KR100555983B1 - Flameproof Styrenic Resin Composition - Google Patents

Abstract

Flame retardant rubber-reinforced polystyrene resin composition of the present invention (A) 50 to 90 parts by weight of rubber-reinforced polystyrene resin; (B) 50 to 10 parts by weight of polyphenylene ether resin; (C) 5 to 30 parts by weight of an aromatic phosphate ester compound based on 100 parts by weight of the base resin (A) + (B); And (D) 0.5 to 5 parts by weight of red (phosphorus) based on 100 parts by weight of the base resin (A) + (B). The present invention also provides a flame retardant rubber-reinforced polystyrene resin composition further comprising a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a pigment, a dye and / or an inorganic additive, depending on the use of the resin composition.

Description

Flame retardant rubber reinforced polystyrene resin composition {Flameproof Styrenic Resin Composition}             

Field of invention

The present invention relates to a styrene resin composition which is excellent in environmental friendliness and satisfies flame retardant standards because it does not use a halogen-based flame retardant, which has been tightened in terms of environmental stability. More specifically, the present invention relates to a resin composition in which a phosphate ester flame retardant is used in a rubber-reinforced polystyrene resin copolymer and a polyphenylene ether resin blend, and a red phosphorus is added to enhance flame retardancy.

Background of the Invention

Styrene resin, which is used as an exterior material of electronic products, is applied to almost all electronic products due to its excellent processability and mechanical properties, but the styrene resin itself has a property of easy combustion and is not resistant to fire. Therefore, the styrene-based resin can be easily burned by the external ignition source, and may play a role of further spreading the fire. In view of this, the United States, Japan and Europe, etc., are regulated by law to use only polymer resin that meets flame retardant standards as an exterior material in order to ensure the safety of fire of electronic products.

The most widely known flame retardant method is to impart flame retardant properties by applying a halogen-based compound and an antimony-based compound together to the rubber-reinforced styrene resin. As the halogen-based compound, polybromodiphenyl ether, tetrabromobisphenol A, brominated substituted epoxy compounds, chlorinated polyethylene and the like are mainly used. Antimony trioxide and antimony pentoxide are mainly used as an antimony compound.

The application of halogen and antimony compound together to impart flame retardancy has the advantage of easy flame retardancy and little property deterioration.However, the hydrogen halide gas generated during processing can damage the mold and burn during combustion. The occurrence of such a gas is likely to have a fatal effect on the human body. In particular, polybrominated diphenyl ethers, which are mainly halogen-based flame retardants, have a high possibility of generating very toxic gases such as dioxins and furans during combustion.

As a flame retardant containing no halogen, a method of imparting flame retardancy to a resin composition by adding a compound such as phosphorus or nitrogen has been studied. The application of the log is limited.

The present invention is to provide a rubber-reinforced polystyrene resin composition that can be used as an exterior material of an electronic product while satisfying the flame retardant standard by using a non-halogen-based flame retardant in response to the environmental problems and fire safety as described above.

In order to solve the problems of the existing flame retardant thermoplastic resins, the present inventors do not contain phenolic resin, and use a phosphate ester compound in a base resin made of a rubber-reinforced polystyrene resin and a polyphenylene ether resin, and to enhance flame retardancy. The addition of red-phosphorus has led to the development of resin compositions with environmental and fire safety.

An object of the present invention is to provide a thermoplastic flame retardant rubber-reinforced polystyrene resin composition that is stable against fire.

Another object of the present invention is to provide a rubber-reinforced polystyrene resin composition having environmental stability by using an environmentally friendly compound as a flame retardant, without using a halogen compound that causes environmental pollution during processing or combustion of the resin as a flame retardant.

Still another object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties, thermal stability, and flame retardancy.

Still another object of the present invention is to provide a flame retardant rubber-reinforced polystyrene resin composition which is excellent in workability and can be used as an exterior material such as electronic products.                         

The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

The flame-retardant rubber-reinforced polystyrene resin composition of this invention consists of (A) rubber-reinforced polystyrene resin, (B) polyphenylene ether resin, (C) aromatic phosphate ester compound, and (D) red-phosphorus.

The rubber modified styrene resin (A) is 50 to 90 parts by weight, the polyphenylene ether resin (B) is 50 to 10 parts by weight, and the aromatic phosphate ester compound (C) is the base resin (A) + (B) 100 5-30 weight part with respect to a weight part, and (D) are added in 0.5-5 weight part with respect to 100 weight part of said (A) + (B).

Hereinafter, each component of the resin composition of the present invention will be described in detail.

