JPS5941462B2 - Method for thermally stabilizing flame retardant resin compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to acrylonitrile butadiene styrene resin (hereinafter referred to as ABS).

), a bromine-based flame retardant, and antimony trioxide. Regarding stabilization methods. ABS is suitable for injection molded products due to various conditions such as economic efficiency, moldability, and physical properties, and is often used as a material for electrical parts.

Recently, regulations on flame retardant materials used in household electrical appliances have become stricter in order to prevent fire accidents. ABS has the disadvantage of being easily combustible, and in order to provide flame retardancy, it is necessary to blend ABS with a flame retardant such as a bromine flame retardant, antimony trioxide, or a phosphorus compound. However, A
When these flame retardants are added to BS, the thermal stability is significantly reduced, so the development of an excellent stabilizer that prevents thermal deterioration has been awaited. The present inventors used ABSlOO in parts by weight, 3 to 30 parts by weight of bromine-based flame retardant, and 2 to 1 part by weight of antimony trioxide.
As a result of various studies on the thermal stabilization method of a flame retardant resin composition consisting of a weight ratio of 5 parts by weight, we found that the general formula (where R and Rl are alkyl groups having 4 to 8 carbon atoms) can be,
They can be the same or different.

n is an integer from 2 to 10. ) and 0.2 to 6 parts by weight of a dialkyltin maleate polymer having the formula (wherein R2
, R3 are alkal groups having 1 to 8 carbon atoms, and may be the same or different. R4 and R5 are an alkyl group or an alkoxyalkyl group having 4 to 18 carbon atoms, and may be the same or different. ) is added to ABS in a proportion of 10 to 60% by weight based on the dialkyl tin maleate polymer shown in the general formula 2 to provide excellent thermal stability. This discovery was made and the present invention was completed. To explain in more detail, a bromine-based flame retardant is generally used to make ABS flame retardant, but since this bromine-based flame retardant alone is insufficient for flame retardation, antimony trioxide is used in combination to improve flame retardancy.

It is generally known to use organic tin mercaptite as a stabilizer for ABS.

However, for flame-retardant resin compositions made by adding bromine-based flame retardants and antimony trioxide to ABS, organotin mercaptite has an insufficient thermal stabilizing effect and can hardly be processed at high temperatures. However, when thermally stabilizing this flame retardant resin composition, dialkyltin maleate stabilizers, which are generally ineffective in thermally stabilizing ABS, are particularly effective, and among dialkyltin maleate stabilizers, It was found that dialkyltin maleate polymers do not lower the flexibility temperature of molded products.

However, the thermal stabilizing effect of this dialkyltin maleate polymer alone is still insufficient.

The present inventors found that the thermal stabilization effect was significantly improved by using organotin mercaptite in combination with dialkyltin maleate polymer, and after carrying out various studies, they found that , dialkyltin bis(alkyl 3-
mercaptopropionate), dialkyltin bis(alkylmercaptoacetate), dialkyltin sulfide, dialkyltin dialkylmercaptite, dialkyltin S, O-mercaptoacetate, dialkyltin S,
O-3-mercaptopropionate, monoalkyltin tris (alkylmercaptoacetate), monoalkyltin tris (alkyl 3-mercaptopropionate),
Monoalkylthiostannic acid, bis(dialkyltinalkyl 3
-mercaptopropionate) oxide, among which dialkyltin bis(alkylmercaptoacetate) was found to have particularly excellent thermal stabilizing effects. This effect is particularly remarkable in the case of flame-retardant resin compositions in which ABS is added with a bromine-based flame retardant and antimony trioxide.

The combined ratio of dialkyltin maleate polymer and dialkyltin bis(alkylmercaptoacetate) is
For dialkyltin maleate polymer, dialkyltin bis(alkylmercaptoacetate) is 10 to 6
0% by weight is preferred, particularly preferably 20 to 30% by weight. The amount of dialkyltin maleate polymer added is preferably 0.2 to 6 parts by weight based on the weight of ABSlOO, and if it is less than 0.2 parts by weight, there is almost no thermal stabilizing effect, and if it exceeds 6 parts by weight, it is economical. The amount is preferably 0.5 to 5 parts by weight, subject to limitations. The dialkyltin maleate polymer represented by the general formula [1] used in the present invention includes di-n-butyltin maleate polymer, di-n-octyltin maleate polymer, and n-butyltin maleate polymer.
n-octyltin maleate polymer) and the like.

