JPH06879B2 - Method for stabilizing styrene resin composition - Google Patents

Description

The present invention relates to heat stabilization of a styrene resin composition containing a halogen-containing compound as a flame retardant,
It can be widely used in fields where flame retardancy is required for styrene resins.

[Conventional technology]

In general, a method of adding a halogen-containing compound has been conventionally performed to make a styrene resin flame-retardant. However, in general, when the styrene-based resin is made flame-retardant by the above method, there is a drawback that the thermal stability originally possessed by the styrene-based resin is significantly lowered.

Therefore, conventionally, in order to thermally stabilize the styrene resin composition containing a halogen-containing compound, as a stabilizer, an organotin compound, various metal soaps, epoxy compounds,
A method of adding a phosphorus compound or an antioxidant or adding a maleic acid metal salt (Japanese Patent Publication No. 56-54023) is disclosed.

[Problems to be solved by the invention]

Among the above-mentioned stabilization methods, the method of adding an organotin compound is widely used because it suppresses a decrease in thermal stability of a styrene-based resin composition flame-retarded with a halogen-containing compound. Is not yet satisfactory,
Furthermore, the development of a stabilizer having an excellent heat stabilizing effect has been awaited.

[Means for solving problems]

From such a viewpoint, the inventors of the present invention have earnestly studied a stabilizer having an excellent heat stabilizing effect on a styrene-based resin composition flame-retarded with a halogen-containing compound, and as a result, 100 parts of the styrene-based resin are obtained. Flame-retardant styrene resin composition 10 comprising 10 to 150 parts of a halogen-containing compound
0.05 to 10 parts by weight of (a) the organotin maleate compound and / or the organotin mercaptide compound, and (b) the general formula (1) MOOC (CH ₂ ) _n COOM ′ (1 (In the formula, M and M ′ represent monovalent metal atoms and may be the same or different. N represents an integer of 1 to 18.) Saturated dicarboxylic acid dimetal salt 0.005 to 5 ．
It has been found that, when added in combination with 0 part by weight, these stabilizers exert an unexpected synergistic effect from the thermal stabilizing effect when these stabilizers are added to the resin composition alone. completed.

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.

The halogen-containing compound used in the present invention is a halogen-containing resin such as vinyl chloride resin, chlorinated vinyl chloride resin or chlorinated polyethylene; chlorinated paraffin, chlorinated polyphenyl, brominated polyphenyl, perchlorpentacyclodecane, tetrabromide. Butane, hexabromocyclododecane, tetrabromobenzene, vinyl chloroacetate,
Bromstyrene, bromophenyl allyl ether, diallyl chlorendate, hettic acid, hettic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chloropropanediol, tetrabromobisphenol A,
Decabromodiphenyl ether, tris (2,3 dibromopropyl) isocyanurate, a carbonate oligomer of tetrabromobisphenol A, a halogen compound such as bis (tribromophenoxy) ethane, and the like.

In the present invention, the mixing ratio of the styrene resin and the halogen-containing compound is different in the requirement of flame retardancy depending on the purpose of use of the molded product, and the mixing ratio also varies depending on the purpose, but generally,
The amount of the halogen-containing compound added is 10 to 150 parts by weight with respect to 100 parts by weight of the styrene resin.

Examples of the organotin maleate compound used in the present invention include commonly used compounds.
(2) and (3) [In the formulas (2) and (3), R ¹ is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an alkoxyalkyl group, R ² is an alkyl group, A is oxygen or -OOCCH = C.
In the group represented by HCOO-, k is 0 or 1, and l is an integer of 1-10. ] Is mentioned.

When the general formulas (2) and (3) are described in detail, R ¹ has ¹ carbon atom.
~ 18 alkyl groups, cycloalkyl groups, alkenyl groups,
Examples thereof include aralkyl group and alkoxyalkyl group, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl,
2-ethylhexyl, decyl, dodecyl, tridecyl,
Octadecyl, oleyl, benzyl, methylbenzyl,
Examples include groups such as isopropylbenzyl, cyclohexyl, methoxyethyl, ethoxyethyl, methoxybutyl, butoxyethyl and the like.

