JPH054980B2 - - 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. By adding to a styrenic resin composition a boron compound in which a polyhydric alcohol is esterified with at least one fatty acid and at least one boric acid, the thermal stability of the resin composition is significantly improved. They found this and completed the present invention. 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
-dibromopropyl) phosphate, tris(bromochloropropyl) phosphate, chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenyl, perchlorpentacyclodecane, brominated polyphenyl, tetrabromoethane, tetrabromobutane, hexabromocyclododecane, Tetrabromobenzene, vinyl chloroacetate, bromustyrene, bromophenyl allyl ether,
Diallyl chlorendoate, hettic acid, hettic anhydride, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride, chlorpropanediol, tetrabromo bisphenol A, decabrom diphenyl ether, tris(2,3-dibromobropyl) isocyanurate, tetra Brombisphenol A
Carbonate oligomers and the like can be mentioned. The amount of these halogen-containing flame retardants added is not particularly limited, but may be varied as appropriate depending on the degree of flame retardation required, and generally 5 to 35 parts by weight of styrenic resin alone or It is preferable to use two or more kinds 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. 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, cabroic acid, enanthic acid, cabrylic acid, 2-ethylhexylic acid, pelargonic acid, cabric acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids having 2 to 29 carbons such as myristic acid, pentadecylic acid, palmitic acid, hebutadecylic 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】

【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
A residue obtained by removing two hydroxyl groups from a polyhydric alcohol or polyhydric phenol having 6 to 6 hydroxyl groups, or a polyhydric alcohol having 2 to 5 hydroxyl groups partially esterified with at least one fatty acid. Residues with two hydroxyl groups removed are shown,
R ₇ represents a residue obtained by removing three hydroxyl groups from a polyhydric alcohol partially esterified with at least one fatty acid and 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. Among the boron compounds represented by the above general formula, examples of preferred compounds that are easy to produce and are commonly used include: (G) C ₁₇ H ₃₃ COO (CH ₂ ) ₄ −O−B=0 etc. The amount of boron compound used in the present invention is
Although it is determined appropriately depending on the type of halogen-containing flame retardant used for flame retardation, 0.5 to 50 parts by weight per 100 parts by weight of the halogen-containing flame retardant,
It is usually 1 to 20 parts by weight. In carrying out the present invention, a halogen-containing flame retardant may be added to a styrene resin, the boron compound of the present invention may be further added, and the mixture may be blended using a mixer such as a Henschel mixer or a Banbury mixer. Alternatively, a mixture of a halogen-containing flame retardant and the boron compound of the present invention 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 25 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 250°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 boron compound used in the present invention has an excellent thermal stabilizing effect.

【table】

[Table] Example 2 Acrylonitrile-butadiene-styrene resin [manufactured by Japan Synthetic Rubber Co., Ltd., JSRABS#10NP] 100 parts,
Carbonate oligomer of tetrabromobisphenol A [Teijin Kasei Ltd., Fire Guard 7500]
A mixture of 25 parts 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 the resulting sheet was cut into 8 sheets and heated at 260°C for 30 minutes, 60 minutes, and
Pressing was performed for 90 minutes, and the sample pieces after pressing were taken out and the degree of coloration was determined visually. As can be seen from [Table 2], the boron treatment used in the present invention has an excellent thermal stabilizing effect.

[Table] Example 3 Styrene resin [Styron 492, manufactured by Asahi Kasei Corporation]
A mixture of 100 parts of decabromodiphnyl ether (manufactured by Mitsui Toatsu Chemical Co., Ltd., DB-100), 15 parts of antimony trioxide, and 1.0 part of the stabilizer shown in [Table 3] was heated to 115°C. The mixture was kneaded for 5 minutes using a controlled 8-inch test roll to produce a sheet with a thickness of 0.7 mm.
After cutting the obtained sheets, stack 8 sheets and heat at 265℃ for 50 minutes.
Pressing was carried out for 100 minutes and 150 minutes, and the test pieces were taken out after pressing and the degree of coloration was judged with the naked eye. As can be seen from [Table 3], the boron compound used in the present invention has an excellent thermal stabilizing effect.

【table】

Claims (1)

[Claims] 1. A halogen-containing flame retardant characterized in that a boron compound in which a polyhydric alcohol is esterified with at least one fatty acid and at least one boric acid is added to a styrenic resin composition containing a halogen-containing flame retardant. A method for stabilizing a styrenic resin composition containing a refractory agent.