(A) Rubber reinforced polystyrene resin

The rubber-reinforced styrene resin used in the present invention is prepared by mixing a rubber with an aromatic monoalkenyl monomer and / or an alkyl ester monomer and polymerizing it using a polymerization initiator.

The rubber used herein is selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene, alkyl acrylate rubbers, and the like, and preferably 3 to 30 parts by weight, preferably 5 to 15 parts by weight. Do.

The monomers used herein are also selected from the group consisting of aromatic monoalkenyl monomers, alkyl ester monomers of acrylic acid or methacrylic acid, 70 to 97 parts by weight, preferably 85 to 95 parts by weight, of at least one monomer selected from the group. It is preferable to add wealth.

The polymerization initiator used in the present invention may be used by one or more selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumene hydroperoxide, the resin using a bulk polymerization Can be prepared.

The rubber-reinforced polystyrene resin may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof, and the bulk polymerization method may be preferably used as described above.

In order to give optimum physical properties in the blend of the rubber-reinforced polystyrene resin and the polyphenylene ether resin, the rubber particle size is preferably 1.5 to 2.0 µm.

(B) polyphenylene ether resin

Since rubber-reinforced styrene resins are insufficient in flame retardancy, and their rigidity and heat resistance are lowered, polyphenylene ether resin is added and used as the base resin. Such compounds include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl -6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly Copolymer of (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,5-triethyl- Copolymers of 1,4-phenylene) ether. Preferably a copolymer of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl- 1,4-phenylene) ether is used, of which poly (2,6-dimethyl-1,4-phenylene) ether is most preferred.

Although the polymerization degree of polyphenylene ether is not specifically limited, It is preferable that the intrinsic viscosity measured in 25 degreeC chloroform solvent is 0.2-0.8 in consideration of the thermal stability and workability of a resin composition.

(C) Aromatic Phosphate Ester Compounds

In the present invention, an aromatic phosphate ester compound represented by the following structural formula (1) is used:

Structural Formula 1

In formula (1), R ₁ , R _2, and R ₃ are each independently hydrogen or a C _1-4 alkyl group, X is a C _6-20 aryl group or a C _6-20 aryl group substituted with an alkyl group. It is derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A and bisphenol-S, and N has a value of 0-4. As the compound corresponding to Structural Formula 1, when N value is 0, triphenyl phosphate, tricresyl phosphate, trigylenyl phosphate, tri (2,6-dimethylphenyl) phosphate, and tri (2,4,6-tri Methylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, when N is 1, resorcinol bis (diphenyl) phosphate, Resorcinol bis (2,6-dimethylphenyl) phosphate, Resorcinol bis (2,4-dibutylbutylphenyl) phosphate, hydroquinol bis (2,6-dimethylphenyl) phosphate, hydroquinol bis (2,4 -Dibutylbutylphenyl) phosphate and the like are typical examples. These may be used alone or mixtures thereof may be used.

An aromatic phosphate ester compound (C) comprises 5-30 weight part with respect to 100 weight part of base resins (A) + (B).

(D) red-phosphorus

The enemy (D) used in the present invention is used to maintain flame retardancy. The above-mentioned (D) is a material which easily ignites itself, and in order to improve stability, it is concentrated in a product coated with a polymer resin or polyvinylacetate, polyamide, polystyrene and other types of polymer resins. The master-batch is used.

The said (D) uses 0.5-5 weight part with respect to 100 weight part of base resins (A) + (B) of this invention. If it is used less than 0.5 can not maintain the proper flame retardancy, when added 5 parts by weight or more is not preferable because the impact strength is lowered.

Red is a material that easily ignites itself, but it is a material that imparts flame retardancy when added to a polymer resin, and it can minimize the amount of the aromatic phosphate ester compound that reduces the heat resistance of the polystyrene resin when excessively added. Excellent workability can be obtained by minimizing the amount of polyphenylene ether resin used to form char, which is a flame retardant film that is generated.

In the thermoplastic resin manufacturing method of the present invention, an antidripping agent, an impact enhancer, a plasticizer, an inorganic additive, a heat stabilizer, an antioxidant, a compatibilizer, a light stabilizer, a pigment, and / or a dye may be added according to each use. The inorganic additives to be added include asbestos, glass fibers, talc, ceramics and sulfates, which may be used in an amount of 0 to 50 parts by weight based on 100 parts by weight of the base resin of the present invention.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Preparation and specifications of (A) rubber-reinforced styrene resin, (B) polyphenylene ether resin, (C) aromatic phosphate ester compound and (D) product used in the resin compositions of the following Examples and Comparative Examples are as follows. same.