R ² 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 maleate compound represented by the general formula (2) include the following.

Dimethyltin bis (methyl maleate), dimethyltin bis (ethyl maleate), dimethyltin bis (isopropyl maleate), dimethyltin bis (butyl maleate),
Dimer tin bis (hexyl maleate), dimethyl tin bis (octyl maleate), dimethyl tin bis (isooctyl maleate), dimethyl tin bis (2-ethylhexyl maleate), dimethyl tin bis (decyl maleate),
Dimethyltin bis (dodecyl maleate), dimethyltin bis (tridecyl maleate), dimethyltin bis (octadecyl maleate), dimethyltin bis (oleyl maleate), dimethyltin bis (benzyl maleate), dimethyltin bis ( Methyl endyl maleate), dimethyl tin bis (cyclohexyl maleate), dimethyl tin bis (methoxybutyl maleate), dibutyl tin bis (methyl maleate), dibutyl tin bis (ethyl maleate), dibutyl tin bis (propyl male) A), dibutyltin bis (isopropyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (amyl maleate), dibutyltin bis (hexyl maleate), dibutyltin bis (heptyl maleate), dibutyltin bis ( Octyl maleate), Butyltin bis (isooctyl maleate), dibutyltin bis (2-ethylhexyl maleate), dibutyltin bis (Nonirumareeto)
Dibutyltin bis (decyl maleate), dibutyltin bis (dodecyl maleate), dibutyltin bis (tridecyl maleate), dibutyltin bis (octadecyl maleate), dibutyltin bis (allyl maleate), dibutyltin bis (oleyl maleate) Ate), dibutyltin bis (benzyl maleate), dibutyltin bis (cyclohexyl maleate), dibutyltin bis (methoxybutyl maleate), dioctyltin bis (ethyl maleate), dioctyltin 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 (isooctyl maleate), dioctyl tin bis (2) -Eti Hexyl 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 maleate), dioctyl tin bis (cyclohexyl maleate), dioctyl tin 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 (dimethyltin methyl maleate) maleate, bis (dimethyltin ethyl maleate) maleate,
Bis (dimethyltin isopropyl maleate) maleate, bis (dimethyltin butyl maleate) maleate,
Bis (dimethyltin hexyl maleate) maleate, bis (dimethyltin octyl maleate) maleate, bis (dimethyltin 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 (dibutyltin 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) malee 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 (dilauryltin butyl maleate) maleate, bis (dilauryltin hexyl maleate) maleate, bis (dilauryltin octyl maleate) maleate, bis (dilauryltin isooctyl maleate) Ate) maleate, bis (dilauryltin 2-ethylhexyl maleate) maleate, bis (dilauryltin decyl maleate) maleate, bis (dilauryltin 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) Ate) maleate, bis (dilauryltin methoxybutyl maleate) maleate, 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 Ate) oxide, bis (dioctyltin benzyl maleate) oxide, bis (dilauryl tin butyl maleate) oxide, bis (dilauryl tin isooctyl maleate)
Oxide, bis (dilauryl tin benzyl maleate)
Oxide and the like, and preferable examples are dibutyltin bis (methyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (isooctyl maleate), dibutyltin bis (2-ethylhexyl maleate), dibutyltin. Bis (tridecyl maleate), dibutyl tin bis (octadecyl maleate), dibutyl tin bis (oleyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin bis (cyclohexyl maleate), dioctyl tin bis (butyl male) Ato), dioctyltin bis (isooctyl maleate), dioctyltin bis (2-ethylhexyl maleate), dioctyltin bis (tridecyl maleate), dioctyltin bis (octadecyl maleate), dioctyltin bis (oleyl maleate) ), Geoc Le tin bis (benzyl maleate), dioctyltin bis (cyclohexyl maleate), bis (dibutyltin 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, bis (dioctyltin butyl maleate) Maleate, bis (dioctyltin isooctyl maleate) maleate, bis (dioctyltin 2-ethylhexyl maleate) maleate, bis (dioctyltin tridecyl maleate) maleate, bis (dioctyltin octadecyl maleate) maleate, bis (dioctyltin) Oleyl maleate) maleate, bis (dioctyltin benzyl maleate) maleate, bis (cyclohexyl maleate dioctylate) maleate, bis (dibutyltin methyl maleate) G) oxide, may be mentioned bis (dibutyltin butyl maleate) oxide, bis (dibutyltin benzyl maleate) oxide, bis (dioctyltin butyl maleate) oxide, bis (dioctyltin benzyl maleate) oxide, and the like. Specific examples of the organotin maleate metering compound represented by the general formula (3) include the following. Examples include dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, dilauryltin maleate and polymers thereof. Among the organotin maleate compounds represented by the general formulas (2) and (3), particularly preferable examples are dibutyltin bis (methyl maleate), dibutyltin maleate polymer, dioctyltin maleate polymer and the like.

