KR100778008B1 - Flameproof styrenic resin composition - Google Patents

Abstract

A flame retardant styrene-based resin composition, a pellet obtained by extruding the composition, and an exterior material of an electronic device molded from the composition are provided to improve the balance of physical properties such as heat resistance and workability and to obtain excellent flame retardancy even by using a small amount of a flame retardant. A flame retardant styrene-based resin composition comprises 100 parts by weight of a base resin which comprises 50-99 wt% of a styrene-based resin and 1-50 wt% of a polyphenylene ether resin; and 0.1-30 parts by weight of a phosphonium-based compound represented by the formula 1, wherein R1 is a C1-C6 alkyl group, an aryl group, or a C1-C6 alkyl group having a carboxyl group at terminal; and X is a halogen atom.

Description

Flame retardant styrenic resin composition {Flameproof Styrenic Resin Composition}

Field of invention

The present invention relates to a flame retardant styrene resin composition. More specifically, the present invention relates to a flame retardant styrene resin composition having excellent flame retardancy by applying a phosphonium compound as a flame retardant to a base resin composed of a styrene resin and a polyphenylene ether resin.

Background of the Invention

Generally, styrene resins, which are used as exterior materials for electronic products, are applied to almost all electronic products due to their excellent processability and mechanical properties. However, 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 serve to further spread the fire. In view of this, the United States, Japan and Europe countries regulate the law to use polymer resin that meets the flame retardant standards to ensure the safety of fire of electronic products.

The most widely known flame retardant method is to apply a halogen compound or a phosphorus compound as a flame retardant to rubber-reinforced styrene resins. However, since the flame retardant alone does not obtain sufficient flame retardancy, halogen-based compounds impart flame retardant properties by applying antimony-based compounds together, and phosphorus-based compounds may be flame retardant by using a char forming agent such as polycarbonate resin or polyphenylene ether resin. To achieve. Examples of the halogen compound used herein include polybromodiphenyl ether, tetrabromobisphenol A, brominated substituted epoxy compounds and chlorinated polyethylene, and antimony compounds include antimony trioxide and antimony pentoxide, and phosphorus compounds include triphenylphosphate. Aromatic phosphate esters such as are mainly used.

US Patent No. 3,639,506 discloses a flame retardant resin composition using an aromatic phosphate ester and a halogen flame retardant as a flame retardant in a polyphenylene ether resin and a styrene resin. However, this patent uses a large amount of polyphenylene ether resin and flame retardant to obtain sufficient flame retardancy.

Therefore, the inventors of the present invention to solve the problems of the conventional flame-retardant thermoplastic resin by using a styrene resin and polyphenylene ether resin as a base resin and applying a phosphonium-based compound to the flame retardant, thereby producing a fire-retardant styrene resin composition excellent in fire safety It is early to develop.

An object of the present invention is to provide a flame retardant styrene resin composition that is stable against fire.

Another object of the present invention is to provide a flame retardant styrene resin composition which can achieve v-0 flame retardancy even with a small flame retardant.

Still another object of the present invention is to provide a flame retardant styrene resin composition having excellent balance of physical properties such as heat resistance and workability.

The above and other objects of the present invention can be achieved by the present invention described below.

Summary of the Invention

Styrene-based resin composition according to the present invention (A) 50 to 99% by weight of styrene resin; And (B) 0.1-30 weight part of (C) phosphonium compounds with respect to 100 weight part of basic resins (A) + (B) which consist of 1-50 weight% of polyphenylene ether resins.

The resin composition of the present invention may optionally further include an organophosphorus flame retardant in addition to the above components. An aromatic phosphoric acid ester compound may be used as the organic phosphorus flame retardant.

The resin composition of the present invention may further include an additive selected from the group consisting of plasticizers, thermal stabilizers, antidrip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, lubricants, inorganic additives, and mixtures thereof.

The present invention includes pellets extruded from the composition. The present invention also includes an exterior material of an electrical and electronic product molded into the resin composition. Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

(A) styrene resin

The styrene resin (A) used in the resin composition according to the present invention includes polystyrene resin, styrene copolymer resin, rubber modified styrene copolymer resin and the like. Preferably a rubber modified styrene copolymer may be used. The resin may be used alone or in a mixture of two or more thereof.

In one embodiment of the present invention, the styrene resin may be a polymer obtained by polymerizing a rubber and an aromatic monoalkenyl monomer.

In another embodiment of the present invention, the styrene resin is prepared by mixing a rubber, an aromatic monoalkenyl monomer, an alkyl ester monomer, and / or an unsaturated nitrile monomer, and polymerizing the polymer using thermal polymerization or a polymerization initiator thereto.

