KR19990052379A - Flame retardant styrene resin composition - Google Patents

Abstract

The present invention uses 5 to 30 parts by weight of an imide halogen compound (B) having excellent weathering stability except decabromodiphenyl oxide based on 100 parts by weight of rubber-reinforced polystyrene resin (A) as the main flame retardant, and the processing temperature of the styrene resin. 1 to 10 parts by weight of phenoxy hydride halogen compound (C), which does not decrease impact strength and fluidity by melting with styrene resin, is used as a nonflammable agent, and 1 to 10 parts by weight of antimony trioxide (D) is used as an auxiliary flame retardant. E) It is related with the flame-retardant styrene resin composition improved further by the impact strength, fluidity | liquidity, and heat stability which add 0.5 to 10 weight part and 0.1-5 weight part of olefin type active agents (F).

Description

Flame retardant styrene resin composition

The present invention relates to a styrene resin composition having improved weather resistance and excellent impact strength, fluidity, thermal stability, and flame retardancy. More specifically, a non-melting halogen compound is used as a main flame retardant in a rubber-reinforced polystyrene resin copolymer, The present invention relates to a flame retardant styrene resin composition which is used as a flame retardant aid and further improves impact strength, fluidity and thermal stability while maintaining excellent weather resistance by adding a molten halogen compound as a nonflammable agent.

Generally, styrene-based resin has good processability and mechanical strength, so it is mainly used in the exterior of electric and home appliances, but the resin itself is not resistant to fire and when the flame is ignited by deepening factors, the resin itself helps combustion. It acts as an energy, but rather has a disadvantage of continuously spreading fire.

In view of this, countries such as the United States and Europe have legalized to use only flame retardant resins for the manufacture of molded parts of electronic products in order to ensure stability against fire of electronic products.

As a method of imparting flame retardancy to a resin having such characteristics, it can be classified into an additional flame retardant method in which a flame retardant and a flame retardant aid are added, and a polymerized flame retardant method in which a resin is prepared using a special monomer containing a flame retardant atom during polymerization. Although many studies have been conducted in the experimental stage of the double polymerization flame retardant method, commercialized products have not been released due to high cost and difficulty in achieving flame retardancy. Therefore, most commercialized flame retardant resins are prepared by an additive flame retardant method in which a flame retardant containing halogen or phosphorus, which is an inert element, is added during compounding.

An additional flame retardant method in which a flame retardant is added to impart flame retardancy to a styrene resin is prepared by adding one or more components selected from halogen-containing organic compounds and antimony-containing inorganic compounds to the resin. Halogen-containing organic compounds, mainly bromine or chlorine compounds, are very flame retardant when added to styrene resins, while causing serious degradation in overall physical properties such as impact strength, weather stability, heat resistance and processability of the resin itself. Accordingly, in manufacturing a flame retardant resin, a technique for minimizing the side effects such as deterioration of physical properties and processability, appearance defects, and weather resistance stability while maintaining excellent flame retardancy has become very important.

The flame retardant most commonly applied to rubber-reinforced polystyrene among bromine compounds is decabromodiphenyl oxide (DBDPO), which is used in combination with a flame retardant aid such as antimony trioxide, but has a disadvantage in that weather resistance is lowered. For this reason, when decabromodiphenyl oxide-based flame retardant resin is applied to a product that requires light gray and ivory light colors, it is easily discolored, and thus it is necessary to improve weather resistance separately.

In this case, in order to solve the problem of weather resistance, a method of mixing and using a large amount of weathering stabilizer in a compounding process or a combination of hindered amine light stabilizers and ultraviolet absorbers, which are known to have synergistic effects, are simultaneously used. Although it adopts the method, it acts as a factor of the cost increase due to the additional input, and it causes the deterioration of thermal stability when excessively input for the excellent weather stability effect. As another method for improving weather resistance, a method of adding a large amount of titanium dioxide has been proposed, but has a disadvantage in that impact strength is lowered.

Recently, for the purpose of cost reduction, the conversion of a copier or FAX exterior material mainly applied to flame retardant ABS (Acrylonitrile-Butadiene-Styrene copolymer) into a rubber-reinforced polystyrene resin having a flame retardancy has been considered. Unlike the TV exterior material, which is black, the copier or FAX exterior material is applied with a lot of colors of light gray or ivory type, and therefore, particularly excellent weather resistance is required. In addition, since the shape of the molded article is very complicated, excellent thermal stability that can be molded without appearance defects even under various molding conditions in which injection defects have a high possibility of appearance defects such as gas silver or black streak due to decomposition gas. Required.

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame retardant styrene resin composition having improved impact strength, flowability and thermal stability while solving the conventional problems and maintaining excellent weather resistance.

