JPH0676527B2 - Method for stabilizing 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, or antimony trioxide has been conventionally performed. Among these flame retardants, Halogen-based compounds, especially bromine-based 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 compounds (Japanese Patent Publication No. 59-41462)
No.), a method of adding a maleic acid metal salt (Japanese Patent Publication No. 56-540).
No. 23), phosphorus compounds, antioxidants and the like.

[Problems to be Solved by the Invention]

Among the above methods, the method of adding an organic tin compound or a metal salt of maleic acid is a stabilizer which suppresses a decrease in thermal stability but does not yet satisfy the thermal stabilizing effect, and which has a further excellent thermal stabilizing effect. Development was awaited.

[Means for Solving Problems] From such a viewpoint, the present inventors have conducted diligent research on a stabilizer having an excellent heat stabilizing effect on a resin composition obtained by adding a bromine flame retardant to a styrene resin. As a result, with respect to the resin composition comprising the bromine flame retardant and the styrene resin,
The present invention has been completed by finding that the thermal stability of the resin composition is remarkably improved by the additive effect by adding the maleate compound and boric acid or boric anhydride together.

The styrene 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 blend resin thereof, and a styrene compound monomer such as styrene or α-methyl. Polymers of side chain-substituted styrene such as styrene and monomers such as vinyltoluene and nucleus-substituted styrene such as o-chlorostyrene, and styrene compound monomers and other compound monomers such as vinyl compound monomers And a copolymer with a conjugated diene compound monomer 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, vinyl carboxylic acid esters such as methyl ester and ethyl ester thereof, vinyl pyridine, vinyl carbazole such as vinyl carbazole. Examples thereof include heterocyclic compounds.
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, bromophenyl allyl ether, tetrabromophthalic anhydride, tribromophenol, tetrabromobisphenol A, decabromodiphenyl ether, octabromodiphenyl ether, tris (2,3-dibromopropyl) isocyanurate, polydibromo Phenylene oxide, carbonate oligomer of tetrabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether),
Tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (propyl ether), bis (tribromophenoxy) Examples include ethane. The amount of the brominated flame retardant added is not particularly limited, but may be appropriately varied depending on the degree of flame retardancy required, and generally 5 to 35 parts by weight with respect to 100 parts by weight of the styrene resin, either alone or in two kinds. It is preferable to use them together.

Examples of maleate compounds used in the present invention include:
Examples thereof include organic tin maleate compounds and metal maleate compounds.

Examples of the organic tin maleate compound include compounds that are commonly used, and examples thereof include the general formula (1) and the general formula (2). [In the formulas (1) and (2), 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 = CH
In the group represented by COO-, k is 0 or 1, and l is an integer of 1-10. ] The compound shown by these is mentioned.

To describe the general formulas (1) and (2) in more detail,
R ¹ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group,
Examples thereof include an alkenyl group, an aralkyl group and an alkoxyalkyl group, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl,
Isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, octadecyl, oleyl, benzyl,
Examples thereof include groups such as methylbenzyl, 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 ester maleate compound represented by the general formula (1) 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 ( Methyltin 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) 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) Ate) maleate, bis (dioctyltin oleyl maleate) maleate, bis (dioctyltin benzyl maleate) maleate, bis (cyclohexyl dioctylate 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 (2) include the following. Dimethyl tin maleate, dibutyl tin maleate, dioctyl tin maleate,
Examples include dilauryl tin maleate and polymers thereof. Among the organotin maleate compounds represented by the general formulas (1) and (2), particularly preferred examples are dibutyltin bis (methyl maleate), dibutyltin maleate polymer, dioctyltin maleate polymer and the like.

Examples of metal maleate compounds include Li, Na, K, Mg, Ca, Z
Mention may be made of metal maleates of n, Sr, Ba and Sn, and metal ester maleates, which may be neutral salts, acidic salts or basic salts.

Examples of the metal ester maleate may include a compound composed of a residue of a half ester of maleic acid and an alcohol, for example, an aliphatic alcohol, an aliphatic unsaturated alcohol, an aromatic alcohol and the metal. For example, Li, Na, K, Mg, Ca, Zn, Sr, Ba, Sn, butyl maleate,
Metal salts such as hexyl maleate, isooctyl maleate, 2-ethylhexyl maleate, dodecyl maleate, tridecyl maleate, octadecyl maleate, oleyl maleate, benzyl maleate, cyclohexyl maleate, methoxybutyl maleate, etc. It is possible to use, as particularly preferable examples, Mg, Zn, Ba maleate and Mg, Zn, Ba octadecyl maleate.

