JPH0627233B2 - Method for stabilizing styrene resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to thermal stabilization of a styrene-based resin composition containing a bromine-based compound as a flame retardant, and is flame-retardant to styrene-based resins. It can be widely used in the fields where is required.

[Conventional technology]

Generally, in order to make a styrene resin flame-retardant, a method of adding a so-called flame retardant or a flame retardant auxiliary such as a halogen compound, a phosphorus compound, antimony trioxide, etc., has been conventionally performed. Compounds, especially bromine compounds, are often used.

However, in general, when a brominated flame retardant is added to a styrene resin, the thermal stability of the resin composition is remarkably reduced. Method of adding compound (Japanese Patent Publication No. 59-414
No. 62), a method of adding a maleic acid metal salt (Japanese Patent Publication No.
6-54023), a method of adding a metal salt of ethylenediaminetetraacetic acid (Japanese Patent Publication No. 61-2695), a method of adding an inorganic metal salt, a borate ester compound, a phosphorus compound, an antioxidant, and the like.

[Problems to be Solved by the Invention]

Among the above methods, organotin compounds and maleic acid metal salts, the method of adding ethylenediaminetetraacetic acid metal salt suppresses the decrease in thermal stability of the styrene resin, but the thermal stabilizing effect of these stabilizers is still Since it is not satisfied, the development of a stabilizer having a further excellent heat stabilizing effect has been awaited.

[Means for solving problems]

From such a viewpoint, the present inventors have made extensive studies on a stabilizer having an excellent thermal stabilizing effect on a resin composition obtained by adding a bromine flame retardant to a styrene resin, and as a result, a bromine flame retardant and a styrene flame retardant are obtained. When stabilizing a resin composition comprising a resin, it was found that the thermal stability of the resin composition is remarkably improved by adding an organic sulfonic acid metal salt and / or a sulfuric acid ester metal salt, and further the above composition To
The present invention has been completed by finding that the thermal stability of the resin composition is further improved by adding the organotin maleate compound.

The styrenic resin used in the present invention is a resin having a structure derived from a styrene skeleton in at least a part thereof and a blended resin thereof, and is a styrenic compound monomer such as styrene or α-methylstyrene. Polymers of side chain-substituted styrenes such as styrene and vinyltoluene, monomers of nucleus-substituted styrenes such as O-chlorostyrene, and styrene compound monomers and other compound monomers such as vinyl compound monomers, Examples thereof include copolymers with conjugated diene compound monomers and the like. Examples of vinyl compound monomers include cyan-containing vinyl compounds such as acrylonitrile,
Vinyl carboxylic acids such as acrylic acid and methacrylic acid,
Examples thereof include vinyl carboxylic acid esters such as methyl ester and ethyl ester, and vinyl heterocyclic compounds such as vinyl pyridine and vinyl carbazole. Examples of the conjugated diene compound include butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, ethylene-propylene-diene compound and the like.
The styrene resin may be a binary or more multi-component copolymer of a styrene compound monomer and the above compound monomer.

As the bromine-based flame retardant used in the present invention, those usually used in this field can be used without limitation, for example, tetrabromoethane, tetrabromobutane, hexabromocyclododecane, tetrabromobenzene, bromine. Styrene, bromophenylallyl ether, tetrabromophthalic anhydride, tribromophenol, pentabromotoluene, pentabromophenylpropyl ether, tetrabromobisphenol A, decabromodiphenylether, octabromodiphenylether, tris (2,3-dibromopropyl) isocyanurate , Polydibromophenylene oxide, carbonate oligomer of tetrabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether), tetrabu Arm bisphenol A bis (2,
3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (propyl ether),
2,3-dibromopropyl pentabromophenyl ether, bis (tribromophenoxy) ethane and the like can be mentioned. The amount of the brominated flame retardant added is not particularly limited, but may be appropriately changed depending on the required degree of flame retardancy, and is generally 5 to 100 parts by weight of the styrene resin.
It is preferable to use 35 parts by weight alone or in combination of two or more kinds.

Examples of the organic sulfonic acid metal salt or sulfuric acid ester metal salt used in the present invention include the general formula (1) and the general formula (2) [R ¹ (SO ₃ ) _n ] _m M (1) [In the formulas (1) and (2), R ¹ is an alkyl group, an alkylene group, an alkenyl group, an alkoxy group, a phenyl group, a naphthyl group and a phenyloxy group, R ² is an alkyl group, and n is 1 to 4 and m.
Is 1 to 4 and p is an integer of 1 to 4, and M is a monovalent to tetravalent metal. ] The compound shown by these is mentioned.

