JPS6086143A - Stabilization of styrene resin composition containing halogen-containing flame-retardant - Google Patents

Abstract

PURPOSE:To provide a styrene resin composition resistant to the lowering of the thermal stability caused by the addition of a halogen-containing flame-retardant, by adding a specific hydrotalcite to the styrene resin. CONSTITUTION:A styrene resin composition containing 5-35pts.(wt.) of a halogen-containing flame-retardant based on 100pts. of the resin, is compounded with 1-20pts., based on 100pts. of the flame-retardant, of a hydrotalcite of formula (0<x<=0.5; m is 0-5). The effect can be remarkably improved by adding a boron compound obtained by esterifying a polyhydric alcohol with at least one fatty acid and at least one boric acid, in addition to the above additive. The hydrotalcite may be surface-treated with e.g. metal stearate, etc. The ratio of hydrotalcite to the boron compound is 9:1-1:9, preferably 8:2-4:6, and the sum of the hydrotalcite and the boron compound is 1-20pts. based on 100pts. of the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermal stabilization of a styrenic resin composition containing a halogen-containing compound as a flame retardant.

Styrenic resins have excellent properties such as electrical insulation, dimensional stability, and workability, and are used for various purposes including stain-repellent equipment parts. However, the flammability of the resin is an obstacle to expanding its use, and in order to overcome this obstacle, efforts have been made to make the resin flammable.

In order to achieve this flame retardancy, halogen-containing compounds,
Conventionally, a method of adding so-called flame retardants or flame retardant aids such as phosphorus compounds and antimony trioxide has been carried out. Among these flame retardants, halogen-containing compounds, particularly 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 are methods of adding organic tin compounds, epoxy compounds, phosphorus compounds, antioxidants, etc., or adding maleic acid metal salts (% Publication No. 56-54023, etc.). The thermal stabilizing effect of 2000 is still not satisfactory, and the development of a stabilizer with even better thermal stabilizing effect has been 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. For the styrene resin composition, the general formula [I]yy, 7zX(OH)2(00B)! /2-
Thermal stability of the resin composition can be achieved by adding hydrotalcite represented by mH2O[I) (wherein X is O (x≦0.5, and m is a number from 0 to 5). Furthermore, by adding to the above composition a boron compound containing less polyhydric alcohol (both esterified with one fatty acid and at least one boric acid), The present invention was completed by discovering that the thermal stability of the resin composition was significantly improved.

The styrenic resin used in the present invention refers to polymers of styrene, vinyl aromatic compound monomers such as α-substituted styrene such as α-methylstyrene, and nuclear-substituted styrene such as vinyltoluenlene; Mainly compound monomers, other monomers copolymerizable with them, such as acrylonitrile, acrylic acid and methacrylic acid, vinyl compounds such as their methyl or ethyl esters, vinyl heterocycles such as vinyl pyridine, vinyl carbazone, etc. copolymers with other compounds, conjugated diene compounds such as butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, and saturated rubbers such as KPDM, butyl rubber, and vinyl aromatic compound monomers alone, or Examples include graft polymers obtained by grafting this material with the above-mentioned vinyl compounds.

As the halogen-containing flame retardant used in the present invention, those normally used in this field can be used without limitation, but examples include tris(β-chloroethyl) phosphate and tris(dichloropropy/l/) phosphate. , tris(2,3-dibromopropyl) phosphate, tris(promchloropropylene phosphate 7ate, chlorinated paraffin, chlorinated polyethylene, chlorinated polyphenyl, perchlorpentacyclotecan, brominated polyphenyl, tetra Bromoethane, tetrabromobutane, hexabromocyclototicane, tetrabromobenzene, vinylchloroacetate), bromoestyrene, bromphenylyl ether, diallyl chlorendoate,
Het acid, het acid anhydride, tetrachlorophthalic anhydride,
Tetrabromo phthalic anhydride, chlorpropanediol,
Examples include tetrabromobisphenol A, decabromodiphenyl ether, tris(2,3-')frompropyl)isocyanurate, and carbonate oligomers of tetrabromobisphenol A.

There is no particular limit to the amount of these halogen-containing flame retardants added, but the amount may be changed as appropriate depending on the degree of flame retardancy required.
Generally, it is preferable to use 5 to 35 parts by weight of the styrenic resin alone or in combination of two or more kinds based on 100 parts by weight of the styrene resin. Furthermore, when a flame retardant aid such as antimony trioxide is used in combination, the flame retardant effect is even better, and the amount added is usually 1/1 of the styrene resin.
It is preferably 1 to 20 parts by weight per 00 parts by weight.

