JPH0859927A - Flame retardant styrenic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition, excellent in flame retardancy, light and heat resistances and fluidity and reduced in adhesion to metallic parts of an extruder, etc., by blending a polystyrenic resin with a halogenated epoxy- based resin containing a specific compound as a flame retardant. CONSTITUTION: This resin composition contains (A) a polystyrenic resin and (B) a halogenated epoxy-based resin (e.g. tetrabromobisphenol A type epoxy resin) containing a 10-40C alkyl glycidyl ether compound (e.g. decyl glycidyl ether) so as to provide preferably 10-50 pts.wt. amount of the component (B) based on 100 pts.wt. component (A). When a flame retardant assistant such as antimony trioxide is further blended in the composition, the flame retardant effects are preferably more improved. The content of the 10-40C alkyl glycidyl ether compound is preferably 0.1-10 pts.wt. based on the total amount of the component (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant styrenic resin composition, which is highly flame-retardant and has excellent light resistance, heat resistance and fluidity, as well as screws and cylinders for extruders and injection molding machines. -, And relates to a flame-retardant styrene-based resin composition that reduces adhesion to a mold or the like.

[0002]

2. Description of the Related Art Highly impregnated polystyrene (HIP
Styrene resins such as S) and ABS have good mechanical properties, and have excellent electrical insulation and molding processability. In recent years, it has been widely used in office automation equipment, housings for home electric appliances, automobile parts and the like. However, since the styrene resin is flammable, it is required to be flame retardant from the viewpoint of safety. Further, in the field of OA equipment, home appliances, etc., it is used indoors, but since it is exposed to a fluorescent lamp or light entering from the outside, importance is attached to light resistance.

Conventionally, various halogenated organic compounds have been proposed for imparting flame retardancy to styrene resins. Typically, tetrabromobisphenol A (TB
A), decabromodiphenyl ether (DBDPE), a brominated epoxy resin, and a compound obtained by blocking the epoxy group of this brominated epoxy resin with tribromophenol (TBP) are known. Especially because the former two are cheaper,
Many are used. However, when TBA is blended with a styrene resin, it has a drawback that heat resistance and light resistance are significantly lowered, and an epoxy resin blocked with DBDPE and TBP has a drawback that light resistance is lowered. Further, since the brominated epoxy resin has adhesiveness to a screw such as an extruder at the time of melt-kneading or an injection molding machine at the time of molding, when continuously produced, the adhered matter becomes a high temperature for a long time. Exposed
It has a drawback that it is discolored and deteriorated and is mixed as foreign matter into the compound or the molded product.

[0004]

DISCLOSURE OF THE INVENTION As a result of earnest research, the present inventors have found that halogenated epoxy resins, particularly brominated epoxy resins, have alkyl glycidyl ethers and / or alkyl glycidyl ethers and phenols. It was found that the reaction product of, or a reaction product of an alkyl glycidyl ether and a phenol end in an epoxy resin is extremely effective as a flame retardant for a styrene resin,
The present invention has been completed, and the present invention is excellent in light resistance, heat resistance and fluidity as well as a high degree of flame retardancy, and for metal parts such as screws, cylinders and molds of extruders and injection molding machines. It is an object of the present invention to provide a flame-retardant styrene resin composition with reduced adhesiveness.

[0005]

SUMMARY OF THE INVENTION The gist of the present invention is a polystyrene resin (A) and a halogenated epoxy resin (B) containing an alkylglycidyl ether compound having 10 to 40 carbon atoms. A flame-retardant styrene-based resin composition comprising: That is, the present invention is to make the polystyrene resin (A) flame-retardant by using the halogenated epoxy resin (B) containing an alkylglycidyl ether compound having 10 to 40 carbon atoms. As for the compounding amount, polystyrene resin 10
It is 10 to 50 parts by weight of a halogenated epoxy resin (B) containing an alkylglycidyl ether compound having 10 to 40 carbon atoms with respect to 0 parts by weight. Further, it is preferable to use a flame retardant auxiliary together, if necessary, and it is preferable to contain about 1 to 10 parts by weight. Furthermore, it is preferable to use a compound in which the epoxy group of the brominated epoxy resin is blocked with a halogenated phenol and other additives, if necessary.

