KR100778010B1 - Non-halogen flameproof styrenic resin composition - Google Patents

Abstract

A nonhalogenated 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 weather resistance, moldability and environmental friendliness by using no halogen-based flame retardant and reducing the amount of polyphenylene ether. A resin composition comprises 100 parts by weight of a base resin which comprises 80-95 wt% of a styrene-based resin and 5-20 wt% of a polyphenylene ether resin; 1-25 parts by weight of a pentaerythritol diphosphonate represented by the formula 1; and 1-25 parts by weight of an organic phosphorus-based compound, wherein R1 is a C1-C12 alkyl group, an aryl group, an alkyl-substituted aryl group, or an aralkyl group. The organic phosphorus-based compound is at least one selected from the group consisting of an alkyl phosphinic acid metal salt compound represented by the formula 2 (wherein R is a C1-C6 alkyl group, a cyclic alkyl group, or a C6-C10 aryl group; M is Al, Zn or Ca; and n is 2 or 3), an aromatic phosphate compound represented by the formula 3 (wherein R3, R4 and R5 are independently H or a C1-C4 alkyl group; X is a C6-C20 aryl group substituted or unsubstituted with an alkyl group derived from resorcinol, hydroquinol or bisphenol A; and n is 0-4), and a phosphazene compound represented by the formula 4 or 5.

Description

Non-halogen flame retardant styrene resin composition {Non-halogen Flameproof Styrenic Resin Composition}

Field of invention

The present invention relates to a non-halogen flame retardant styrene resin composition. More specifically, the present invention is applied to a non-halogen flame retardant styrene resin composition having excellent flame retardancy and weather resistance by applying a compound having pentaerythritol diphosphonate and an organophosphorus compound as a flame retardant to a blend using a styrene resin and a polyphenylene ether resin. It is about.

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, styrenic resins themselves have the property of easy combustion and are 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, 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 used here, polybromodiphenyl ether, tetrabromobisphenol A, brominated substituted epoxy compounds, chlorinated polyethylene and the like are mainly used. As the antimony compound, antimony trioxide and antimony pentoxide are mainly used.

The method of applying the halogen and antimony compound together to impart flame retardancy has the advantage of easily obtaining flame retardancy and not deteriorating physical properties. However, hydrogen halide gas generated during processing may 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.

In general, rubber-modified styrene-based resin has a disadvantage in that it is difficult to expect a flame retardant effect in a solid phase because there is little char remaining during combustion (Journal of Applied Polymer Science, 1998, vol. 68, p. 1067). Therefore, by adding an additional char forming agent so that the char can be produced smoothly to obtain the desired flame retardancy.

US Patent No. 4,520, 152 discloses a flame retardant resin composition which achieves flame retardancy by using pentaerythritol diphosphonate as a flame retardant in polyphenylene ether resin and styrene resin. However, in this patent, more than 20% by weight of polyphenylene ether resin should be used, which has the disadvantage of poor weather resistance.

In order to solve the problems of conventional flame retardant thermoplastic resins, the present inventors use styrene-based resins and polyphenylene ether resins as base resins, and by applying pentaerythritol diphosphonate and phosphorus compounds as flame retardants, excellent fire stability and weather resistance are achieved. It is to develop a halogen flame-retardant styrene resin composition.

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

Another object of the present invention is to provide a non-halogen flame retardant styrene resin composition using an environmentally friendly compound as a flame retardant without using a halogen flame retardant that causes environmental pollution during processing or combustion of the resin.

Another object of the present invention is to provide an environmentally friendly non-halogen flame retardant styrene resin composition having excellent weather resistance and moldability by reducing the amount of polyphenylene ether added.

Still another object of the present invention is to provide a non-halogen flame retardant styrene resin composition having excellent weather resistance as well as flame resistance.

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 with respect to 100 parts by weight of the base resin (A) + (B) consisting of (A) 80 to 95 parts by weight of styrene resin, (B) 5 to 20 parts by weight of polyphenylene ether resin, (C) 1 to 25 parts by weight of pentaerythritol diphosphonate and 1 to 25 parts by weight of (D) organophosphorus compound. Hereinafter, specific contents of the present invention will be described in detail below.

Detailed Description of the Invention

(A) styrene resin

The styrene resin (A) used in the resin composition according to the present invention is a polymer of an aromatic monoalkenyl monomer, preferably a rubber modified styrene resin modified with a rubbery polymer.

The rubber-modified styrene resin is prepared by mixing a rubbery polymer and an aromatic monoalkenyl monomer, thermally polymerizing without a polymerization initiator, or polymerizing by a conventional method using a polymerization initiator.

As the rubbery polymer, butadiene type rubber, isoprene type rubber, copolymer of butadiene and styrene, acrylic rubber, etc. may be used. Preferably, butadiene, styrene-butadiene, acrylonitrile-butadiene rubber, isoprene rubber, alkylacryl Rubber, ethylene / propylene / diene terpolymer (EPDM). These can be used in mixture of 2 or more types. The rubbery polymer preferably has a particle size of 0.1 to 2.0 µm in order to provide optimum physical properties in the blend of the styrene resin (A) and the polyphenylene ether resin (B). The rubbery polymer is 3 to 30% by weight, preferably 5 to 15% by weight based on 100% by weight of the styrene resin (A).