The general formulas (1) and (2) will be described in more detail. Examples of the alkyl group of R ¹ and R ² include an alkyl group having 1 to 30 carbon atoms, and specific examples include methyl, ethyl and propyl. And groups such as isopropyl, butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl and triaconyl.

Examples of the alkylene group, alkenyl group and alkoxy group represented by R ^{1 in} the general formula (1) include an alkylene group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms. Specifically, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, hexadecamethylene, octadecamethylene, allyl, oleyl, methoxy, ethoxy,
Propoxy, isopropoxy, butoxy, pentyloxy, octyloxy, decyloxy, dodecyloxy,
Mention may be made of groups such as tetradecyloxy, hexadecyloxy and octadecyloxy.

Further, the phenyl group, naphthyl group and phenyloxy group of R ^{1 in} the general formula (1) are an acyloxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 7 carbon atoms. ~ 24 alkylphenoxy group, hydroxyl group, carboxyl group, phenoxy group, vinyl group,
And may be substituted with halogen.

M is a metal having a valency of 1 to 4 and preferred among them is a metal of group I to group V, examples of which include Li, Na, K and M.
Examples thereof include metals such as g, Ca, Zn, Sr, Ba, Al, Sb, In, Zr and Sn.

Specific examples of the organic sulfonic acid metal salt and sulfuric acid ester metal salt represented by the general formula (1) include, for example, Li, Na, K, Mg, Ca,
Mention may be made of salts of Zn, Sr, Ba, Al, Sb, In, Zr, Sn with the following organic sulfonic acids and sulfates. Examples of the acid include methylsulfonic acid, butylsulfonic acid, octylsulfonic acid, decylsulfonic acid, dodecylsulfonic acid, octadecylsulfonic acid, allylsulfonic acid, oleylsulfonic acid, benzenesulfonic acid, P-toluenesulfonic acid, O. -Toluenesulfonic acid, P-octylbenzenesulfonic acid, O-octylbenzenesulfonic acid, P
-Dodecylbenzenesulfonic acid, m-dodecylbenzenesulfonic acid, O-dodecylbenzenesulfonic acid, 1,2
-Ethanedisulfonic acid, 1,3-propanedisulfonic acid, 1,4-butanedisulfonic acid, 1,6-hexanedisulfonic acid, 1,8-octanedisulfonic acid, 1,10
-Decanedisulfonic acid, 1,12-dodecanedisulfonic acid, benzenedisulfonic acid, P-vinylbenzenesulfonic acid, O-chlorobenzenesulfonic acid, P-fluorobenzenesulfonic acid, m-chlorobenzenesulfonic acid, P
-Chlorobenzenesulfonic acid, 2,4-dichlorobenzenesulfonic acid, P-bromobenzenesulfonic acid, P-iodobenzenesulfonic acid, phenol-2-sulfonic acid, anisole-O-sulfonic acid, phenetole-O-
Sulfonic acid, anisole-m-sulfonic acid, phenol-4-sulfonic acid, phenol-2,4-disulfonic acid, 2-oxytoluene-4-sulfonic acid, 2-oxytoluene-5-sulfonic acid, pyrocatexy-4- Sulfonic acid, resorcin-4-sulfonic acid, O-sulfobenzoic acid, m-sulfobenzoic acid, P-sulfobenzoic acid, 2-methyl-4-sulfobenzoic acid, methyl P-sulfobenzoate,
Octyloxybenzenesulfonic acid, octylphenoxybenzenesulfonic acid, octylphenoxyethoxyethylsulfonic acid, 5-sulfosalicylic acid, α-naphthalenesulfonic acid, 2-naphthol-1-sulfonic acid, 2-
Methylnaphthalene-1-sulfonic acid, and methylsulfate, butylsulfate, octylsulfate, dodecylsulfate, tetradecylsulfate, hexadecylsulfate, octadecylsulfate, phenylsulfate, octylphenylsulfate, dodecylphenylsulfate, polyoxyethyleneoctylethersulfate, polyoxy Examples thereof include ethylene octyl phenyl ether sulfuric acid and polyoxyethylene dodecyl phenyl ether sulfuric acid. Specific examples of the organic sulfonic acid metal salt represented by the general formula (2), for example, Li, Na, K, Mg, Zn, Sr, Ba, A
Mention may be made of salts of l, Sb, In, Zr, Sn with the following organic sulfonic acids. Examples of the acid include dibutylsulfosuccinic acid, dioctylsulfosuccinic acid, didecylsulfosuccinic acid, dioctadecylsulfosuccinic acid and the like.