Organotin mercaptide compounds used in the present invention can include compounds commonly used, for example, the general formula (4) and (5) [In the formulas (4) and (5), R ³ is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an alkoxyalkyl group, R ⁴ is an alkyl group, an alkoxycarbonylalkyl group, B is oxygen, and B ′ is sulfur. Or -S (CH ₂ ) _p COO
- group represented by, p is an integer of 1 or 2, X is group represented by ^{R 4} or ^{_{-S (CH 2) p COOR 3}} , m is 0 or 1, n is an integer from 1 to 10. ] Is mentioned.

When the general formulas (4) and (5) are described in detail, R ³ has 1 carbon atom.
~ 18 alkyl groups, cycloalkyl groups, alkenyl groups,
Examples thereof include aralkyl group and alkoxyalkyl group, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl,
2-ethylhexyl, decyl, dodecyl, tridecyl,
Octadecyl, oleyl, benzyl, methylbenzyl,
Examples include groups such as cyclohexyl, isopropylbenzyl, methoxyethyl, ethoxyethyl, methoxybutyl, butoxyethyl and the like.

R ⁴ is an alkyl group having 1 to 12 carbon atoms or an alkoxycarbonylalkyl group, and specific examples thereof include methyl, butyl, octyl, lauryl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylethyl, Examples thereof include groups such as 2-octoxycarbonylethyl. Specific examples of the organotin mercaptide compound represented by the general formula (4) include the following.

