletized. It was immersed in the glass for 5 hours, and the corrosiveness was evaluated in two stages.

◯: No corrosion X: Corrosion

[0027]

[Table 1]

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[Procedure amendment]

[Submission date] October 4, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

1. Polyolefin A: Ethylene-propylene block copolymer (Tokuyama Polypro PN670G, manufactured by Tokuyama) B: Propylene homopolymer (Tokuyama Polypro PN150)
G, made by Tokuyama) 2. Flame retardant C: Tetrabromobisphenol A bis (2,3-dibromopropyl) ether D: Tetrabromobisphenol S bis (2,3-dibromopropyl) ether 3. 3. Flame retardant aid E: Antimony trioxide Salt of fatty acid F: Aluminum stearate G: Aluminum laurate H: Calcium stearate Examples and Comparative Examples The preparation and test methods for the flame-retardant resin composition were carried out as follows, and the results are shown in Table 1.

Claims (1)

[Claims] 1. A bis (2) of tetrabromobisphenol A (B) relative to 100 parts by weight of (A) polyolefin.
1 to 30 parts by weight of a mixture containing 3-dibromopropyl) ether and bis (2,3-dibromopropyl) ether of tetrabromobisphenol S in a weight ratio of 0.5: 9.5 to 3: 7 and (C). A flame-retardant resin composition comprising 0.1 to 3.0 parts by weight of a fatty acid aluminum salt.