That is, the present invention uses 5 to 30 parts by weight of an imide halogen compound (B) having excellent weather stability except decabromodiphenyl oxide based on 100 parts by weight of rubber-reinforced polystyrene resin (A) as a main flame retardant, and processing of styrene resin. 1 to 10 parts by weight of a phenoxy clock halide compound (C), which does not decrease impact strength and fluidity by melting with styrene resin at temperature, is used as a nonflammable agent, and 1 to 10 parts by weight of antimony trioxide (D) is used as an auxiliary flame retardant. (E) 0.5 to 10 parts by weight, and olefin-based activator (F) 0.1 to 5 parts by weight, characterized in that the impact resistance, fluidity and thermal stability of the flame retardant styrene resin composition further improved.

Hereinafter, the present invention will be described in detail.

The rubber-reinforced polystyrene resin (A) used in the present invention is prepared by mixing a rubber with an aromatic monoalkenyl monomer and / or an alkylester monomer and polymerizing it using a polymerization initiator.

As rubber used in rubber-reinforced polystyrene resin (A), 3 to 30 parts by weight, preferably 5 to 15 parts by weight of rubber selected from butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene or alkyl acrylate rubbers In addition, it is preferable to add 70-97 parts by weight, preferably 85-95 parts by weight of one or more monomers selected from aromatic monoalkenyl monomers, alkyl ester monomers of acrylic acid or methacrylic acid.

As polymerization initiator, bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof is used by using one or more initiators selected from benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumenehydro peroxide. It may be prepared by, but preferably may be prepared by bulk polymerization.

In the present invention, as a flame retardant used to improve weather resistance while maintaining flame retardancy, a halogen compound (B) having excellent weather resistance with little decomposition or change of structure by ultraviolet rays is used among bromine compounds except decabromodiphenyl oxide. As the flame retardant, it is preferable to use a flame retardant selected from an aliphatic compound such as an imide-based compound substituted with halogen having excellent heat resistance and weather resistance, a brominated diphenyl ethane compound or a chlorinated polyethylene resin or a vinyl chloride resin, and particularly impact strength and fluidity. In order to reinforce, it is preferable to use a halogen compound (C) which melts with the styrene resin at the processing temperature of the styrene resin.

The imide halogen compound used in the halogen compound (B) of the present invention is a substance represented by the following formula (1).

In Formula 1, n is an integer of 0 or more, and X is an integer of 1 to 4.

The flame retardant is preferably used 5 to 30 parts by weight based on 100 parts by weight of rubber-reinforced polystyrene resin (A). If the amount is less than 5 parts by weight, the flame retardant effect is insufficient, and if it exceeds 30 parts by weight it is not preferable because the deterioration of workability and mechanical strength, which impairs the balance of physical properties.

In addition, a phenoxy clock halogen compound (C) which can be represented by the following Chemical Formula 2, which is melted with a styrene-based resin at a processing temperature of the styrene-based resin, prevents a decrease in laminar strength, improves fluidity, and has excellent weather stability, is used as a flame retardant. It is preferable to use.

n is an integer of 2 or more, and R is And R in X is an integer from 1 to 5.

The flame retardant is preferably used 1 to 10 parts by weight based on 100 parts by weight of rubber-reinforced polystyrene-based resin (A). If the amount is less than 1 part by weight, the flame resistance effect impact strength and fluidity is lowered, and if it exceeds 10 parts by weight, weather resistance is poor.

Antimony trioxide (C) added to impart flame retardancy in the present invention is preferably used 1 to 10 parts by weight, preferably 2 to 7 parts by weight based on 100 parts by weight of the rubber-reinforced polystyrene resin (A) of the present invention. If the amount of the antimony trioxide (C) is less than 1 part by weight, a sufficient flame retardant effect cannot be obtained. If the amount of the antimony trioxide (C) is used in excess of 10 parts by weight, the balance of the physical properties of the resin composition is impaired, which is not preferable.

In the present invention, it is preferable to add 0.5 to 10 parts by weight of the styrene-butadiene copolymer to 100 parts by weight of the rubber-reinforced polystyrene resin (A) to reinforce the impact strength of the resin composition. It is preferable to add 0.1-5 weight part with a molecular weight 1000-5000.

In addition, inorganic additives, thermal stabilizers, antioxidants, other light stabilizers, pigments and dyes may be added in the required amounts according to the use of the present invention.

The flame retardant styrene resin composition of the present invention uses a halogen compound as a flame retardant in rubber-reinforced polystyrene resin, antimony trioxide as a flame retardant adjuvant, adds an impact modifier and an olefin lubricant, and then mixes in a conventional mixer and mixes the mixture To prepare a resin composition in the form of pellets through an extruder.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by the following Examples.

First, each component used in the Example and the comparative example is as follows.