Examples of dialkyltin bis(alkylmercaptoacetate) represented by the general formula are dimethyltin bis(amylmercaptoacetate), dimethyltin bis(hexylmercaptoacetate), dimethyltin bis(2-ethylhexylmercaptoacetate), and dimethyltinbis(amylmercaptoacetate). Tin screw (
isooctyl mercaptoacetate), dimethyltin bis(oleyl mercaptoacetate), di-n-butyltin bis(butyl mercaptoacetate), di-n-butyltin bis(methoxybutyl mercaptoacetate), di-n-butyltin bis( 2-ethylhexylmercaptoacetate), di-n-butyltin bis(isooctylmercaptoacetate), di-n-butyltin bis(nonylmercaptoacetate), di-n-octyltin bis(hexylmercaptoacetate), di-n-butyltin bis(hexylmercaptoacetate) −Octyltin screw (
2-ethylhexylmercaptoacetate), di-n-
Octyltin bis(isooctylmercaptoacetate)
, di-n-octyltin bis(tridecylmercaptoacetate), etc. Particularly preferred examples include dimethyltin bis(isooctylmercaptoacetate), dimethyltin bis(2-ethylhexylmercaptoacetate), -n-butyltin bis(isooctylmercaptoacetate), di-n-butyltin bis(2-
ethylhexylmercaptoacetate), di-n-octyltin bis(isooctylmercaptoacetate), di-n-octyltin bis(2-ethylhexylmercaptoacetate), and the like.

Examples of preferred bromine-based flame retardants that can be used in the present invention include hexapromobenzene, tetrabromophthalic anhydride, decapromodiphenyl ether, and tetrabromobisphenol A.

Further, in the present invention, vinyl chloride resin, chlorinated polyethylene, chlorinated vinyl chloride resin, vinylidene chloride resin, lubricant, antioxidant, filler, pigment, etc. can be added as necessary.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

In the examples, parts mean parts by weight. Example 1 100 parts of ABS (Toyorak 100 manufactured by Toray Industries, Inc.), 20 parts of tetrapromobisphenol A (Fire Guard 2000 manufactured by Teijin Kasei Ltd.), 5 parts of antimony trioxide, and 4 parts of stabilizer (Table 1) ) was kneaded for 5 minutes using a test roll adjusted to 1605C to form a sheet with a thickness of 0.5 mm.

Each of these sheets was cut into a size of 25 mm x 75 mm, and then placed in a gear type aging tester adjusted to 210° C. to test thermal stability. The results are shown in (Table 1). As for thermal stability, the sheet was taken out from the gear type aging test rock every 15 minutes and the degree of coloration of the sheet was visually determined and indicated.

Also, stack 8 sheets of each roll and heat at 180°C11.
The degree of coloration obtained by pressing at 5k9/CTi for 60 minutes is also shown in Table 1.

The degree of polymerization n of the di-n-butyltin maleate polymer and the di-n-octyltin maleate polymer is 2.5 and 2.8, respectively.

Example 2 100 parts of ABS (Toyorak 100 manufactured by Toray Industries, Inc.) and vinyl chloride resin (GeOnlO3EP manufactured by Nippon Zeon Co., Ltd.)
-8) A mixture of 10 parts of decapromodiphenyl ether (Brannellon DB-100 manufactured by Mitsui Toatsu Co., Ltd.), 5 parts of antimony trioxide, and 5 parts of stabilizer (Table 2) was added to 160 parts.
Example 1 was kneaded for 5 minutes using a test roll adjusted to 0C.
I conducted a similar test.

The results are shown in (Table 2). The degree of polymerization n of the di-n-butyltin maleate polymer and the di-n-octyltin maleate polymer is 2.5 and 2.8, respectively.

Claims (1)

[Claims] 1 Acrylonitrile-butadiene-styrene resin 10
0 parts by weight, 3 to 30 parts by weight of bromine-based flame retardant, and 2 to 15 parts by weight of antimony trioxide. On the other hand, the general formula [ I
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R and R^1 are alkyl groups having 4 to 8 carbon atoms, and can be the same or different. n is an integer of 2 to 10. 0.2 to 6 parts by weight of a dialkyltin maleate polymer having the general formula [I
I]▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^2 and R^3 are alkyl groups having 1 to 8 carbon atoms, and can be the same or different. R^4, R ^5 is an alkyl group or alkoxyalkyl group having 4 to 18 carbon atoms, and they can be the same or different. 1. A method for thermally stabilizing a flame retardant resin composition, which comprises adding tin maleate to an acrylonitrile butadiene/styrene resin in a proportion of 10 to 60% by weight.