The rubbers include butadiene rubbers, copolymers of butadiene and styrene, diene rubbers such as poly (acrylonitrile-butadiene), saturated rubbers hydrogenated with the diene rubber, isoprene rubber, acrylic rubber and ethylene-propylene-diene. The monomer terpolymer (EPDM) and the like can be used, and preferably polybutadiene, a copolymer of butadiene and styrene, isoprene rubber, alkyl acrylate rubbers, and the like are used. The content of the rubber is 3 to 30% by weight, preferably 5 to 15% by weight of the total weight of the styrene resin. The particle size of the rubber is preferably 0.1 to 4.0 ㎛ in order to give optimum physical properties in the blend of styrene resin (A) and polyphenylene ether resin (B).

As the aromatic monoalkenyl monomer, styrene, α-methyl styrene, β-methyl styrene, p-methyl styrene, para t-butyl styrene, ethyl styrene, or the like may be used. The aromatic monoalkenyl monomer is copolymerized by adding 70 to 97% by weight, preferably 85 to 95% by weight of the total weight of the styrene resin.

The styrene resin of the present invention may be polymerized by adding monomers such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like to impart properties such as chemical resistance, processability, and heat resistance during manufacture. . The amount to be added may be added at 40% by weight or less based on the total styrene resin.

The styrene-based resin may be polymerized by thermal polymerization without the presence of an initiator, or may be polymerized in the presence of an initiator. Polymerization initiators that can be used include one or more selected from peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumenehydro peroxide, and azo initiators such as azobis isobutyronitrile. May be, but is not necessarily limited thereto.

The styrene-based resin (A) may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, and among these polymerization methods, a bulk polymerization method may be preferably used.

Styrene-based resin (A) in the present invention comprises 50 to 99% by weight of the base resin.

(B) polyphenylene ether resin

Since the resin composition which concerns on this invention lacks flame retardance and heat resistance falls only by the said styrene resin (A), polyphenylene ether resin (B) is added and used as a base resin.

Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-di Propyl-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 ) Copolymer of poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,5) Copolymers of -triethyl-1,4-phenylene) ether and the like, and mixtures thereof can also be applied. 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 degree of polymerization of the polyphenylene ether (B) in the present invention is not particularly limited, the intrinsic viscosity measured in a chloroform solvent at 25 ° C. is preferably 0.2 to 0.8 in consideration of thermal stability and workability of the resin composition.

Polyphenylene ether resin (B) in the present invention is used in the range of 1 to 50% by weight. When used at less than 1% by weight, sufficient heat resistance may not be obtained, and when it exceeds 50% by weight, workability may decrease.

(C) phosphonium compounds

The phosphonium compound (C) of the present invention is used as a flame retardant to impart flame retardancy to a base resin composed of a styrene resin and a polyphenylene ether resin. The phosphonium compound (C) of the present invention has a structure represented by the following formula (1).

[Formula 1]

In the R ₁ is an alkyl group of C ₁ -C ₆ having a carboxyl group in the C ₁ -C ₆ alkyl group or an aryl group, or terminal, X is a halogen atom.

Specific examples of the phosphonium-based compound include methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, carboxy ethyl triphenyl phosphonium bromide, tetraphenyl phosphonium bromide And methyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium chloride, carboxy ethyl triphenyl phosphonium chloride, tetraphenyl phosphonium chloride and the like. The phosphonium-based compound may be applied alone or in mixture of two or more thereof.

Methods for preparing the phosphonium-based compound are well known in the art to which the present invention pertains, and are available for commercial purchase.

In the present invention, the phosphonium compound is used in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably 3 to 15 parts by weight, based on 100 parts by weight of the base resin. When applied in excess of 30 parts by weight, the mechanical properties Can be degraded.

The present invention may further include an organophosphorus flame retardant together with the phosphonium compound. The organophosphorous flame retardant may be applied in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the base resin.

In a preferred embodiment of the present invention, an aromatic phosphate ester compound is used as the organophosphorus flame retardant. The aromatic phosphate ester compound is represented by the structure of the following formula (2).

[Formula 2]

In the formula R _3, R ₄ and R ₅ are independently hydrogen or alkyl of one another C ₁ -C _4, X is an aryl group of C ₆ -C ₂₀ aryl group or a substituted C ₆ -C ₂₀ alkyl group And desorcinol, hydroquinol, or bisphenol-A dialcohol derived from n having a range of 0 to 4.

Examples of the compound corresponding to Chemical Formula 2 include triphenyl phosphate and tri (2,6-dimethyl) phosphate when n is 0, and when n is 1, resorcinol bis (diphenyl) phosphate or resorcinol bis (2,6-dimethylphenyl) phosphate, resorcinolbis (2,4-dibutylbutylphenyl) phosphate, hydroquinolbis (2,6-dimethylphenyl) phosphate, hydroquinolbis (2,4-dibutylbutyl) Phenyl) phosphate etc. are mentioned. These aromatic phosphate ester compounds may be applied alone or in each mixture.

