JPH054979B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermal stabilization of styrenic resin compositions containing halogen-containing compounds as flame retardants. Styrenic resin has electrical insulation, dimensional stability,
It has excellent properties such as workability and is used for various purposes including electrical equipment parts. However, its flammability is an obstacle to expanding its uses, and efforts are being made to make the resin flame retardant to overcome this obstacle. In order to achieve this flame retardancy, the conventional method has generally been to add so-called flame retardants or flame retardant aids such as halogen-containing compounds, phosphorus compounds, antimony trioxide, etc. Among these flame retardants, halogen-containing Compounds, especially bromine compounds, are effective. However, it is generally known that when a halogen-containing flame retardant is added to a styrene resin, the thermal stability of the resin composition is significantly reduced. Conventionally, there have been methods of adding organic tin compounds, epoxy compounds, phosphorus compounds, antioxidants, etc., or adding maleic acid metal salts (Japanese Patent Publication No. 54023/1983), but the thermal The stabilizing effect was not yet satisfactory, and the development of a stabilizer with even better thermal stabilizing effects was awaited. From this point of view, the present inventors have conducted extensive research on stabilizers with excellent thermal stabilization effects for resin compositions containing styrene-based resins and halogen-containing flame retardants. It has been discovered that by adding an aluminum carboxylate to a styrenic resin composition, the initial coloring of the resin composition can be significantly reduced. discovered that by adding a boron compound esterified with at least one fatty acid and at least one boric acid, the initial coloring of the resin composition was significantly reduced and the sustained thermal stability was improved, and the present invention was completed. did. The styrenic resin used in the present invention refers to polymers of styrene and vinyl aromatic compound monomers such as α-substituted styrene such as α-methylstyrene, vinyltoluene, and nuclear-substituted styrene such as o-chlorostyrene; Mainly vinyl aromatic compound monomers, other monomers copolymerizable with them, such as vinyl compounds such as acrylonitrile, acrylic acid and methacrylic acid, their methyl or ethyl esters, vinyl pyridine, vinyl carbazone, etc. Copolymers with vinyl heterocyclic compounds, other conjugated diene compounds such as butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isobrene, and saturated rubbers such as EPDM, butyl rubber, vinyl aromatic compound monomer alone, Alternatively, a graft polymer obtained by grafting this and the above-mentioned vinyl compound can be mentioned. As the halogen-containing flame retardant used in the present invention, those normally used in this field can be used without limitation, but for example, tris(β-chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(2,3-dibromobropyl) phosphate,
Tris (bromochloropropyl) phosphate, chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenyl, perchlorpentacyclodecane, brominated polyphenyl, tetrapromeethane,
Tetrabromobutane, hexabromocyclododecane, tetrabromobenzene, vinyl chloroacetate, bromustyrene, bromophenyl allyl ether, diallyl chlorendoate, hetzic acid, hetzic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorbro pandiol,
Examples include carbonate oligomers of tetrabromobisphenol A, decabromodiphenyl ether, tris(2,3-dibromopropyl)isocyanurate, and tetrabromobisphenol A. There is no particular limit to the amount of these halogen-containing flame retardants added, but it may be varied as appropriate depending on the degree of flame retardation required, and generally 5 to 35 parts by weight alone or 2 parts by weight per 100 parts by weight of styrene resin. It is preferable to use more than one species in combination. Further, by using a flame retardant aid such as antimony trioxide in combination, the flame retardant effect is excellent, and the amount added is usually preferably 1 to 20 parts by weight per 100 parts by weight of the styrene resin. Examples of carboxylic acid residues constituting the aluminum carboxylate used in the present invention include acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neoacid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid,
Palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl- 4
-Hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, salicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopyrolic acid Monovalent carboxylic acid residues such as pionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid , chlorophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid. Examples of preferred residues include lauric acid, myristic acid, palmitic acid, oleic acid, 12-hydroxystearic acid, stearic acid,
Examples include monoester residues of ricinoleic acid and maleic acid. In the boron compound used in the present invention, in which a polyhydric alcohol is esterified with at least one fatty acid and at least one boric acid, examples of the residues of the polyhydric alcohol constituting it include ethylene glycol, Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dibropylene glycol,
Polypropylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, hexamethylene glycol, tetramethylene glycol, 1,6-hexanediol, methylpropylpropanediol, octanediol, 2,2,4-trimethylpentanediol,
2,2,4,4-tetramethylcyclobutanediol, cyclohexane-1,4-dimethanol,
1,4-butanediol, 1,3-butanediol, glycerin, polyglycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, erythritol, pentaerythritol, dipentaerythritol, sorbidol, mannitol, etc. Examples include residues of polyhydric alcohols having 2 to 30 carbon atoms and 2 to 6 hydroxyl groups, with hydrogen atoms removed from at least two hydroxyl groups, preferably ethylene glycol, 1,4-butanediol, Examples include residues such as glycerin and pentaerythritol, particularly preferably 1,4-butanediol,
Examples include residues such as glycerin. Examples of other fatty acid residues include acetic acid, propionic acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids having 2 to 29 carbons such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, isostearic acid, hydroxystearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, montanic acid, and Examples include residues obtained by removing the hydroxyl group from the carboxyl group of unsaturated fatty acids having 3 to 22 carbons such as alluric acid, crotonic acid, undecylenic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, and linolenic acid. Preferred are residues of higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, behenic acid, oleic acid, and linoleic acid, and particularly preferred are residues of higher fatty acids such as stearic acid and oleic acid. Examples include residues. Furthermore, examples of boric acid residues having other configurations include residues of boric acid from which at least one hydroxyl group has been removed, such as orthoboric acid, metaboric acid, and tetraboric acid, and preferably orthoboric acid. , metaboric acid, and the like. Next, an example of the boron compound is shown in the general formula:

[Formula] ()R ₁ OB=O

【formula】

[General formula (), (), (), (), (),
In () and (), R ₁ is at least 1
Represents a residue obtained by removing one hydroxyl group from a polyhydric alcohol partially esterified with R ₂ ,
R ₃ and R ₄ are hydrogen atoms, monovalent or polyvalent alcohols or phenols with one hydroxyl group removed, or polyhydric alcohols partially esterified with at least one fatty acid with one hydroxyl group removed. However, if at least two of R ₂ , R ₃ and R ₄ are simultaneously present in the molecule, they may be the same or different from R ₁ . R ₅ and R ₆ are 2
to a residue obtained by removing two hydroxyl groups from a polyhydric alcohol or phenol having six hydroxyl groups,
or a residue obtained by removing two hydroxyl groups from a polyhydric alcohol having 2 to 5 hydroxyl groups that has been partially esterified with at least one fatty acid, and R ₇ is partially esterified with at least one fatty acid. It shows a residue obtained by removing three hydroxyl groups from a polyhydric alcohol having three to five hydroxyl groups. ], etc. The boron compound can be obtained, for example, by producing a partially esterified product from a fatty acid and a polyhydric alcohol, and then reacting the product with boric acid. Specific examples of the boron compounds include: (G) C ₁₇ H ₃₃ COO (CH ₂ ) ₄ −O−B=0 etc. The amount of aluminum carboxylate used in the present invention is appropriately determined depending on the type of halogen-containing flame retardant used for flame retardation, but it is 100 parts by weight of the halogen-containing flame retardant. against
The amount is 0.5 to 50 parts by weight, usually 1 to 20 parts by weight. The amount of the aluminum carboxylate and boron compound used in the present invention is appropriately determined depending on the type of halogen-containing flame retardant used for flame retardation. fuel
The total amount of aluminum carboxylate and boron compound is 0.5 to 50 parts by weight, usually 1 to 20 parts by weight, relative to 100 parts by weight. There is no particular restriction on the combined ratio of aluminum carboxylate and boron compound, but aluminum carboxylate: boron compound = 9:1 to 1:9.
is preferable, particularly preferably 4:6 to 8:2
It is. In addition, when actually blending, the aluminum carboxylate and the boron compound may be added separately to the styrenic resin containing the halogen-containing flame retardant, or a pre-mixed mixture of the aluminum carboxylate and the boron compound may be added. It's okay. In carrying out the present invention, a halogen-containing flame retardant is added to a styrene resin, aluminum carboxylate alone or an aluminum carboxylate and a boron compound are added, and a Henschel mixer or a Banbury mixer is used. It can be blended using a mixer such as Alternatively, a mixture of a halogen-containing flame retardant, an aluminum carboxylate, or a halogen-containing flame retardant, an aluminum carboxylate, and a boron compound may be added to the styrene resin. In addition to the stabilizer of the present invention, organic tin compounds, epoxy compounds, organic phosphite esters,
Antioxidants, various metal soaps, flame retardant aids, pigments, fillers, lubricants, foaming agents, etc. can be added. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. In these examples, parts mean parts by weight. Example 1 100 parts of acrylonitrile-butadiene-styrene resin [manufactured by Japan Synthetic Rubber Co., Ltd., JSRABS #10NP],
A mixture of 20 parts of tetrabromobisphenol A (Teijin Kasei Co., Ltd. Fire Guard 2000) and 1.0 part of the stabilizer shown in [Table 1] was kneaded for 5 minutes using an 8-inch test roll adjusted to 130°C. A sheet with a thickness of 0.5 mm was produced. After cutting, eight of the obtained sheets were stacked and pressed at 240°C for 20 minutes, 40 minutes, and 60 minutes. After pressing, test pieces were taken out and the degree of coloration was visually judged. As can be seen from [Table 1], the aluminum carboxylate used in the present invention has an excellent ability to prevent initial coloring.