Among the organic sulfonic acid metal salts of the general formulas (1) and (2) and the sulfuric acid ester metal salts, particularly preferable examples are P-toluenesulfonic acid, O-sulfobenzoic acid, 5-sulfosalicylic acid, octylsulfonic acid, dioctyl. It is a metal salt of Na, Zn, Ba and Ca of sulfosuccinic acid and dodecyl sulfate.

Examples of the organotin maleate compound used in the present invention include compounds generally used, and examples thereof include general formula (3) and general formula (4). [In the formulas (3) and (4), R ³ is an alkyl group, a cycloalkyl group,
Alkenyl group, aralkyl group, or alkoxyalkyl group, R ⁴ is an alkyl group, A is oxygen or —OOCCH═CHCOO—
, K is 0 or 1, and q is an integer of 1 to 10. ] The compound shown by these is mentioned.

More specifically describing formulas (3) and (4), R ³ may be an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, an aralkyl group or an alkoxyalkyl group. , Methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl,
Tridecyl, octadecyl, oleyl, benzyl, methylbenzyl, isopropylbenzyl, cyclohexyl,
Mention may be made of groups such as methoxyethyl, ethoxyethyl, methoxybutyl, butoxyethyl and the like.

R ⁴ is an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include groups such as methyl, butyl, octyl and lauryl.

Specific examples of the organotin ester maleate compound represented by the general formula (3) include the following.