Monomethyltin tris (isooctyl mercaptoacetate), monomethyltin tris (2-ethylhexyl malecaptoacetate), monomethyltin tris (octadecyl mercaptoacetate), monomethyltin tris (oleyl mercaptoacetate), monomethyltin tris (methoxybutyl mercaptoacetate), Monobutyltin tris (butylmercaptoacetate), monobutyltin tris (octylmercaptoacetate), monobutyltin tris (isooctylmercaptoacetate), monobutyltin tris (2-ethylhexylmercaptoacetate), monobutyltin tris (octadecylmercaptoacetate), monobutyltin Tris (oleyl mercaptoacetate), monobutyltin tris (benzyl mercaptoacetate), Butyltin tris (methoxybutyl mercaptoacetate), monooctyltin tris (butylmercaptoacetate), monooctyltin tris (octylmercaptoacetate), monooctyltin tris (isooctylmercaptoacetate), monooctyltin tris (2-ethylhexylmercapto) Acetate), monooctyltin tris (methoxybutylmercaptoacetate), mono (2-methoxycarbonylethyl) tin tris (isooctylmercaptoacetate),
Mono (2-ethoxycarbonylethyl) tin tris (isooctylmercaptoacetate), mono (2-butoxycarbonylethyl) tin tris (isooctylmercaptoacetate), mono (2-octoxycarbonylethyl) tin tris (isooctylmethylcapto) Acetate), dimethyltin bis (isooctylmethylcaptoacetate), dimethyltin bis (2-ethylhexylmercaptoacetate), dimethyltin bis (octadecylmercaptoacetate), dimethyltin bis (oleylmercaptoacetate), dimethyltin bis (methoxybutylmercapto) Acetate), dibutyltin bis (butylmercaptoacetate), dibutyltin bis (octylmercaptoacetate), dibutyltin bis (isooctylmethylcaptoacetate), Butyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin bis (octadecylmethylcaptoacetate), dibutyltin bis (oleylmercaptoacetate), dibutyltin bis (benzylmercaptoacetate), dibutyltin bis (cyclohexylmethylcaptoacetate), dibutyl Tin bis (methoxybutyl mercaptoacetate), dioctyl tin bis (butyl mercapto acetate), dioctyl tin bis (octyl mercapto acetate), dioctyl tin bis (isooctyl mercapto acetate), dioctyl tin bis (2-ethylhexyl captoacetate), dioctyl tin Bis (methoxybutylmercaptoacetate), bis (2-methoxycarbonylethyl) tin bis (isooctylmercaptoacetate), bis 2
-Ethoxycarbonylethyl) tin bis (isooctylmethylcaptoacetate), bis (2-butoxycarbonylethyl) tin bis (isooctylmercaptoacetate), bis (2-octoxycarbonylethyl) tin bis (isooctylmethylcaptoacetate) , Bis (dimethyltin isooctyl mercaptoacetate) oxide, bis (dimethyltin 2-ethylhexylmercaptoacetate) oxide, bis (dibutyltin isooctylmercaptoacetate) oxide, bis (dibutyltin 2-ethylhexylmercaptoacetate) oxide, bis (dioctyl) Tin isooctyl mercaptoacetate) oxide, bis (dioctyltin 2-ethylhexylmethylcaptoacetate) oxide, monomethyltin tris (isooctyl) - mercaptopropionate), monomethyl tin tris (2-ethylhexyl 3-mercaptopropionate), monomethyl tin tris (octadecyl 3-mercaptopropionate), monomethyl tin tris (oleyl 3-mercaptopropionate),
Monomethyltin tris (methoxybutyl 3-mercaptopropionate), monobutyltin tris (butyl 3-methylcaptopropionate), monobutyltin tris (octyl 3-mercaptopropionate), monobutyltin tris (isooctyl 3-mercaptopropionate) Peonate),
Monobutyltin tris (2-ethylhexyl 3-mercaptopropionate), monobutyltin tris (octadecyl 3-mercaptopropionate), monobutyltin tris (oleyl 3-mercaptopropionate), monobutyltin tris (benzyl 3-mercaptopropionate) Pionate), monobutyltin tris (methoxybutyl 3-mercaptopropionate), monooctyltin tris (butyl 3-mercaptopropionate), monooctyltin tris (octyl 3-mercaptopropionate), monooctyltin tris (Isooctyl 3-mercaptopropionate), monooctyltin tris (2-ethylhexyl 3-mercaptopropionate), monooctyltin tris (methoxybutyl 3-mercaptopropionate),