The present invention will be described in more detail below. The polystyrene resin used in the present invention is a homopolymer or copolymer of styrene compounds such as styrene, α-methylstyrene, vinyltoluene and o-chlorostyrene, and if necessary, these monomers and acrylonitrile, polybutadiene rubber. And the like, maleimide-based copolymers such as maleimide and N-phenylmaleimide, and the like. Typically, polystyrene, HIPS (high impact polystyrene resin), AS resin, ABS resin, AES
Resin, MBS resin, and the like. Furthermore, polymer alloys containing these polystyrene-based resins can be mentioned.

The flame retardant used in the present invention is a halogenated epoxy resin (B) containing an alkylglycidyl ether compound having 10 to 40 carbon atoms. The halogenated epoxy-based resin (B) containing an alkylglycidyl ether compound is: --- Halogenated epoxy-based resin and alkylglycidyl ether-
A mixture with a ter compound, a halogenated epoxy resin or a halogenated bisphenol, an epihalohydrin, and an alkylglycidyl ether.
A reaction product of a ter compound, or a mixture of the reaction product and a halogenated epoxy resin, an adduct of an alkylglycidyl ether compound and a phenol, and a mixture of this and a halogenated epoxy resin. May be. As for the halogenated epoxy resin, 0-60% of the epoxy groups of the halogenated epoxy resin may be blocked with halogenated phenols, for example, in order to increase the content of bromine. Alternatively, the epoxy group of the halogenated epoxy resin may be 80
% To 60% by weight of a compound capped with at least 100% and a carbon number of 1
You may melt-mix with 100-40 weight part of halogenated epoxy resins containing 0-40 alkyl glycidyl ether compounds. The content of the halogenated epoxy resin having a structure blocked with halogenated phenols is not particularly limited, but is preferably 60 parts by weight or less,
50 parts by weight or less is more preferable. If it is more than 60 parts by weight, light resistance cannot be expected.

The alkylglycidyl ether compound having 10 to 40 carbon atoms is an alkylglycidyl ether having 10 to 40 carbon atoms, the alkylglycidyl ether having 10 to 40 carbon atoms and phenols. And at least one selected from the group consisting of a reaction product of an alkyl glycidyl ether having 10 to 40 carbon atoms with a phenol end of an epoxy resin, and having 10 carbon atoms.
The content of the ~ 40 alkyl glycidyl ether compounds is not particularly limited, but is 0.1 ~ 10% of the total amount of the flame retardant.
10 parts by weight is preferable, and 0.5 to 8 parts by weight is more preferable. If it is less than 0.1 part by weight, the effect of reducing the adhesion to metal cannot be expected, and if it exceeds 10 parts by weight, the flame retardant effect and the heat distortion temperature of the flame-retardant resin composition tend to be lowered. If necessary, other releasing agents and lubricants may be used in combination with the above compounds.

The halogenated epoxy resin used here is a reaction product of a halogenated bisphenol and epihalohydrin, a reaction product of a halogenated phenol novolak and epihalohydrin, or a halogenation of these reaction products. Examples thereof include addition reaction products of epoxy resins and halogenated bisphenols. Specific examples of the halogenated epoxy resin include tetrachlorobisphenol A.
Diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol
Examples thereof include diglycidyl ether of S, dichloroside of tetrachlorobisphenol S, polyglycidyl ether of dibromophenol novolak, and the like.

The halogenated phenols for blocking the epoxy group of the halogenated epoxy resin are 2,4,6-tribromophenol, dibromophenol, monobromophenol and 2,4,6-. Examples thereof include trichlorophenol, dichlorophenol, monochlorophenol and the like.