The aromatic monoalkenyl monomer used in the styrene resin of the present invention is applied by copolymerizing by adding 70 to 97% by weight, preferably 85 to 95% by weight. Styrene, α-methylstyrene, halogen or alkyl substituted styrene may be used as the aromatic monoalkenyl monomer.

In the present invention, in addition to the aromatic monoalkenyl monomer, an alkyl ester monomer and / or an unsaturated nitrile monomer may be added and polymerized.

In addition to the monomers, monomers such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like may be polymerized to impart properties such as chemical resistance, processability, and heat resistance. The amount to be added may be added to 40 parts by weight or less based on the entirety of the styrene resin.

In the polymerization of the resin composition according to the present invention, it can be carried out by thermal polymerization without the presence of an initiator and can also be carried out in the presence of an initiator. The polymerization initiator that may be used may be selected from one or more of peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumenehydro peroxide and azo initiators such as azobis isobutyronitrile. have.

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.

In the present invention, the styrene resin (A) is used in the range of 80 to 95 parts by weight based on 100 parts by weight of the base resin. Preferably it is used in the range of 80-90 weight part.

(B) polyphenylene ether resin

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

In the present invention, the polyphenylene ether resin (B) is used in the range of 5 to 20 parts by weight based on 100 parts by weight of the base resin. Preferably it is used in the range of 10 to 20 parts by weight. When the polyphenylene ether resin (B) is used at less than 5 parts by weight, the flame retardancy is lowered, and when used at 20 parts by weight or more, weather resistance and moldability are inferior.

(C) pentaerythritol diphosphonate

Pentaerythritol diphosphonate that can be used in the present invention is a cyclic compound represented by the following formula (1).

[Formula 1]

R ₁ in Formula 1 represents an alkyl group, an aryl group, an alkyl substituted aryl group, or an aralkyl group of C ₄ -C ₁₀ .

In the present invention, flame retardance can be further improved by using the pentaerythritol diphosphonate in combination with a phosphorus compound. The pentaerythritol diphosphonate is used in the range of 1 to 25 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the base resin. When used in excess of 25 parts by weight, there is a problem that the mechanical properties are lowered.

(D) organophosphorus compounds

      The organophosphorus compound used in the present invention may be used in the form of one or two or more mixtures selected from the group consisting of alkyl phosphinic acid compounds, aromatic phosphate esters, and aromatic phosphazene compounds. The organophosphorus compound is used in the range of 1 to 25 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the base resin. When used in excess of 25 parts by weight, there is a problem that the mechanical properties are lowered.

(D1) alkyl phosphinic acid metal salt compounds

The alkyl phosphinic acid metal salt compound (D1) used in the present invention is represented by the structure of the following formula (2).

[Formula 2]

In the above formula, R is a C ₁ -C ₆ alkyl group, a cyclic alkyl group or a C ₆ -C ₁₀ aryl group, M is a metal such as Al, Zn, Ca and n is an integer of 2 or 3.

Preferably, R is a methyl, ethyl, propyl, butyl or phenyl group, and M is Al, Zn.

In addition, it is preferable to use an alkyl phosphinic acid metal salt compound having an average particle size of 10 μm or less in consideration of impact strength.

(D2) Aromatic Phosphate Ester Compounds

The aromatic phosphate ester compound (D2) used in the present invention has a structure represented by the following general formula (3).

[Formula 3]

In the above formula, R ₃ , R ₄ , and R ₅ are each independently hydrogen or an alkyl group of C ₁ -C ₄ , X is an aryl group of C ₆ -C ₂₀ or an aryl group of C ₆ -C ₂₀ substituted with an alkyl group As derived from resorcinol, hydroquinol, bisphenol-A, and n ranges from 0 to 4.

Examples of the compound corresponding to Formula 3 include triphenyl phosphate and tri (2,6-dimethyl) phosphate when n is 0, and when n is 1, resorcinol bis (diphenyl) phosphate and 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 phosphoric acid ester compounds (D2) may be applied alone or in each mixture.

(D3) phosphazene compounds

The phosphazene compound which can be used in the present invention is a linear phosphazene compound represented by the formula (4) or a cyclic phosphazene compound represented by the following formula (5).

[Formula 4] [Formula 5]

R1, R2, and R3 of Formulas 4 and 5 represent a substituent optionally selected from C ₁ -C ₁₅ alkyl, aryl, alkyl substituted aryl, aralkyl, alkoxy, aryloxy, amino or hydroxy groups, k Is an integer of 0 to 10.

The thermoplastic resin composition according to the present invention may be added with a plasticizer, a heat stabilizer, an antioxidant, an antidrip agent, a compatibilizer, a light stabilizer, a pigment, a dye, and / or an inorganic filler according to each use. Examples of added inorganic fillers include asbestos, fiberglass, talc, ceramics and sulfates. The added additives may be used in an amount of 30 parts by weight or less based on the total resin composition.