Hydrotalcites represented by the general formula CI] used in the present invention include natural and synthetic hydrotalcites, and those with various metal ratios such as M#≧At.

Also used are hydrotalcite minerals, such as higher fatty acid alkali metal salts such as stearic acid and alkali metal oleate, and alkali metal salts such as dodecylbenzenesulfonic acid! j The surface may be treated with an organic sulfonic acid alkali metal salt such as gold R salt.

The polyhydric alcohol used in the present invention contains at least one
In boron compounds esterified with 1 fatty acid and less than 1 boric acid.

Examples of polyhydric alcohol residues that make it up include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, holiflopylene glycol, butylene glycol, hexylene glycol, and neopentyl glycol. , hexamethylene glycol, tetramethylene glycol, 1.6-hexanediol, methylpropylpropanediol, octanediol, 2.2.4-)limethylbentanediol, 2,
2.4.4-Tetramethylcyclobutanediol, cyclohexane-1,4-dimetatool, 1.4-butanediol, 1.3-butanediol, glycerin, polyglycerin, trimethylolemethane, trimethylolethane , trimethylolpropane, trimethylolbutane, erythritol, pentaerythritol, cichentaerythritol, sorbitol, mannitol, etc., of polyhydric alcohols having 2 to 30 carbon atoms and 2 to 6 hydroxyl groups. Examples include residues from which atoms have been removed, preferably ethylene glycol,
Examples include residues such as 1.4-butanediol, glycerin, and pentaerythritol, particularly preferably residues such as 1.4-butanediol and glycerin. In addition, examples of other configurations of deoxyacid residues include acetic acid,
propionic acid, cabroic acid, enanthic acid, caprylic acid,
2-ethylhexylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, balmitic acid, heptadecylic acid, stearic acid, isostearic acid.

Hydroxystearic acid, nonadecanoic acid, arachidic acid,
2 to 29 of behenic acid, lignoceric acid, montanic acid, etc.
Carboxyl groups of saturated fatty acids with 1 to 22 carbons, as well as unsaturated fatty acids with 3 to 22 carbons, such as acrylic acid, crotonic acid, undecylic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, and lylunic acid. Examples include residues excluding hydroxyl groups, preferably lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
Examples include residues of higher fatty acids such as hydroxystearic acid, behenic acid, oleic acid, and linoleic acid, and particularly preferred are residues of stearic acid and oleic acid.

Furthermore, examples of boric acid residues with other configurations include:
Examples include residues of boric acid such as orthoboric acid, metaboric acid, and tetraboric acid from which at least one hydroxyl group has been removed, and preferred examples include residues of orthoboric acid and metaboric acid.

Next, an example of the boron compound is shown by a general formula: [General formula (I) l (M) , (2), t (v) +
(9) and in ceramic, R1 represents a residue obtained by removing one hydroxyl group from a polyhydric alcohol partially esterified with at least one fatty acid, and R2y, R5 and R4 are , 1r---ri-tottltI
r\- or phenol, the residue from which 91 hydroxyl groups have been removed,
or a polyhydric alcohol partially esterified with at least one fatty acid, from which 91 hydroxyl groups have been removed, but if at least two of R2, R, and R4 are simultaneously present in the molecule, R1 May be the same or different.

R5 represents a residue of a polyhydric alcohol having 2 to 5 hydroxyl groups partially esterified with at least one fatty acid, from which 92 hydroxyl groups have been removed, and R6 represents a polyhydric alcohol having 2 to 6 hydroxyl groups, partially esterified with at least one fatty acid. Residues of alcohol or polyhydric phenol from which 92 hydroxyl groups have been removed, or residues from polyhydric alcohol having 2 to 5 hydroxyl groups partially esterified with at least one fatty acid from which 92 hydroxyl groups have been removed. and R7 is a polyhydric alcohol having 3 to 5 hydroxyl groups partially esterified with at least one fatty acid.
Residues with hydroxyl groups removed are shown. ], 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 1 0H20H0H20000,,H,.

1 0H20000, 5H2, 0H200CC, 5HS.

ljM2(JsuυU, 7H55CH200CC17H5
5 (3H200002, H weak (G) L!,, R5, Coo (OH2 n 4-0- et al.
0H20k1 C11200t30. ,mass.

etc.

The amount of 1-hydrotalcite (used in the present invention) is:
It is determined as appropriate depending on the type of the chlorine-containing flame retardant used for flame retardation, but it is usually 0.5 to 50 parts by weight based on the weight of the chlorine-containing flame retardant. It is 1 to 20 parts by weight.