The alkylglycidyl ether compound having 10 to 40 carbon atoms is an alkylglycidyl ether compound having 10 to 40 carbon atoms, preferably 12 to 35 carbon atoms. Specific examples include decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether. Tell, heptadecyl glycidyl ether, Octadecyl glycidyl ester
Ter, nonadecyl glycidyl ether, eicosyl glycidyl ether, hexacosyl glycidyl ether, heptacosyl glycidyl ether, and the like, further, branched alkyl ether and the above alkyl glycidyl ether. Mention may be made of mixtures.

Further, an epoxy resin having a terminal phenol capable of reacting with an alkylglycidyl ether is a bisphenol-
Type epoxy resin, halogenated epoxy resin, hydroxyquinone type epoxy resin, novolac type epoxy resin,
An epoxy resin such as an ortho-cresol type epoxy resin, a biphenyl type epoxy resin, a fluorene type epoxy resin, or a naphthalene type epoxy resin in which a part or all of the terminal groups are phenol groups was used. Examples of the phenols capable of reacting with the alkylglycidyl ether include the phenols which are the raw material of the epoxy resin. Of course, any phenol that can react with the glycidyl group can be used.

Further, a reaction product of the epoxy group of the above epoxy resin with an alkyl alcohol having 10 to 40 carbon atoms or a branched alkyl alcohol can also be used. Representative examples of the alkyl alcohol include hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, hexacosyl alcohol, heptacosyl alcohol, octacosyl alcohol and the like. To be

As a method for producing a halogenated epoxy resin containing an alkylglycidyl ether compound which is a flame retardant used in the present invention, halogenated bisphenols and epihalohydrin are treated with an alkali metal hydroxide and a non-reactive solvent. In the presence of a halogenated epoxy resin obtained by reaction with alkyl glycidyl ether, or a low molecular weight halogenated epoxy resin and halogenated bisphenols in the presence of a catalyst at 80 ° C to 220
There is a method in which an alkyl glycidyl ether is added to the obtained medium- and high-molecular weight halogenated epoxy resin, which is reacted by heating at ℃. If necessary, 60% or less of the epoxy group of the halogenated epoxy resin may be further treated with halogenated phenol.
May be blocked with a le. Alternatively, a halogenated phenol is previously prepared.
It is also possible to mix a halogenated epoxy resin blocked with a wax in an amount of 60 parts by weight or less.

Further, a method obtained by reacting an alkyl glycidyl ether or an alkyl alcohol with a halogenated bisphenol and an epihalohydrin in the presence of an alkali metal hydroxide and a non-reactive solvent, or an alkyl glycidyl A method obtained by reacting an ether or an alkyl alcohol, a halogenated bisphenol and a halogenated epoxy resin in the presence of a catalyst, or an alkylglycidyl ether and an epoxy group having the terminal phenol group There is a method in which a compound obtained by previously reacting a resin or a raw material phenol of an epoxy resin in the presence of a catalyst is added to the halogenated epoxy resin. Of course, if necessary, a halogenated epoxy resin blocked with halogenated phenols may be added.

Known reaction catalysts are alkali metal hydroxides, tertiary amines, imidazoles, quaternary ammonium salts, phosphines, phosphonium salts and the like. The method for producing the flame retardant is not particularly limited,
It can be easily manufactured by a known method.

As the flame retardant aid (C), for example, antimony trioxide, antimony pentoxide, molybdenum oxide, etc. are added to the styrene resin composition containing the styrene resin (A) and the flame retardant (B) of the present invention. When used in combination, the flame retardant effect is further enhanced. Further, the composition of the present invention comprises
If necessary, generally used ultraviolet absorbers, antioxidants, lubricants, colorants, release agents, fillers, dyes and pigments, etc. can be added.

[0018]

EXAMPLES AND COMPARATIVE EXAMPLES The effects of the present invention will be described in more detail below with reference to Examples and Comparative Examples, but the method for producing the flame retardant and the method for producing the composition of the present invention are not particularly limited. Not a thing. In addition, all parts and% in the examples are based on weight.