Dimethyltin bis (methyl maleate), dimethyltin bis (ethyl maleate), dimethyltin bis (isopropyl maleate), dimethyltin bis (butyl maleate),
Dimethyltin bis (hexyl maleate), dimethyltin bis (octyl maleate), dimethyltin bis (isooctyl maleate), dimethyltin bis (2-ethylhexyl maleate), dimethyltin bis (decyl maleate), dimethyltin bis ( Dodecyl maleate), dimethyl tin bis (tridecyl maleate), dimethyl tin bis (octadecyl maleate), dimethyl tin bis (oleyl maleate), dimethyl tin bis (benzyl maleate), dimethyl tin bis (methyl benzyl maleate) ),
Dimethyltin bis (cyclohexyl maleate), dimethyltin bis (methoxybutyl maleate), dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate), dibutyltin bis (propyl maleate), dibutyltin bis ( Isopropyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (amyl maleate), dibutyl tin bis (hexyl maleate),
Dibutyltin bis (heptyl maleate), dibutyltin bis (octyl maleate), dibutyltin bis (isooctyl maleate), dibutyltin bis (2-ethylhexyl maleate), dibutyltin bis (nonyl maleate), dibutyltin bis ( Decyl maleate), dibutyl tin bis (dodecyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (octadecyl maleate), dibutyl tin bis (allyl maleate), dibutyl tin bis (oleyl maleate), dibutyl Tin bis (benzyl maleate), dibutyl tin bis (cyclohexyl maleate), dibutyl tin bis (methoxy butyl maleate), dioctyl tin bis (ethyl maleate),
Dioctyl tin bis (propyl maleate), dioctyl tin bis (isopropyl maleate), dioctyl tin bis (butyl maleate), dioctyl tin bis (hexyl maleate), dioctyl tin bis (octyl maleate), dioctyl tin bis (iso Octyl maleate),
Dioctyltin bis (2-ethylhexyl maleate),
Dioctyl tin bis (decyl maleate), dioctyl tin bis (dodecyl maleate), dioctyl tin bis (tridecyl maleate), dioctyl tin bis (octadecyl maleate), dioctyl tin bis (oleyl maleate), dioctyl tin bis (benzyl male) Ato), dioctyltin bis (cyclohexyl maleate), dioctyltin bis (methoxybutyl maleate), dilauryl tin bis (ethyl maleate), dilauryl tin bis (isopropyl maleate), dilauryl tin bis (butyl maleate), dilauryl Tin bis (hexyl maleate), dilauryl tin bis (octyl maleate), dilauryl tin bis (isooctyl maleate), dilauryl tin bis (2-ethylhexyl maleate), dilauryl tin bis (decyl maleate) Dilauryl tin bis (dodecyl maleate), dilauryl tin bis (tridecyl maleate), dilauryl tin bis (octadecyl maleate),
Dilauryl tin bis (oleyl maleate), dilauryl tin bis (benzyl maleate), dilauryl tin bis (cyclohexyl maleate), dilauryl tin bis (methoxybutyl maleate), bis (dimethyl tin methyl maleate) maleate, bis (dimethyl Tin ethyl maleate) maleate, bis (dimethyltin isopropyl maleate) maleate, bis (dimethyltin butyl maleate) maleate, bis (dimethyltin hexyl maleate) maleate, bis (dimethyltin octyl maleate) maleate, bis (dimethyl) Tin isooctyl maleate) maleate, bis (dimethyltin 2-ethylhexyl maleate) maleate, bis (dimethyltin decyl maleate) maleate, bis (dimethyltin dodecyl maleate) maleate, bis Dimethyltin tridecyl maleate) maleate, bis (dimethyltin octadecyl maleate) maleate, bis (dimethyltin oleyl maleate) maleate, bis (dimethyltin benzyl maleate) maleate, bis (dimethyltin cyclohexyl maleate) maleate, bis (Dimethyltin methoxybutyl maleate) maleate, bis (dimethyltin methyl maleate) maleate, bis (dibutyltin ethyl maleate) maleate, bis (dibutyltin propyl maleate) maleate, bis (dibutyltin isopropyl maleate) maleate, Bis (dibutyltin butyl maleate) maleate, bis (dibutyltin amyl maleate)
Maleate, bis (dibutyltin hexyl maleate) maleate, bis (dibutyltin heptyl maleate) maleate, bis (dibutyltin octyl maleate) maleate, bis (dibutyltin isooctyl maleate) maleate, bis (dibutyltin 2-ethylhexyl) Maleate) Maleate, bis (dibutyltin nonyl maleate)
Maleate, bis (dibutyltin decyl maleate) maleate, bis (dibutyltin dodecyl maleate) maleate, bis (dibutyltin tridecyl maleate) maleate, bis (dibutyltin octadecyl maleate) maleate, bis (dibutyltin allyl maleate) maleate , Bis (dibutyltin oleyl maleate) maleate, bis (dibutyltin benzyl maleate) maleate, bis (dibutyltin cyclohexyl maleate) maleate, bis (dibutyltin methoxybutyl maleate)
