JPH1160853A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having nondrippiness without detriment to mechanical properties, heat stability and surface gloss by mixing a styrene resin with a bromine-containing flame retardant, antimony trioxide and a multi- component copolymer having a specified compositional ratio. SOLUTION: This composition comprises 100 pts.wt. styrene resin, 10-30 pts.wt. bromine-containing flame retardant, 3-10 pts.wt. antimony trioxide and 0.3-12 pts.wt. multi-component copolymer having a composition of 5-99.5 wt.% epichlorohydrin, 94.5-0 mol.% ethylene oxide and 0.5-10 mol.% allyl glycidyl ether. The styrene resin is based on a homopolymer of styrene or a styrene derivative such as α-methylstyrene, vinyltoluene or chlorostyrene or a copolymer thereof with other monomers. The bromine-containing flame retardant used is decabromodiphenyl oxide or the like. The multi-component copolymer is prepared by copolymerizing the monomers in the presence of a catalyst such as an organoaluminum compound.

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 more particularly to molding of industrial or household materials requiring flame retardance, such as electrical equipment, OA equipment, and household kitchenware. And a flame-retardant resin composition to be used.

[0002]

2. Description of the Related Art Styrene resins widely used for molding electric equipment, OA equipment, automobile parts, household goods, and the like are generally very flammable and may be used as a part of molded articles. There is a drawback that if the flame is started close to burning, it will continue to burn naturally even if the flame is moved away. recent years,
Due to the need for fire safety, the demand for flame retardancy has become strict. Especially for electrical equipment and OA equipment, UL (Underwriters Laboratory) U.S.A.
Fields required to pass the L-94V0 standard are expanding. Conventionally, as a method of making a styrene resin flame-retardant, it is known to mix a flame retardant such as an organic bromine compound or a flame retardant auxiliary such as antimony trioxide with the styrene resin in combination. In this case, dripping cannot be prevented, so that it does not pass UL-94V0, and furthermore, a large amount of a flame retardant is mixed in, so that the excellent mechanical properties of the styrenic resin are significantly reduced. I was As a method for preventing dripping, for example, a method in which an inorganic filler such as talc, clay, or glass fiber is mixed into the above composition, or a polytetrafluoroethylene (for example, JP-A-50-4424)
1), chlorinated polyethylene (for example, JP-A-50-94)
066) has been proposed, but the method of mixing an inorganic filler or polytetrafluoroethylene has poor compatibility with the resin, resulting in a decrease in physical properties, and the method of mixing chlorinated polyethylene does not. There was a problem that the thermal stability of the styrene resin was reduced.

[0003]

Means for Solving the Problems The inventors of the present invention have focused on these problems and as a result of intensive studies, they have found that by adding an epichlorohydrin-ethylene oxide-allyl glycidyl ether multi-component copolymer to a flame-retardant styrene resin compound. ,
The inventors have found that the anti-drip property can be improved without lowering the physical properties of the styrenic resin, and have reached the present invention. The present invention is, (a) styrene-based resin 100 parts by weight, (b)
10 to 30 parts by weight of a bromine-based flame retardant, (c) 3 to 10 parts by weight of antimony trioxide, and (d) copolymerization ratio of epichlorohydrin 5 to 99.5 mol%, ethylene oxide 94.5.
A flame-retardant resin composition comprising 0.3 to 12 parts by weight of a multicomponent copolymer, which is 0 to 0 mol% and 0.5 to 10 mol% of allyl glycidyl ether.

The styrene resin used in the present invention is styrene, α-methylstyrene, vinyltoluene,
Mainly a homopolymer of a styrene derivative such as chlorostyrene or a copolymer with another monomer, for example, polystyrene, styrene-acrylonitrile copolymer (AS resin), α-methylstyrene-acrylonitrile copolymer Or an impact-resistant polystyrene resin reinforced with rubber, an acrylonitrile-butadiene-styrene copolymer (ABS resin), a methyl methacrylate-butadiene-styrene copolymer (MBS resin), and the like. It is optional to use two or more resins in combination. As the brominated flame retardant of the present invention, those commonly used can be used as they are, but examples thereof include decabromodiphenyl oxide, tetrabromobisphenol A, hexabromobenzene, brominated bisphenol-based carbonate oligomer, and brominated epoxy. be able to. The compounding amount of the flame retardant is 10 to 30 parts by weight of the brominated flame retardant and 3 to 10 parts by weight of antimony trioxide per 100 parts by weight of the styrene resin. If the amount is less than the respective ranges, sufficient flame retardancy cannot be obtained. If the amount exceeds the range, the mechanical properties are remarkably deteriorated, and it is economically disadvantageous.