The test method in each example was carried out by the method described below. Test method (1) Epoxy equivalent: JIS K-7234 (2) Softening point: JIS K-7236 (3) Light resistance ΔE: 48 hour exposure test (rain) at 63 ° C using a sunshine weather meter None).
The color difference of the test piece before and after the exposure was measured with a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.). (4) Flammability test: Based on UL-94 test method. (5) Adhesion test: In a metal heat roll, the first roll
Set the roll to 200 ° C and the second roll to 60 ° C,
The test piece was lightly pressure-bonded to the first roll for 3 minutes, and after operating for 3 minutes, the test piece was peeled off and the state of adhesion to the roll was observed.

Synthesis Example 1 Epoxy equivalent of 650 g / eq. Tetrabromobisphenol A (hereinafter abbreviated as TBA) type epoxy resin YDB
-406 (bromine content 50%, manufactured by Tohto Kasei Co., Ltd.) 98
0 g was placed in a 1 liter separable flask equipped with a thermometer, a stirrer, and a condenser, the inside was replaced with nitrogen gas, and the mixture was heated and melted at 150 ° C. -Add 20 g of Teru (Nippon Oil & Fat Co., Ltd. Epiole SK, the same below),
After stirring for 1 hour, put the mixture in a stainless steel vat,
After cooling and pulverizing, flame retardant-a was obtained. The properties are shown in Table 1.

Synthesis Example 2 Epoxy equivalent of 400 g / eq. TBA type epoxy resin YDB-400 (49% bromine content, Tohto Kasei Co., Ltd.)
Made, abbreviated as YDB-400 hereinafter) 400 g and TBA75
After charging g, heating and melting at 120 ° C., 0.08 g of catalyst triphenylphosphine was added, and after reacting at 160 ° C. for 5 hours, 25 g of alkyl glycidyl ether containing 4.9% of oxirane oxygen was added, The mixture was stirred for another hour. The properties of the obtained flame retardant-b are shown in Table 1.

Synthesis Example 3 Brominated epoxy resin TB-62 (bromine content 58%, manufactured by Tohto Kasei Co., Ltd., hereinafter referred to as TB-62) in which 350 g of flame retardant-I was capped with an epoxy group with tribromophenol. Abbreviated) 150 g was melt-blended in the same manner as in Synthesis Example 1. The properties of the obtained flame retardant-c are shown in Table 1.

Synthesis Example 4 544 g of TBA, 25 g of alkyl glycidyl ether having oxirane oxygen of 4.9% and epichlorohydrin (hereinafter referred to as E
134 g of CH) and 268 g of methyl isobutyl ketone (hereinafter abbreviated as MIBK) were placed in a 3 liter separable flask equipped with a thermometer, a stirrer, a dropping device, and a condenser, and dissolved while heating with nitrogen purging. , 75 ° C
Then, add 24 g of 48% NaOH aqueous solution, and add 4 at 90 ° C.
After reacting for a time, 300 g of MIBK and NaOH
120 g of an aqueous solution was added and the reaction was continued for 4 hours. After the reaction, the resin solution was diluted with MIBK, salt by-produced with ion-exchanged water was dissolved and washed, separated and removed, and then MIBK was removed by evaporation to obtain a pale yellow flame retardant-d. Its properties are shown in Table 1.
Shown in

Synthesis Example 5 90 g of TBA, 15 g of alkyl glycidyl ether having 4.0% oxirane oxygen and YD-400 and 400 g were charged in the same manner as in Synthesis Example-2, and 160 with nitrogen purging.
The reaction was carried out at 0 ° C for 5 hours. The properties of the obtained flame retardant-e are shown in Table 1.

Synthesis Example 6 YDB-400 (400 g) and octadecyl alcohol 1
5 g and 90 g of TBA were charged and reacted in the same manner as in Synthesis Example 2. Table 1 shows the properties of the obtained flame retardant-f.

