JPS5818948B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant resin composition, and more specifically, by blending mesitylene resin with a styrene-based resin together with a common flame retardant, it is possible to maintain the excellent physical properties of the styrene-based resin while achieving a high degree of The present invention relates to a resin composition exhibiting flame retardancy.

In general, thermoplastic resins such as styrene resins are easily flammable, so their fields of use are restricted from the viewpoint of safety.

Therefore, in order to improve the flame retardancy of these resins, flame retardants such as organic (organic) chloride compounds and phosphoric acid ester compounds, as well as flame retardant aids such as antimony trioxide, are added.

Incidentally, in recent years, flame retardant standards such as UL standards have been strengthened year by year, so it has become necessary to add a large amount of flame retardant in order to obtain a resin that exhibits excellent flame retardancy.

However, when the amount of flame retardant added increases, it not only causes a decrease in the physical properties of the resin composition, but also discoloration due to thermal decomposition of the flame retardant during melt molding, generation of toxic and corrosive gases, and the weather resistance of the resulting resin molded product. Problems may arise, such as deterioration of the flame retardant, the generation of toxic gas during combustion, or the toxicity of the flame retardant itself.

The present inventors have already developed and proposed a resin composition containing a xylene resin in order to solve the problems of the prior art described above.

(% Gansho 54-86076').

The present inventors further conducted extensive research to develop a resin composition with superior flame retardancy. As a result, the present inventors added mesitylene resin to a styrene-based resin together with an organic compound, which is a conventionally used flame retardant. It was discovered that the desired resin composition could be obtained by blending it with a resin, and the present invention was completed.

That is, the present invention provides a flame-retardant resin composition comprising (A) a styrene resin, (B) an organic chloride compound, and (C) a mesitylene resin.

The styrenic resin, which is component (A) of the present invention, is a base component of the composition of the present invention.

Examples of the styrene resin include polystyrene, rubber-modified polystyrene (HI polystyrene), styrene-butadiene copolymer, and styrene-acrylonitrile copolymer (A
S resin), styrene-butadiene-acrylonitrile copolymer (ABS resin), and the like.

In particular, styrenic resin containing rubber is most preferably used.

Next, the organic compound which is component (B) of the present invention acts as a flame retardant, and is an aromatic compound containing a halogen atom such as bromine, chlorine, or fluorine in its molecular structure;
It includes all organic compounds that have a flame retardant effect, such as alicyclic compounds and aliphatic compounds.

Specifically, hexabromobenzene; pentabromotoluene; piphenyl bromide: triphenyl chloride: diphenyl ether bromide; tetrachlorophthalic acid: tetrabromo phthalic anhydride; triflomophenol; tribromophenyl; dibromo alkyl ether; tetrabromo bisphenol. S: Tetrachlorobisphenol A; 2,2-bis(4-hydroxy-3,5-dibromophenyl)-propane (hereinafter referred to as "tetrabromobisphenol A").

), aromatic compounds such as Al or monochloropentabromocyclohexane; hexabromocyclododecane: perchloropentacyclohexane; alicyclic halogen compounds such as hexachloroendomethylenetetrahydrophthalic anhydride, and even chlorinated Paraffin; Chlorinated polyethylene: Tetrabromoethane; Tetrabromophthane; Tris (β-chloroethyl) phosphate; Tris (dichlorofurobir) phosphate; Tris (dibromophenyl) phosphate; Aliphatic systems such as tris (chlorobromopropyl) phosphate ...Rogen compounds can be mentioned.

The blending ratio of the above-mentioned organic compound, which is the component (B) of the present invention, varies depending on the types of other components, the amount added, and other conditions, and cannot be unambiguously determined, but it is usually (5
) 5 to 100 parts by weight of the styrene resin component
It should be 30 parts by weight, preferably 8 to 20 parts by weight.

If it is less than 5 parts by weight, the resulting composition will have insufficient flame retardancy, while if it exceeds 30 parts by weight, the physical properties of the composition will deteriorate, toxic gas will be generated during melt molding and combustion, and corrosivity will increase, etc. This will cause some inconvenience.