The epichlorohydrin-ethylene oxide-allyl glycidyl ether multi-component copolymer used in the present invention is used as a catalyst for ring-opening polymerization in a catalyst system mainly composed of organoaluminum, a catalyst system mainly composed of organic zinc, and an organic tin-phosphorus. Using an acid ester condensate catalyst system or the like, each monomer is reacted at a reaction temperature of 10 to 8 in the presence or absence of a solvent.
It is obtained by reacting at 0 ° C. The copolymer composition of the multicomponent copolymer is 5 to 99.5 mol% of epichlorohydrin, 94.5 to 0 mol% of ethylene oxide, 0.5 to 10 mol% of allyl glycidyl ether, more preferably 5 to 98 mol% of epichlorohydrin, and 9 to 9 mol% of ethylene oxide.
3 to 0 mol% allyl glycidyl ether is 2 to 6 mol%
It is. When epichlorohydrin is less than 5 mol%, the compatibility with the styrene resin is inferior and the physical properties deteriorate. On the other hand, if the amount of allyl glycidyl ether is less than 0.5 mol%, sufficient anti-drip property cannot be obtained, and if it exceeds 10 mol%, the surface gloss of the molded product is lost, which is not preferable. The compounding amount of the multi-component copolymer is 0.3 to 12 parts by weight, more preferably 1 to 7 parts by weight. If the amount is less than 0.3 parts by weight, the anti-drip property is inferior. If the amount exceeds 12 parts by weight, the surface gloss of the molded product is lost.

[0006] The flame-retardant resin composition of the present invention can be obtained by mixing predetermined components by a conventional method using a mixing roll, a kneader, a Banbury mixer, a kneading extruder or the like. Further, in addition to the composition, various compounding agents such as fillers, reinforcing agents, stabilizers, pigments, and the like can be compounded as is usually performed in the art, and an even more excellent anti-drip Polytetrafluoroethylene, chlorinated polyethylene, or the like can be arbitrarily blended in order to obtain the property, as long as the physical properties of the styrene resin are not impaired.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below by way of examples.

[0008]

[Example] As a styrene resin, AB manufactured by Toray Industries, Inc.
S resin Toyolac 100 and H made by Asahi Kasei Kogyo Co., Ltd.
IPS resin Stylon 494 was used. As an epichlorohydrin-ethylene oxide-allyl glycidyl ether multi-component copolymer, each component was 54 mol% and 39 mol%, respectively.
Mol%, 7 mol% (GECO1), and 41 mol%, 5 mol%
6 mol%, 3 mol% (GECO2), and 97 mol%,
0 mol% and 3 mol% (GECO3) were used. For comparison, polytetrafluoroethylene (Polyflon FA-100 manufactured by Daikin Industries, Ltd.) and chlorinated polyethylene (Daisolac G-23 manufactured by Daiso Co., Ltd.)
5) was used. Izod impact test is JISK-687
0, and the flame retardancy was measured in accordance with UL-94. A test piece having a thickness of 2 mm and a width of 12.7 mm was used. The measurement results of the flame retardancy are represented by V0, V1, and V2, where V0 is "with anti-drip property" and V2 is "without anti-drip property".

Examples 1 to 6 and Comparative Examples 1 to 6 Each of the compositions shown in Table 1 was applied to an 8 inch roll at 170 ° C. for 6 hours.
It was kneaded for a minute and made into a sheet. The obtained sheet was hot-pressed at 100 Kg / cm ² for 5 minutes by a hot press set at 190 ° C. As for the surface gloss, the gloss of the injection-molded molded product was visually confirmed, and は indicates “particularly good”, indicates “good”, and X indicates “bad”. Regarding the thermal stability, the roll sheet was hot-pressed at 250 ° C. for 30 minutes, and the degree of discoloration of the molded product was visually observed. 1 was “good”, 3 was “bad”, and 2 was between 1 and 3. . It is clear that the resin composition of the present invention exhibits particularly excellent physical properties in comparison with Comparative Examples.

[0010]

[Table 1]

[0011]

Industrial Applicability The resin composition of the present invention is excellent in flame retardancy and its mechanical strength is remarkably improved. Therefore, it is expected to be applied as a molding material used for molding industrial or household materials requiring flame retardancy, such as electric equipment, OA equipment, and household kitchenware.

Claims (2)

[Claims] (1) 100 parts by weight of a styrene resin, (b) 10 to 30 parts by weight of a brominated flame retardant, and (c) antimony trioxide 3
10 to 10 parts by weight, and (d) a copolymer composition ratio of epichlorohydrin of 5 to 99.5 mol% and ethylene oxide of 94.5 to 94.5%
A flame-retardant resin composition comprising 0.3 to 12 parts by weight of a multicomponent copolymer that is 0 mol% and 0.5 to 10 mol% of allyl glycidyl ether. 2. The copolymer composition ratio of the multi-component copolymer is 5 to 98 mol% of epichlorohydrin and 93 to 0 of ethylene oxide.
2. The flame-retardant resin composition according to claim 1, wherein the amount is 2 to 6 mol% of allyl glycidyl ether.