Synthesis Example 7 114 g of bisphenol A and 327 g of alkylglycidyl ether (oxirane oxygen 4.9%) were charged, 0.1 g of catalyst triphenylphosphine was added, and 160 ° C.
And reacted for 5 hours. Obtained alkyl glycidyl ether
50g of ter compound and YDB-406, 950g and TB
-62 and 600 g were melt-blended to obtain a flame retardant-g. Synthetic Example 8 272 g of TBA and 327 g of alkylglycidyl ether
Was charged in the same manner as in Synthesis Example 7, triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C. for 5 hours. 30 g of the obtained alkylglycidyl ether compound and YD
B-406 and 470 g are melt-blended, and flame retardant-h
And

Synthetic Example 9 YDB-406 (650 g) and 2,4,6-tribromophenol (100 g) were charged, the reaction was carried out in the same manner as in Synthetic Example 8, and then alkyl glycidyl ether having oxirane oxygen of 4.0%. -Tel 23g was blended to make a flame retardant-i. Synthesis Example 10 YDB-406 (500 g) and TB-62 (500 g) were melt-blended to obtain a flame retardant-j.

Examples 1 to 9 and Comparative Examples 1 to 3 The flame retardants obtained from Synthesis Examples 1 to 9 and the flame retardant of Synthesis Example 10 and YDB-406 and TB-62 were blended in the compositions shown in Table 2, respectively. , A Henschel mixer, and then melt-mixed with a twin-screw extruder (Ikegai PCM-30) to obtain a compound. A test piece was prepared from the obtained compound by injection molding. Using this test piece, flammability, adhesion, and light resistance were measured. The results are shown in Table 2.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

The flame-retardant styrene resin composition of the present invention has excellent light resistance and extruder or injection molding by introducing alkyl glycidyl ether or its compound into halogenated epoxy resin as a flame retardant. It is possible to exert the effect of improving the adhesiveness to the screw and cylinder parts of the machine and is useful for improving the continuous productivity.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Noriko Naito 3-17-14 Higashikasai, Edogawa-ku, Tokyo Toto Kasei Co., Ltd.

Claims (6)

[Claims] 1. A flame-retardant styrene comprising a polystyrene resin (A) and a halogenated epoxy resin (B) containing an alkylglycidyl ether compound having 10 to 40 carbon atoms. -Based resin composition. 2. An alkylglycidyl ether compound having 10 to 40 carbon atoms is an alkylglycidyl ether having 10 to 40 carbon atoms, or an alkylglycidyl ether having 10 to 40 carbon atoms and phenols. Or a reaction product of an alkylglycidyl ether having 10 to 40 carbon atoms with a phenol end in an epoxy resin, or 10
1. At least one reaction product of 40 alkyl alcohols with epoxy groups of an epoxy resin is contained.
The flame-retardant styrene resin composition as described in 1. 3. The flame-retardant styrene according to claim 1, wherein the halogenated epoxy resin (B) has a structure in which 0 to 60% of the epoxy groups of the halogenated epoxy resin are blocked with halogenated phenols. -Based resin composition. 4. A compound in which 40 to 100 parts by weight of a halogenated epoxy resin (B) and 80% or more of the epoxy groups of the halogenated epoxy resin are blocked with halogenated phenols in an amount of 60 to 0 parts by weight. The flame-retardant styrene resin composition according to claim 1, wherein the flame-retardant styrene-based resin composition is a mixture obtained by melt-mixing a part of 5. The content of the alkyl glycidyl ether compound having 10 to 40 carbon atoms is 0.1 to 10 parts by weight based on the total amount of the halogenated epoxy resin (B). The flame-retardant styrene resin composition according to any one of 1. 6. With respect to 100 parts by weight of the styrene resin,
2. 10 to 50 parts by weight of a halogenated epoxy resin containing an alkyl glycidyl ether compound having 10 to 40 carbon atoms and 1 to 10 parts by weight of a flame retardant aid are contained. Flame-retardant styrene resin composition.