Monolauryl tin tris (2-ethylhexyl 3-mercaptopropionate), mono (2-methoxycarbonylethyl) tin tris (isooctyl 3-mercaptopropionate), mono (2-ethoxycarbonylethyl) tin tris (isooctyl 3- Mercaptopropionate), mono (2-butoxycarbonylethyl) tin tris (isooctyl-3-mercaptopropionate), mono (2-octoxycarbonylethyl) tin tris (isooctyl-3-mercaptopropionate), dimethyltin bis (Isooctyl 3-mercaptopropionate), dimethyltin bis (2-ethylhexyl 3-mercaptopropionate), dimethyltin bis (octadecyl 3-mercaptopropionate), dimethyltin bis (oleyl 3)
-Mercaptopropionate), dimethyltin bis (methoxybutyl 3-mercaptopropionate), dibutyltin bis (butyl 3-mercaptopropionate), dibutyltin bis (octyl 3-mercaptopropionate), dibutyltin bis (Isooctyl 3-mercaptopropionate) dibutyltin bis (2-ethylhex-3-
Mercaptopropionate), dibutyltin bis (octadecyl 3-mercaptopropionate), dibutyltin bis (oleyl 3-mercaptopropionate), dibutyltin bis (benzyl 3-mercaptopropionate), dibutyltin bis (cyclohexyl 3) -Mercaptopropionate), dibutyltin bis (methoxybutyl 3-mercaptopropionate), dioctyltin bis (butyl 3-)
Mercaptopropionate), dioctyltin bis (octyl 3-mercaptopropionate), dioctyltin bis (isooctyl 3-mercaptopropionate), dioctyltin bis (2-ethylhexyl 3-mercaptopropionate), dioctyltin bis (Methoxybutyl 3
-Mercaptopropionate), dilauryl tin bis (2
-Ethylhexyl 3-mercaptopropionate), bis (2-methoxycarbonylethyl) tin bis (isooctyl 3-mercaptopropionate), bis (2-ethoxycarbonylethyl) tin bis (isooctyl 3-mercaptopropionate), Bis (2-butoxycarbonylethyl) tin bis (isooctyl 3-mercaptopropionate), bis (2-octoxycarbonylethyl)
Tin bis (isooctyl 3-mercaptopropionate), bis (dimethyltin isooctyl 3-mercaptopropionate) oxide, bis (dimethyltin 2-ethylhexyl 3-mercaptopropionate) oxide, bis (dibutyltin isooctyl 3-mercapto) Propionate) oxide, bis (dibutyltin 2-ethylhexyl 3-mercaptopropionate) oxide,
Examples thereof include bis (dioctyltin isooctyl 3-mercaptopropionate) oxide and bis (dioctyltin 2-ethylhexyl 3-mercaptopropionate) oxide. Preferred examples are dibutyltin bis (isooctylmercaptoacetate) and dibutyltin bis. (2-ethylhexyl mercapto acetate), dioctyl tin bis (isooctyl mercapto acetate), dioctyl tin bis (2-ethyl hexyl mercapto acetate),
Dibutyltin bis (isooctyl 3-mercaptopropionate), dibutyltin bis (2-ethylhexyl 3-mercaptopropionate), dibutyltin bis (methoxybutyl 3-mercaptopropionate), dioctyltin bis (isooctyl 3-mercapto) Propionate),
Dioctyltin bis (2-ethylhexyl 3-mercaptopropionate), bis (dibutyltin isooctyl 3-
Mercaptopropionate) oxide, bis (dibutyltin 2-ethylhexyl 3-mercaptopropionate) oxide, bis (dioctyltin isooctyl 3-)
Examples thereof include mercaptopropionate) oxide and bis (dioctyltin 2-ethylhexyl 3-mercaptopropionate) oxide. Particularly preferred examples are dibutyltin bis (isooctylmercaptoacetate) and dibutyltin bis (2-ethylhexylmercapto). Acetate), dioctyl tin bis (isooctyl mercapto acetate), dioctyl tin bis (2-ethylhexyl mercapto acetate), and the like.