Maleate, bis (dioctyltin ethyl maleate) maleate, bis (dioctyltin propyl maleate) maleate, bis (dioctyltin isopropyl maleate) maleate, bis (dioctyltin butyl maleate) maleate, bis (dioctyltin hexyl maleate) Maleate, bis (dioctyltin octyl maleate) maleate, bis (dioctyltin isooctyl maleate) maleate, bis (dioctyltin 2-ethylhexyl maleate) maleate, bis (dioctyltin decyl maleate) maleate, bis (dioctyltin dodecyl maleate) ) Maleate, bis (dioctyltin tridecyl maleate) maleate, bis (dioctyltin octadecyl maleate) maleate, bis (dioctyltin oleyl maleate) Maleate, bis (dioctyltin benzyl maleate) maleate, bis (dioctyltin cyclohexyl maleate) maleate, bis (dioctyltin methoxybutyl maleate) maleate, bis (dilauryltin ethyl maleate) maleate, bis (dilauryltin isopropyl maleate) ) Maleate,
Bis (dilauryl tin butyl maleate) maleate, bis (dilauryl tin hexyl maleate) maleate, bis (dilauryl tin octyl maleate) maleate, bis (dilauryl tin isooctyl maleate) maleate, bis (dilauryl tin 2-ethylhexyl maleate) ) Maleate, bis (dilauryl tin decyl maleate) maleate, bis (dilauryl tin dodecyl maleate) maleate, bis (dilauryl tin tridecyl maleate) maleate, bis (dilauryl tin octadecyl maleate) maleate, bis (dilauryl tin oleyl maleate) Maleate, bis (dilauryl tin benzyl maleate) maleate, bis (dilauryl tin cyclohexyl maleate) maleate, bis (dilauryl tin methoxybutyl maleate) Leate, bis (dimethyltin methyl maleate) oxide, bis (dimethyltin butyl maleate) oxide, bis (dimethyltin isooctyl maleate) oxide, bis (dimethyltin benzyl maleate) oxide, bis (dibutyltin methyl maleate) ) Oxide, bis (dibutyltin butyl maleate) oxide, bis (dibutyltin isooctyl maleate) oxide, bis (dibutyltin benzyl maleate) oxide, bis (dioctyltin butyl maleate) oxide, bis (dioctyltin isooctyl) Maleate) oxide, bis (dioctyltin benzyl maleate) oxide, bis (dilauryl tin butyl maleate) oxide, bis (dilauryl tin isooctyl maleate) oxide, bis (dilauryl) Benzyl maleate) oxide and the like. Preferred examples are dibutyltin bis (methyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (isooctyl maleate), dibutyl tin bis (2-ethylhexyl maleate). ), Dibutyltin bis (tridecyl maleate), dibutyltin bis (octadecyl maleate), dibutyltin bis (oleyl maleate), dibutyltin bis (benzyl maleate), dibutyltin bis (cyclohexyl maleate), dioctyltin Bis (butyl maleate), dioctyl tin bis (isooctyl maleate),
Dioctyltin bis (2-ethylhexyl maleate),
Dioctyl tin bis (tridecyl maleate), dioctyl tin bis (octadecyl maleate), dioctyl tin bis (oleyl maleate), dioctyl tin bis (benzyl maleate), dioctyl tin bis (cyclohexyl maleate), bis (dibutyl tin) Methyl maleate) maleate, bis (dibutyltin butyl maleate) maleate, bis (dibutyltin isooctyl maleate) maleate, bis (dibutyltin 2-ethylhexyl maleate) maleate, bis (dibutyltin tridecyl maleate) maleate, Bis (dibutyltin octadecyl maleate) maleate, bis (dibutyltin oleyl maleate) maleate, bis (dibutyltin benzyl maleate) maleate, bis (dibutyltin cyclohexyl maleate) maleate, Sus (dioctyl tin butyl maleate) maleate, bis (dioctyl tin isooctyl maleate) maleate, bis (dioctyl tin 2-ethylhexyl maleate) maleate, bis (dioctyl tin tridecyl maleate) maleate, bis (dioctyl tin octadecyl maleate) Eth) maleate, bis (dioctyltin oleyl maleate) maleate, bis (dioctyltin benzyl maleate) maleate, bis (dioctyltin cyclohexyl maleate) maleate, bis (dibutyltin methyl maleate) oxide, bis (dibutyltin butyl maleate) Acid), bis (dibutyltin benzyl maleate) oxide, bis (dioctyl tin butyl maleate) oxide, bis (dioctyl tin benzyl maleate) oxide, etc. Rukoto can. Specific examples of the organic tin maleate represented by the general formula (4) include the following. Dimethyl tin maleate, dibutyl tin maleate, dioctyl tin maleate,
Examples thereof include dilauryl tin maleate and polymers thereof.