Next, the mesitylene resin (component q) of the present invention, together with the above-mentioned organic halogen compound which is the component (component), exhibits the effect of imparting flame retardancy to the composition, and is particularly effective in preventing melt dripping during combustion. act.

Various types of mesitylene resin can be considered, such as mesitylene-formaldehyde resin obtained by condensing mesitylene and formaldehyde in the presence of a strong acid catalyst, mesitylene resin modified with phenol or alkylphenol, organic acids, alcohols, amines, etc. Modified mesitylene resins such as mesitylene resins modified with

In addition, these mesitylene resins are available in liquid, starch syrup, powder, and
It may be in any form of lumps, and there is no particular restriction on molecular weight.

However, in consideration of the physical properties of the composition such as heat resistance, it is preferable to use a composition having a relatively high melting point, such as a powder or block.

The composition of the present invention exhibits a superior flame retardant effect compared to the previously proposed composition containing xylene resin, and as a result, the blended amount of mesitylene resin and organic halogen compound is reduced (
It has characteristics that can be suppressed.

Here, even if novolac resin, melamine resin, phenokinomMW, etc. are used instead of mesitylene resin, almost no improvement in flame retardancy is observed.

Doma C) The blending ratio of mesitylene resin, which is the component, may be selected appropriately depending on various conditions, but it is usually 0.2 to 3 parts by weight per 100 parts by weight of the styrene resin, which is the component (A).
It should be 0 parts by weight, preferably 0.5 to 15 parts by weight.

If it is less than 0.2 parts by weight, the effect of addition cannot be obtained sufficiently;
Moreover, if it exceeds 30 parts by weight, the physical properties of the composition may be deteriorated, which is not economically preferable.

In the present invention, in addition to the above-mentioned components (B) and (C), flame retardant aids, reinforcing agents, fillers, heat stabilizers, ultraviolet absorbers, plasticizers, lubricants, coloring agents, etc. can be added as appropriate.

Here, antimony trioxide is mainly used as a flame retardant aid, and its processed zirconium oxide, molybdenum oxide,
Aluminum hydroxide, zinc borate, barium metaborate, etc. can also be used.

There are no particular restrictions on the blending of this flame retardant aid, but it is usually
A) 1 per 100 parts by weight of styrene resin as component
~10 parts by weight, preferably 2 to 6 parts by weight.

In addition, various reinforcing agents and fillers can be used depending on the purpose of the resulting composition, such as rubbers, organic fibers or glass fibers, inorganic fibers such as carbon fibers, calcium carbonate, talc, etc. Examples include clay and aluminum hydroxide.

In producing the composition of the present invention, the above-mentioned (A
), (B) and (q component, as well as various additives as necessary) are mixed in a predetermined ratio, and the mixture is sufficiently mixed using a roll mill, Banbury mixer, kneader, Henschel mixer, single screw extruder, twin screw extruder, etc. Knead.

Since the composition of the present invention obtained in this manner contains mesitylene resin, it can exhibit sufficient flame retardant effect with a smaller amount of organic halogen compound than conventional flame retardant resin compositions. can.

Therefore, the halogen content in the composition is reduced, and as a result, various troubles caused by halogens, such as deterioration of physical properties such as weather resistance and mechanical strength, and generation of harmful gases, are effectively prevented.

Furthermore, since the drip resistance of the composition is improved, melt dripping during combustion is hardly observed.

Therefore, the resin composition of the present invention can be effectively used as a material for electrical products, mechanical parts, automobiles, building materials, ornaments, and various other products.

Next, examples of the present invention will be shown.

Examples 1 to 3 and Comparative Examples 1 to 2 Rubber-modified polystyrene (MI O, 9L?/10 minutes, graft copolymer with a content of 8.0 wt% of polybutadiene rubber (Mooney viscosity 35 (100°C)), product Tetrabromobisphenol A, antimony trioxide, and mesitylene resin were blended into 100 parts by weight of Idemitsu Polystyrene HT-58 (manufactured by Idemitsu Petrochemical Co., Ltd.) in a predetermined ratio, and this was melted and kneaded in a Banbury mixer. Pelletized with a sheet pelletizer.