In the present invention, additives such as plasticizers, heat stabilizers, antidrip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, lubricants, and inorganic additives may be added as necessary. The additives may be applied alone or by mixing two or more kinds. The additive is added in the range of 30 parts by weight or less, preferably 0.01 to 30 parts by weight. Examples of the inorganic additives include asbestos, glass fibers, talc, ceramics and sulfates.

The resin composition of this invention can be manufactured by a well-known method. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.

Since the styrene resin composition of the present invention can express excellent flame retardancy even with a small amount, it can be used for molding various products. In particular, it is widely applicable to the exterior materials of electrical and electronic products such as computers, televisions, washing machines, telephones, CD players, audio and video players, computer housings or other office equipment housings.

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

Specifications of the components used in the Examples and Comparative Examples of the present invention are as follows.

(A) Styrene resin: Cheil Industries Co., Ltd., a rubber-reinforced styrene resin HG-1730, was used.

(B) Polyphenylene Ether (PPE) Resin: Poly (2,6-dimethyl-phenylether) (trade name: S-202) of Asahi Kasehi, Japan, was used. The particle size has an average particle diameter of several tens of micrometers. It is in powder form.

(C) phosphonium compounds

Carboxyethyltriphenyl phosphonium bromide from Japan HOKKO Chemical was used.

(D) Aromatic Phosphate Ester Compounds: Bis (dimethylphenyl) phosphate bisphenol A (trade name: CR741S) manufactured by Nippon Suppal Chemical Co., Ltd. was used.

(E) Bromine compound: A decabromodiphenyl oxide (trade name: SAYTEX 102E) of ALBEMARLE was used.

Example  1 to 3

The pellets were prepared by extruding the above components in a temperature range of 200 to 280 ° C. in a conventional twin screw extruder according to the contents shown in Table 1 below. The prepared pellets were dried at 80 ° C. for 2 hours, and then injected into a 6 Oz injection machine under conditions of a molding temperature of 180 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a flame retardant specimen. The prepared specimens were measured for flame retardancy at a thickness of 1/8 "according to the UL 94 VB flame retardant standard.

Comparative Example  1 to 4

An aromatic phosphate ester compound or a bromine compound was applied as a flame retardant without applying the phosphonium compound of the present invention. All the measurement results are shown in Table 1.

From the results in Table 1 above, when using a phosphonium compound as a flame retardant in a blend using a styrene resin copolymer and a polyphenylene ether resin, flame retardant at a thickness of 1/8 "than when applying a bromine compound or a phosphorus compound It can be seen that the degree is excellent.

The present invention provides a flame retardant styrene resin composition that is stable to fire, can achieve V-0 flame resistance even with a small flame retardant, and has excellent balance of physical properties such as heat resistance and workability, and is suitable for use as an exterior material for electronic products. It has the effect of the invention.

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 (10)

(A) 50 to 99% by weight of styrene resin; And (B) 100 parts by weight of the base resin (A) + (B) consisting of 1 to 50% by weight of a polyphenylene ether resin, (C) 0.1 to 30 parts by weight of the phosphonium compound; Consisting of, the phosphonium-based compound (C) is a flame-retardant styrene resin composition having a structure of Formula 1 [Formula 1]

In the R ₁ is an alkyl group of C ₁ -C ₆ having a carboxyl group in the C ₁ -C ₆ alkyl group or an aryl group, or terminal, X is a halogen atom. The flame retardant styrene resin composition of claim 1, wherein the styrene resin (A) is selected from the group consisting of polystyrene resins, styrene copolymer resins, rubber modified styrene copolymer resins, and mixtures thereof. . The flame retardant styrene resin composition according to claim 1, wherein the polyphenylene ether resin (B) is poly (2,6-dimethyl, 1,4-phenylene) ether. delete The method of claim 1, wherein the phosphonium-based compound (C) is methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, carboxy ethyl triphenyl phosphonium bromide Flame retardant styrene selected from the group consisting of tetraphenyl phosphonium bromide, methyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium chloride, carboxy ethyl triphenyl phosphonium chloride, tetraphenyl phosphonium chloride and mixtures thereof System resin composition. The flame retardant styrene resin composition of claim 1, wherein the resin composition further comprises 0.1 to 30 parts by weight of an organophosphorus flame retardant. The flame retardant styrene resin composition according to claim 6, wherein the organophosphorus flame retardant is an aromatic phosphate ester compound. The method of claim 1, wherein the resin composition is 0.01 to 30% by weight of an additive selected from the group consisting of plasticizers, heat stabilizers, anti-drip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, lubricants, inorganic additives and mixtures thereof. Flame retardant styrene resin composition comprising a further. The pellet which extruded the resin composition of any one of Claims 1-3 and 5-8. An exterior material of an electrical and electronic product in which the resin composition of any one of claims 1 to 3 and 5 to 8 is molded.