In the present invention, the addition amount of the organic sulfonic acid metal salt and / or the sulfuric acid ester metal salt can be used without particular limitation based on 100 parts by weight of the styrene resin composition flame-retarded with the bromine flame retardant. However, the effective range is 0.05 to 5.0 parts by weight. If it is less than 0.05 parts by weight, the heat stabilizing effect is not noticeable, and if it exceeds 5.0 parts by weight, the expected heat stabilizing effect is not seen, and preferably, it is not more than 0.
1 to 3.0 parts by weight.

The combination ratio of the organic sulfonic acid metal salt and / or the sulfuric acid ester metal salt and the organic tin maleate compound is not particularly limited, and they can be used in an arbitrary ratio. However, when the ratio of the organic sulfonic acid metal salt and / or the sulfuric acid ester metal salt and the organic tin maleate compound is used in the range of 9: 1 to 3: 7, a preferable effect is obtained, and the total amount of the resin added is The composition can be used without limitation. However, the effective range is 0.05 to 5.0 parts by weight. If it is less than 0.05 parts by weight, the heat stabilizing effect is not noticeable, and if it exceeds 5.0 parts by weight, the expected heat stabilizing effect is not observed, and the amount is preferably 0.1 to 3.0 parts by weight.

The method of adding the stabilizer used in the present invention to a styrene resin composition flame-retarded with a bromine flame retardant may be carried out by a conventionally known technique, for example, the resin composition and the stabilizer. May be mixed with a Henschel mixer, a ribbon blender, a Banbury mixer, or the like, or one obtained by prepacking an organic sulfonic acid metal salt and / or a sulfuric ester metal salt and an organic tin maleate compound in advance with the resin composition. You may mix with the mixer.

Further, known stabilizers such as various metal soaps, organic phosphorus compounds, and organic tin-containing sulfur compounds can be used in combination with these stabilizers.

Further, if necessary, a plasticizer, a lubricant, an antioxidant, a pigment,
Fillers, processing aids and the like can be added.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, parts means parts by weight.

Example 1 Acrylonitrile-butadiene-styrene copolymer [JSR ABS # 1ONP, manufactured by Japan Synthetic Rubber Co., Ltd.] 10
Part 0, Tetrabrom Bisphenol A [Teijin Kasei Co., Ltd.
A mixture having 25 parts of Fireguard 2000] added with the stabilizer shown in [Table 1] was kneaded with an 8-inch test roll adjusted to 130 ° C. for 5 minutes, and then a sample having a thickness of 0.5 mm was prepared. After cutting the obtained sheets, 8 sheets are stacked and 240
Pressing was carried out at 10 ° C and 10 kg / cm ² , and the test piece after pressing was taken out, and the degree of coloring was visually judged, and the deterioration time (minute) until it became blackish brown was judged.

Example 2 Acrylonitrile / butadiene / styrene copolymer [JSR ABS # 10NP, manufactured by Japan Synthetic Rubber Co., Ltd.] 100
Part, tetrabrom bisphenol A [Teijin Kasei Co., Ltd. Fireguard 2000] 20 parts, antimony trioxide 3.
13 parts of the composition obtained by adding the stabilizer shown in [Table-2] to 0 part
After kneading with an 8-inch test roll adjusted to 0 ° C. for 5 minutes, a sample having a thickness of 0.5 mm was prepared.

After cutting the obtained sheets, 8 sheets were piled up at 240 ° C, 10 Kg / c
Pressing was performed at m ² , and the test piece after pressing was taken out, and the degree of coloring was visually judged, and the deterioration time (minute) until it became blackish brown was judged.

Example 3 Styrene resin [Styron 492, manufactured by Asahi Kasei Corporation] 1
00 parts, 10 parts of hexabromocyclododecane [Piroguard SR-103 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] [Table-3]
The composition containing the stabilizer shown in was adjusted to 120 ° C. 8
The sheets were kneaded with an inch test roll for 5 minutes to prepare a sheet having a thickness of 0.8 mm.

After cutting the obtained sheets, 8 sheets were piled up, 220 ° C, 10 Kg / c
After pressing at m ² for 60 minutes, the sample is taken out and the degree of coloring is judged with the naked eye, and the deterioration time (minutes) until it becomes grayish brown
It was judged by.

[Effects of the Invention] When stabilizing a styrene resin composition containing a bromine flame retardant, excellent thermal stability can be imparted by adding an organic sulfonic acid metal salt and / or a sulfuric acid ester metal salt. .

Furthermore, by further adding an organic sulfonic acid metal salt and / or a sulfuric acid ester metal salt and an organic tin maleate compound in combination, it is possible to impart more excellent thermal stability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C08L 55/02 LMC 7142-4J (72) Inventor Hisashi Ihara 788 Hisaji, Takatsu-ku, Kawasaki-shi, Kanagawa Prefecture Sankyo Organic Synthesis Co., Ltd. (72) Inventor Yoshimura Adult 788, Hisachi, Takatsu-ku, Kawasaki City, Kanagawa Sankyo Organic Synthesis Co., Ltd.

Claims (2)

[Claims] 1. Stabilization of a resin composition comprising a bromine flame retardant and a styrene resin, which is characterized by adding an organic sulfonic acid metal salt and / or a sulfuric ester metal salt when stabilizing the resin composition. Chemical method. 2. When stabilizing a resin composition comprising a bromine flame retardant and a styrene resin, an organic sulfonic acid metal salt and / or a sulfuric ester metal salt and an organic tin maleate compound are added together. And a method for stabilizing the resin composition.