By injection molding from this pellet, 3mm x 6.5mm
A test piece of x 127 mm was prepared and tested according to ASTM D28.
The oxygen index (0, 1,) was measured according to 63-70.

The results are shown in Table 1. Example 4, Comparative Example 3 and Reference Example 1 In the above Example 1, instead of rubber modified polystyrene, A
A test piece was prepared using 100 parts by weight of BS resin (trade name: ABS resin JSR-35, manufactured by Japan Synthetic Rubber ■) and the same procedure was performed, and the oxygen index (0, L) was measured.

The results are shown in Table 2. (*1) Tetrabromobisphenol A (*2) Product name: Mesitylene resin Nikanol M, manufactured by Mitsubishi Gas Chemical ■ (*3) Product name: Alkylphenol modified mesitylene resin Nicanol HP150, manufactured by Mitsubishi Gas Chemical ■ (*I) Product name: Alkylphenol-modified mesitylene resin Nicanol HP150, manufactured by Mitsubishi Gas Chemical (*2) Product name: Alkylphenol-modified xylene resin J-20, manufactured by Matsushita Dencho Examples 5 to 10 and comparative example 4 Same as Example 1 above A test piece for flammability test (thickness % inches) was formed using the following procedure, and a UL94 standard vertical flammability test was conducted.

The results are shown in Table 3. The thermoplastic resin is rubber-modified polystyrene (product name: Idemitsu Polystyrene HT-58).
100 parts by weight (manufactured by Idemitsu Petrochemical Co., Ltd.) was used.

(*1) Product name: Chlorinated wax A-70, manufactured by Toyo Soda Kogyo ■ (*2) Product name: Dechlorane Plus 51
5. Manufactured by Hooker Chemical Co. (*3) Product name: Alkylphenol modified mesitylene resin dicanol HP 150
, manufactured by Mitsubishi Gas Chemical ■ (*4) Product name: Mesitylene resin dicanol M manufactured by Mitsubishi Gas Chemical ■ Comparative example 5 In Example 1 above, 6 parts by weight of each of novolak resin, melamine resin, and phenoxy resin were added in place of mesitylene resin. Except for the above, a test piece was prepared in the same manner as in Example 1, and the oxygen index (0, I-) was measured. Almost no improvement was observed.

Examples 11 to 16 and Comparative Examples 6 to 11 Rubber modified polystyrene (trade name Nideko Polystyrene HT)
-58, manufactured by Idemitsu Petrochemical ■) to 100 parts by weight of tetrabromobisphenol A1 antimony trioxide, chlorinated wax, and mesitylene resin are blended in a predetermined ratio,
A test piece was prepared in the same manner as in Example 1, and the oxygen index (
0,I,) was measured.

The results are shown in Table 4. (*l) Product name: Chlorinated wax A-70, manufactured by Toyo Soda Kogyo ■ (chlorine content near 0% by weight) (*2) Product name: Nikanol Hp150, Mitsubishi Gas Chemical Co., Ltd. (*3 ) Atomic ratio in resin composition Example 17.18 and Comparative Examples 12-15 Above Example 1
Instead of rubber-modified polystyrene, AS resin (product name: Tyril 767, manufactured by Asahi Dow) or general purpose polystyrene (GPPS) (molecular weight 200,000, product name:
Idemitsu Polystyrene NF-20, manufactured by Idemitsu Petrochemical ■) 10
Using 0 part by weight, a test piece was prepared by performing the same procedure except for the test piece, and the oxygen index (0, I,) was measured.

The results are shown in Table 5.

Claims (1)

[Scope of Claims] 1. A flame-retardant resin composition comprising (A) a styrene resin, (B) an organic halogen compound, and (C) a mesitylene resin. 2 (A) 100 parts by weight of styrene resin and (B) organic...
Claim 1 comprising 5 to 30 parts by weight of a chlorogen compound and 0.2 to 30 parts by weight of a (q-mesitylene resin).
Compositions as described in Section.