Rubber-reinforced polystyrene resin (A) was used HR-1360 of Cheil Industries, and the imide halogen compound (B) represented by the formula (1) and the phenoxy clock halogen compound (C) represented by the formula (2), The antioxidant was Ciba-Geigy Iganox 1076 (CYBA-GEIGY IGANOX 1076), and Zn-stearate of Songwon Industrial Co., Ltd. was used.

Examples 1-5

Rubber-reinforced polystyrene resins, imide halogen compounds, phenoxy halogen compounds, antimony trioxide, impact modifiers and olefin lubricants are added in the amounts shown in Table 1, and 0.5 parts by weight of antioxidant and 1 part by weight of stearic acid salt are added to the resin composition. Was prepared.

Comparative Examples 1 to 7

A resin composition was prepared in the same manner as in Example, except that the resin composition was used in the amount shown in Table 1 below.

Example Comparative example One 2 3 4 5 One 2 3 4 5 6 7 A 100 100 100 100 100 100 100 100 100 100 100 100 B 10 10 10 10 15 15 15 15 15 15 15 15 C One 3 5 10 5 - - - - - - - D 5 5 5 5 5 5 5 5 5 5 5 5 E 2 2 2 2 2 One 2 5 8 2 2 2 F 0.5 0.5 0.5 0.5 0.5 - - - - 0.5 One 2

(Unit is parts by weight)

According to the content of Table 1, rubber-reinforced polystyrene resins, imide halogen compounds, phenoxy halogen compounds, antimony trioxide, impact modifiers, olefin lubricants, antioxidants and stearic acid salts of the composition evenly mixed with a Henschel mixer After extrusion by using a twin screw extruder was prepared in the form of pellets. From the prepared pellets were prepared by the injection molding of the test specimen for the physical property of 1/16 "thickness and the physical properties were evaluated and shown in Table 2.

Example Comparative example One 2 3 4 5 One 2 3 4 5 6 7 Izod impact strength 10.9 10.1 9.8 9.1 6.9 5.0 7.4 10.5 15.1 7.5 7.7 7.5 liquidity 1.3 7.1 8.1 11.5 8.1 3.2 3.5 3.9 4.4 4.5 5.5 6.7 Flame retardant V-2 V-1 V-0 V-0 V-0 V-0 V-0 V-1 V-2 V-0 V-0 V-0 Visual defects 0 0 0 0 0 0 0 5 15 0 4 10

Property evaluation method

(1) Flame retardant measurement: Determined by the test according to the UL-94 test method.

(2) Weather resistance measurement: The weather resistance measuring instrument (Weather-O-Meter) was measured for 300 hours according to ASTM D4459 (Indoor Test) method to compare the degree of discoloration (ΔE) of each sample.

(3) Measurement of appearance defects: The number of gas silvers and black streaks appearing on the surface of the molded article after injection was maintained after being kept in the injection machine for 20 minutes (injection temperature 230 ° C.).

As shown in Table 2, in the case of using the imide-based halogen compound and the phenoxy-halogen halogen compound, the amount of the lubricant and the impact modifier lacking the thermal stability added for the reinforcement of the fluidity and the impact strength is reduced to the minimum, thereby providing excellent weather stability and flame retardancy. It can be seen that it is possible to prepare a resin composition that maintains thermal stability without deteriorating impact strength and fluidity while maintaining the degree.

As described above, the flame retardant styrene resin composition of the present invention uses an imide halogen compound as a main flame retardant in rubber-reinforced polystyrene resin, a phenoxy halogen compound as a flame retardant, and antimony trioxide as a flame retardant aid. It is possible to minimize the amount of the lubricant is insufficient to maintain the impact strength, fluidity and excellent thermal stability.

Claims (2)

100 parts by weight of rubber-reinforced polystyrene resin (A); 5 to 30 parts by weight of an imide halogen compound (B) which may be represented by the following Chemical Formula 1 except decabromodiphenyl oxide; 1 to 10 parts by weight of a phenoxy clock halogen compound (C) represented by Formula 2; 1 to 10 parts by weight of antimony trioxide (D); Styrene-butadiene impact modifier (E) 0.5 to 10 parts by weight; A flame retardant styrene resin composition comprising 0.1 to 5 parts by weight of an olefin lubricant (F). Formula 1 n is an integer greater than or equal to 0, and X is an integer of 1-4. Formula 2 n is an integer of 2 or more and R is And R in X is an integer from 1 to 5. The rubber used in the rubber-reinforced polystyrene resin (A) is 3 to 30 parts by weight of a rubber selected from butadiene rubber, isoprene rubber, a copolymer of butadiene and styrene or an alkyl acrylate rubber and an aromatic monoal. A flame retardant styrene resin composition, characterized in that 70 to 97 parts by weight of at least one monomer selected from the alkyl ester monomers of kenyl monomer, acrylic acid or methacrylic acid.