【table】

[Table] Example 2 Acrylonitrile-butadiene-styrene resin [manufactured by Japan Synthetic Rubber Co., Ltd., JSRABS#10NP] 100 parts,
Carbonate oligomer of tetrabromo bisphenol A [Teijin Kasei Ltd., Fire Guard 7500]
A mixture of 20 parts of antimony trioxide, 5 parts of antimony trioxide, and 1.0 part of the stabilizer shown in [Table 2] was made into a sheet in the same manner as in Example 1, and after cutting the obtained sheet, 8 sheets were stacked and heated at 265°C for 30 minutes. , press for 60 minutes and 90 minutes,
After pressing, the test piece was taken out and its degree of coloration was visually determined. As can be seen from [Table 2], the aluminum carboxylate used in the present invention has an excellent ability to prevent initial coloring, and furthermore, when the aluminum carboxylate and a boron compound are used together, the heat stabilizing effect is even more excellent.

【table】

[Table] Example 3 Styrene resin [Styron 492, manufactured by Asahi Kasei Corporation]
100 parts, carbonate oligomer of tetrabromobisphenol A [Teijin Kasei Ltd., Fire Guard 7500] 20 parts, antimony trioxide 6 parts [Table-
The mixture containing 1.0 part of the stabilizer shown in 3) was heated at 115°C.
Knead for 5 minutes with an 8-inch test roll adjusted to
A sheet with a thickness of 0.7 mm was produced. After cutting the obtained sheets, stack 8 sheets and heat at 275℃ for 50 minutes.
After pressing for 100 minutes, 150 minutes, and 150 minutes, the test pieces were taken out and the degree of coloration was visually judged. As can be seen from [Table 3], there is an effect of the aluminum carboxylate used in the present invention and the combined use of the aluminum carboxylate and the boron compound.

【table】

Claims (1)

[Scope of Claims] 1. A method for stabilizing a styrenic resin composition containing a halogen-containing flame retardant, which comprises: adding an aluminum carboxylate to the styrenic resin composition containing a halogen-containing flame retardant. 2. To a styrenic resin composition containing a halogen-containing flame retardant, a boron compound in which an aluminum carboxylate and a polyhydric alcohol are esterified with at least one fatty acid and at least one boric acid is added together. A method for stabilizing a styrenic resin composition containing a halogen-containing flame retardant.