Examples of the organotin mercaptide compound represented by the general formula (5) include the following.

Dimethyltin mercaptoacetate, dibutyltin mercaptoacetate, dioctyltin mercaptoacetate, dilauryltin mercaptoacetate, bis (2-butoxycarbonylethyl) tin mercaptoacetate, dimethyltin 3-mercaptopropionate, dibutyltin 3-mercaptopropionate, Dioctyltin 3-mercaptopropionate, dilauryltin 3-mercaptopropionate, bis (2-butoxycarbonylethyl) tin 3-mercaptopropionate, dimethyltin sulphide, dibutyltin sulphide, dioctyltin sulphide, dilauryltin sulphide, Bis (2-butoxycarbonylethyl) tin sulphide and polymers thereof, etc., preferably dibutyltin 3-mercaptopropionate, dioctyl 3-mercaptopropionate, dibutyltin Sarufuaido can include dioctyltin Sarufuaido and their polymers.

In the general formula (1) used in the present invention, M and M'represent monovalent metal atoms, preferably Li, Na and K, and preferred specific examples of the compound represented by the general formula (1) Are the following:

Dilithium propanedioate, disodium propanedioate,
Dipotassium propanedioate, dilithium butanedioate, disodium butanedioate, dipotassium butanedioate, dilithium pentanedioate, disodium pentanedioate, dipotassium pentanedioate, sodium potassium pentanedioate,
Dilithium hexanedioate, disodium hexanedioate,
Dipotassium hexanedioate, dilithium heptanedioate, disodium heptanedioate, dipotassium heptanedioate, dilithium octanedioate, disodium octanedioate, dipotassium octanedioate, dilithium nonanedioate, disodium nonanedioate, nonanedioate Dipotassium acid, dilithium decanedioate, disodium decanedioate, dipotassium decanedioate, dilithium undecanedioate, disodium undecanedioate, dipotassium undecanedioate, dilithium dodecanedioate, disodium dodecanedioate, dipotassium dodecanedioate , Dilithium tridecanedioate, disodium tridecanedioate, dipotassium tridecanedioate, dilithium tetradecanedioate, disodium tetradecanedioate, dipotassium tetradecanedioate, dilithium pentadecanedioate, pentade Disodium diphosphate, dipotassium pentadecanedioate, dilithium hexadecanedioate, disodium hexadecanedioate, dipotassium hexadecanedioate, dilithium heptadecanedioate, disodium heptadecanedioate, dipotassium heptadecanedioate, dilithium octadecanedioate, octadecanedioate Disodium acid, dipotassium octadecanedioate, dilithium nonadecanedioate, disodium nonadecanedioate, dipotassium nonadecanedioate, dilithium eicosane diacid, disodium eicosane diacid, dipotassium aicosane diate, lithium sodium butanedioate, butane dibutane Sodium / potassium acid, sodium / potassium hexanedioate, lithium / potassium hexanedioate, lithium / sodium hexanedioate, and the like are particularly preferable examples. Is then, hexanedioic acid dilithium, hexanedioic acid disodium,
Examples thereof include dipotassium hexanedioate, lithium / sodium hexanedioate, sodium / potassium hexanedioate, and lithium / potassium hexanedioate.

In the present invention, the addition amount of the organotin maleate compound and / or the organotin mercaptide compound is not particularly limited with respect to 100 parts by weight of the styrene resin composition flame-retarded with the halogen-containing compound, but is usually 0.05 to 10 parts by weight, less than 0.05 parts by weight has a small thermal stabilizing effect,
If it exceeds 10 parts by weight, the expected heat stabilizing effect is not observed, and it is preferably 0.1 to 6.0 parts by weight. Also, the general formula (1)
The addition amount of the saturated dicarboxylic acid dimetal salt is not particularly limited, but is usually 0.005 to 5.0 parts by weight, and 0.005
If it is less than 5 parts by weight, no additional effect is observed, and if it exceeds 5.0 parts by weight, the heat stabilizing effect is rather lowered. Preferably
0.01 to 2.0 parts by weight.