The boric acid or boric anhydride used in the present invention is not particularly limited, and may be, for example, orthoboric acid, metaboric acid, tetraboric acid, diboron dioxide, diboron trioxide, tetraboron trioxide, tetraboron pentaoxide, or the like.

In the present invention, the addition amount of the organotin maleate compound and / or the metal maleate compound, which is a maleate compound, is not particularly limited with respect to 100 parts by weight of the styrene resin composition flame-retarded with the bromine compound. Not but usually
0.05 to 10 parts by weight. If it is less than 0.05 parts by weight, the heat stabilizing effect is small, and if it exceeds 10 parts by weight, the expected heat stabilizing effect is not observed, and it is preferably 0.1 to 5.0 parts by weight.

Also, the addition amount of boric acid or anhydrous boric acid is not particularly limited,
It is usually 0.005 to 3.0 parts by weight. If it is less than 0.005 parts by weight, the effect of phase retention is not remarkable, and if it exceeds 3.0 parts by weight, the heat stabilizing effect is rather lowered. Preferably 0.01 to 2.0
Parts by weight.

The ratio of the maleate compound and boric acid or boric anhydride used together is not particularly limited, but the maleate compound: boric acid or boric anhydride is preferably 20: 1 to 1: 1.

The stabilizer used in the present invention may be added to a styrene-based resin composition flame-retarded with a bromine-based compound by a conventionally known technique. The agent may be mixed with a Henschel mixer, a ribbon blender, a Banbury mixer or the like, or a maleic acid salt compound and boric acid or boric anhydride are pre-packed and mixed with the resin composition by the above-mentioned mixer. Good.

Further known stabilizers to these stabilizers, for example,
Various metallic soaps, organic phosphorus compounds, etc. can be used together.

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 [Tufflex TFX-410] manufactured by Mitsubishi Monsanto Kasei Co., Ltd. 100
Part, tetrabromobisphenol A [Fairguard 2000 manufactured by Teijin Kasei Co., Ltd.], and a stabilizer compound shown in [Table-1] was added to 25 parts for 5 minutes with an 8-inch test roll adjusted to 145 ° C. Kneading was performed to prepare a sheet having a thickness of 0.5 mm.
After cutting the obtained sheets, 8 sheets are piled up and ² at 240 ℃, 10kg / cm 2
Pressing was performed for 0 minutes and 40 minutes, the test piece after pressing was taken out, and the degree of coloring was visually judged. As can be seen from Table 1, the stabilizing effect of the stabilizer according to the present invention is remarkably excellent.

Example 2. 100 parts of styrene resin [Asahi Kasei Co., Ltd., Styron 492],
Tetrabrom bisphenol A [Fairguard 2000 manufactured by Teijin Kasei Co., Ltd.] A mixture containing 25 parts of the stabilizers shown in [Table 2] was kneaded for 5 minutes with an 8-inch test roll adjusted to 130 ° C. A sheet having a thickness of 0.7 mm was produced. The obtained sheets were cut and stacked on eight sheets, and the sheets were pressed at 230 ° C. and 10 kg / cm ² for 20 minutes and 40 minutes, and the test pieces after the pressing were taken out, and the degree of coloring was visually judged.

Example 3. 100 parts of acrylonitrile / butadiene / styrene copolymer [Nippon Synthetic Rubber Co., Ltd., JSR / ABS ^# 10NP] 100 parts, decabrom diphenyl ether [Mitsui Toatsu Chemicals, Inc., DB-1
00] 15 parts, antimony trioxide 5 parts with the stabilizer shown in [Table 3] was kneaded for 5 minutes with an 8-inch test roll adjusted to 160 ° C to prepare a 0.7 mm sheet. After cutting the obtained sheets, 8 sheets are piled up, and it is 20 at 260 ℃, 10kg / cm ² .
After pressing for 40 minutes, the test piece after pressing was taken out and the degree of coloring was visually judged.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08L 51/04 LKX 7308-4J 55/02 LMC 7308-4J (56) Reference JP-A-56-845 (JP , A) JP 57-76042 (JP, A) JP 56-54023 (JP, B2) JP 48-10630 (JP, B2)

Claims (1)

[Claims] 1. A method for stabilizing a resin composition comprising a brominated flame retardant and a styrene resin, which comprises simultaneously adding a maleate compound and boric acid or boric anhydride when stabilizing the resin composition. .