The amount of idrotalcite used in the present invention and the boron compound to be added is appropriately determined depending on the type of halogen-containing flame release agent used, but it is recommended that the amount of the halogen-containing flame release agent be 10G parts by weight. On the other hand, the total amount of hydrotalcite and boron compound is 0.5 to 50 parts by weight, usually 1 to 50 parts by weight.
It is 20 parts by weight.

There is no particular restriction on the combined ratio of hydrotalcite and boron compound, but it is preferably 9:1 to 1:9 of hydrotalcite: boron compound, and the preferred percentage is:
The ratio is 8:2 to 4:6.

In addition, when actually blending, a premixed mixture of hydrotalcite and a boron compound may be added to the styrene resin containing a halogen-containing flame retardant.

In carrying out the present invention, a halogen-containing flame retardant is added to a styrene resin, and hydrotalcite alone or a combination of hydrotalcite and a boron compound is added to the styrene resin, and a Henschel mixer, Banbury mixer, etc. It can be blended using a mixer.

Alternatively, a mixture of a halogen-containing flame retardant and hydrotalcite or a halogen-containing flame retardant, hydrotalcite, and a boron compound may be added and blended into the styrene resin.

In addition to the stabilizer of the present invention, organic tin compounds, epoxy compounds, organic phosphite esters, antioxidants, various soapstones, flame retardant aids, pigments, fillers, lubricants, and foaming agents may be added as necessary. etc. can be added.

EXAMPLES 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 Acrylonitrile-butadiene-styrene resin [JSR-ABS#10 NP manufactured by Japan Synthetic Rubber If', lJ]
1100 parts to tetrabromo bisphenol 〇Carphonate oligo-[Teijin Kasei ■Ret Fire Guard 7500
A mixture of 25 parts 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 to produce a sheet with a thickness of 0.5.0. The obtained sheet was cut into 8 sheets and pressed at 270° C. for 30 minutes, 60 minutes and 90 minutes, and the test pieces after pressing were taken out and the degree of coloration was determined visually. As can be seen from [Table 1], the hydrotalcite used in the present invention has an excellent thermal stabilizing effect. Furthermore, hydrotal was produced.

After cutting the obtained sheets, 8 sheets were stacked at 210℃ for 40 minutes.
Pressing was carried out for 80 minutes and 120 minutes, and the test pieces after pressing were taken out and the degree of coloration was determined visually. As can be seen from [Table 2], it can be seen that the noidrotalcite used in the present invention has an excellent thermal stabilizing effect. Furthermore, it can be seen that the combined use of noidrotalcite and a boron compound significantly improves the thermal stabilization effect.

[Table 2] Procedural amendment (voluntary) November 5, 1980 Manabu Shiga, Commissioner of the Patent Office, Patent Application No. 195779, filed in 1982, 2, Title of Invention: Styrenic resin composition containing halogen-containing flame retardant Stabilization Act 3, Person making the amendment: 4, Agent Residence: 1-2-58-6, Hiromachi, Parts Yo-ku, Tokyo, Subject of amendment [Detailed description of the invention in the specification] -(1) "The above composition" in the first line of page 4 of the specification was corrected to "the resin composition containing the above hydrotalcite."

(2) rMg, , ALo, , (OH)2(Co,) in rows 2.4.5 and 6 of sample numbers in [Table-1] on page 17 of the same
. , 154・0.54H20Jg r Mgo,, AA
o,,(OH)2(C05),15o-0,54H20
Corrected with J.

(3) Sample numbers 2 and 4 in [Table 2] on page 19 of the same
Mausoleum. , 7kto, 5(OH)2(C03). ,,54・
0.54H20''WorMgp,7Mo,,(OH)2(
Co,). ,,5o,Q,54H20J and corrected.

Claims (1)

[Claims] 1. For a styrenic resin composition containing a halogen-containing flame retardant, the general formula % formula % (wherein X is O (x≦0.5), m is
Indicates the number of ) A method for stabilizing a styrenic resin composition containing a halogen-containing flame retardant, which comprises adding hydrotalcite as shown in the following. 2. For the styrenic resin composition containing a halogen-containing flame retardant, hydrocarbons represented by the general formula % (wherein, X represents a number such that O<x≦05, and m represents a number from 0 to 5) Stabilization of a styrenic resin composition containing a halogen-containing flame retardant, characterized in that talcite and a polyhydric alcohol are combined with a boron compound esterified with at least one fatty acid and at least one boric acid. Law.