The method of adding the stabilizer used in the present invention to a styrene resin composition flame-retarded with a halogen-containing compound is
It may be carried out by a conventionally known technique. For example, the resin composition and the stabilizer are mixed with a Henschel mixer, a ribbon blender,
It may be mixed with a Banbury mixer, or
The organotin maleate-based compound and / or the organotin mercaptide-based compound and the saturated dicarboxylic acid dimetal salt represented by the general formula (1) may be mixed in advance with the resin composition by the above mixer.

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

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

[Examples and effects]

Hereinafter, the present invention will be specifically described 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 [Toughlex TFX-410 manufactured by Mitsubishi Monsanto Kasei Co., Ltd.] 50
Section, vinyl chloride resin [Neon Zeon Co., Ltd. Geon 103EP-
8] A mixture containing 50 parts of the stabilizer shown in [Table-1] was kneaded for 5 minutes with an 8-inch test roll adjusted to 155 ° C to prepare a sheet having a thickness of 0.5 mm.

After cutting the obtained sheets, eight sheets were piled up and pressed at 210 ° C. and 20 kg / cm ² for 60 minutes, the test pieces after the pressing were taken out, and the coloring degree was visually judged. As can be seen from [Table-1], the combined use of the organotin maleate compound and / or the organotin metal captide compound of the present invention and disodium hexanedioate improves the heat stabilizing effect.

Example 2 100 parts of acrylonitrile-butadiene-styrene copolymer [JSRABS ^# 10NP, manufactured by Japan Synthetic Rubber Co., Ltd.], tetrabrom bisphenol A [Fairguard manufactured by Teijin Chemicals, Ltd.]
2000] A mixture containing 25 parts of the stabilizer shown in Table 2 was kneaded for 5 minutes with an 8-inch test roll adjusted to 130 ° C. to prepare a sheet having a thickness of 0.5 mm. The obtained sheets were cut and stacked on eight sheets, and the sheets were pressed at 240 ° C. and 10 kg / cm ² for 30 minutes, and the test pieces after the pressing were taken out and their coloring degree was visually judged. As can be seen from [Table-2], the additive effect of the stabilizer according to the present invention is remarkably excellent.

Example 3 Styrene resin [Styron 492, manufactured by Asahi Kasei Corporation] 100
Part, hexabromocyclododecane [Daiichi Kogyo Seiyaku Co., Ltd.
Manufactured by Pyrogard SR-103] 15, 0.3 parts of di-n-butyltin maleate polymer with the stabilizer shown in [Table 3] was kneaded for 5 minutes with an 8-inch test roll adjusted to 120 ° C. A sheet having a thickness of 0.7 mm was produced. After cutting the obtained sheets, eight sheets were stacked and pressed at 230 ° C. and 10 kg / cm ² , and the time (minutes) until the test piece deteriorates (blackened) was measured.

As can be seen from [Table 3], the stabilizing effect of the stabilizer according to the present invention is remarkably excellent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirokazu Ono 788 Hisachi, Takatsu-ku, Kawasaki-shi, Kanagawa Sankyo Organic Synthesis Co., Ltd. (72) Adult Yoshimura 788 Hisachi, Takatsu-ku, Kawasaki-shi, Kanagawa Sankyo Organic Synthesis Co., Ltd. In-house (56) Reference JP 47-43037 (JP, A) JP 61-155438 (JP, A) JP 60-139734 (JP, A)

Claims (1)

[Claims] 1. An organic tin maleate-based compound and / or (a) based on 100 parts by weight of a flame-retardant styrene-based resin composition comprising 100 parts by weight of a styrene-based resin and 10 to 150 parts by weight of a halogen-containing compound. 0.05 to 10 parts by weight of the organotin mercaptide compound, and (b) the general formula MOOC (CH ₂ ) _n COOM '(wherein M and M'represent a monovalent metal atom and may be the same or different. N represents an integer of 1 to 18) 0.005 to 5.
A method for stabilizing the resin composition, characterized in that the resin composition is added together in a proportion of 0 part by weight.