(A) Rubber reinforced styrene resin

As rubber-reinforced polystyrene resin, Cheil Industries HI-1190F was used. The rubber-reinforced polystyrene resin has a particle size of 1.5 to 2.0 µm in rubber form and exhibits the maximum impact strength in the blend of rubber-reinforced polystyrene resin and polyphenylene ether resin.

(B) polyphenylene ether (PPE) resin

Poly (2,6-dimethyl-phenylether) (trade name P-402), manufactured by Asahi Kasei Co., Ltd., Japan, was used. The particle size was in the form of a powder having an average particle diameter of several tens of micrometers.

(C) phosphate ester compound

Triphenylphosphate is a substance having a melting point of 48 ° C.

(D)

Red is a product of Nippon Rin Chemical Co., Ltd. (product name RINKA FR120) which is a powder type product having a particle size of several tens of micrometers and is stabilized by coating the surface of the powder with a polymer.

Each component was added to the content as shown in Table 1 below and extruded in a conventional twin screw extruder at a temperature of 200 ~ 280 ℃ to prepare a pellet. The flame retardancy of the specimens prepared according to the UL 94 VB flame retardant standard was measured and the Izod impact strength (1/8 "notch, kgf · cm / cm) was measured according to ASTM D-256. 1 kg according to ASTM D-1525. The Viquette softening temperature of the prepared specimen was measured at a load of, and the melt flow index (g / 10 min) was measured at 220 ° C. and 10 kg according to ASTM D-1238.

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Ingredients (parts by weight) (A) 75 75 70 65 65 (B) 25 25 30 35 35 (C) 11 11 11 11 14 (D) One - - - - Properties Izod impact strength (kgcm / cm ″) 13 16 17.3 19.2 18.1 Melt flow index 55 55 41 35 38 Bicket Softening Temperature (℃) 85 85 87 89 86 Flame Retardant (1/8 ") V-0 V-2 V-1 V-1 V-1

Example 1

Rubber-reinforced polystyrene resin (A), polyphenylene ether (B), triphenyl phosphate (C) and red (D) were added in the amounts shown in Table 1, and 0.5 parts by weight of an antioxidant was added to prepare a resin composition.

Comparative Examples 1 to 4

In the resin composition of this invention, while adding content of components (A), (B), and (C) as shown in Table 1, the resin composition was produced, without adding (D).

In the case where no enemy (D) is added as in Example 1, char is formed as a non-flammable film during combustion, so that flame retardancy of UL94 standard V-0 grade is ensured even if the amount of polyphenylene ether resin that can ensure flame retardancy is increased. It was difficult to, and the impact strength was improved but the fluidity was significantly decreased as the composition ratio of the polyphenylene ether resin was increased. In addition, it was found that when the amount of triphenyl ester used as a flame retardant was not increased when the product (D) was not added as in Comparative Examples 1 to 4, the flame retardant standard could not be achieved.

The flame-retardant rubber-reinforced polystyrene resin composition of the present invention is excellent in mechanical strength and heat resistance by using a red as a result of minimizing the amount of the polyphenylene ether resin and the amount of the aromatic phosphate ester compound which causes the heat resistance deterioration when used in excess. By using an environmentally friendly compound as a flame retardant, it has the effect of the invention excellent in environmental stability.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (3)

(A) 50 to 90 parts by weight of rubber-reinforced polystyrene resin; (B) 50 to 10 parts by weight of polyphenylene ether resin; (C) 5 to 30 parts by weight of the aromatic phosphate ester compound based on 100 parts by weight of the base resin (A) + (B); And (D) 0.5 to 5 parts by weight of red (phosphorus) based on 100 parts by weight of the base resin (A) + (B); Flame-retardant rubber-reinforced polystyrene resin composition, characterized in that consisting of. The flame-retardant rubber-reinforced polystyrene resin composition according to claim 1, wherein the aromatic phosphate ester compound (C) is a compound represented by the following structural formula (1): Structural Formula 1

R ₁ , R ₂ and R ₃ in the above formula (1) are independently of each other hydrogen or an alkyl group of C _1-4 ; X is a C _6-20 aryl group substituted with a C _6-20 aryl group or an alkyl group derived from dialcohols such as resorcinol, diphenol, hydroquinol, bisphenol-A and bisphenol-S; And N is a value of 0-4. The method according to claim 1, wherein (D) is used in a product form coated with a polymer resin in powder form or as a master-batch in a polymer resin including polyvinylacetate, polyamide and polystyrene. Flame retardant rubber-reinforced polystyrene resin composition.