The styrenic thermoplastic resin composition of the present invention can be produced by a 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. The pellets may be molded in a conventional manner and applied to exterior materials of electrical and electronic products such as televisions, washing machines, telephones, audio, video players, CD players, and the like, and internal and external parts of office automation equipment.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

Example

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

(A) Styrene-type resin: The rubber-reinforced styrene resin HG-1760S of Cheil Industries Co., Ltd. was used.

(B) Polyphenylene Ether (PPE) Resin: Poly (2,6-dimethyl-phenylether) (trade name: PX-100F) manufactured by Mitsubishi Engineering Plastics, Japan was used.

(C) pentaerythritol diphosphonate : Pentaerythritol bis (phenyl phosphonate) was used and prepared as follows. 61.2 g of Pentaerythritol and 142 g of Pyridine were added to 100 mL of Methylene chloride, and 214.5 g of Phenyl phosphonic dichloride was injected and stirred at room temperature for 7 hours. After completion of the reaction, the precipitate was filtered, and the remaining precipitate was poured into 200mL of water and washed 3-4 times. After washing, filtration and drying to prepare a pentaerythritol bis (phenyl phosphonate) with a melting point of 268.

(D) organophosphorus compounds

(D1) Alkyl phosphinic acid metal salt compound: Exolit OP930, a diethyl phosphinic acid metal salt of Clariant, was used.

(D2) Aromatic Phosphate Ester Compounds: Resorcinol bis (2,6-dimethylphenyl) phosphate (trade name: PX200) manufactured by Nippon Scorpion Co., Ltd. was used.

(D3) Aromatic phosphazene compound: SPS100 of Otsuka Chemical, Japan was used.

Example  1 to 4

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 1/10 ″ according to UL 94 VB flame retardancy regulations. The weather resistance was 4 cm × 5 cm × 0.3 cm and the color change of the specimens before and after 300 hours in accordance with ASTM D 4459. Measured.

Comparative Example  1 to 3

As shown in Table 1 below, except that the content of each component was adjusted, the specimens were prepared in the same manner as in Examples 1 to 4, and physical properties thereof were measured. All the measurement results are shown in Table 1.

The results of Table 1 show that when pentaerythritol diphosphonate is used in combination with a phosphorus compound, flame retardancy and weather resistance are superior at a thickness of 1/10 "than when pentaerythritol diphosphonate or an aromatic phosphate ester compound is applied alone. Can be.

The present invention is stable against fire, uses environmentally friendly compounds as flame retardants without the use of halogen-based flame retardants that cause environmental pollution during the processing and combustion of resins, and reduces the amount of polyphenylene ether added. The invention has the effect of providing an environmentally friendly thermoplastic flame retardant styrene resin composition having excellent moldability.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (11)

To 100 parts by weight of the base resin (A) + (B) consisting of 80 to 95 parts by weight of (A) styrene resin and 5 to 20 parts by weight of (B) polyphenylene ether resin, (C) 1 to 25 parts by weight of pentaerythritol diphosphonate of the formula (1); And [Formula 1]

(R ₁ is a C ₄ -C ₁₂ alkyl group, aryl group, alkyl substituted aryl group, or aralkyl group) (D) 1 to 25 parts by weight of an organophosphorus compound; Wherein the organophosphorus compound (D) comprises (D1) an alkyl phosphinic acid metal salt compound of Formula 2, (D2) an aromatic phosphate ester compound of Formula 3, and (D3) a force of Formula 4 or Formula 5 Non-halogen flame retardant styrene resin composition, characterized in that at least one selected from the group consisting of pazen compounds: [Formula 2]

(Wherein R is a C ₁ -C ₆ alkyl group, a cyclic alkyl group or a C ₆ -C ₁₀ aryl group, M is a metal of Al, Zn, Ca, n is an integer of 2 or 3) [Formula 3]

(In the above formula, R ₃ , R ₄ , and R ₅ are independently of each other hydrogen or an alkyl group of C ₁ -C ₄ , X is an aryl group of C ₆ -C ₂₀ or C ₆ -C ₂₀ aryl substituted with an alkyl group. Group derived from resorcinol, hydroquinol, bisphenol-A, n ranges from 0 to 4) [Formula 4]

[Formula 5]

(R ₁ , R ₂ , and R ₃ of Formulas 4 and 5 may be optionally selected from C ₁ -C ₁₅ alkyl, aryl, alkyl substituted aryl, aralkyl, alkoxy, aryloxy, amino or hydroxy groups. Substituents, k is an integer from 0 to 10). The non-halogen flame retardant styrene resin composition according to claim 1, wherein the styrene resin (A) is a rubber modified styrene resin. The non-halogen 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 delete delete delete delete The non-halogen-based system according to claim 1, wherein the resin composition further comprises a plasticizer, a heat stabilizer, an antidrip agent, an antioxidant, a compatibilizer, a light stabilizer, a pigment, a dye, and an inorganic filler alone or a mixture thereof. Flame retardant styrene resin composition. The pellet which extruded the composition of any one of Claims 1-3. An exterior material of an electrical and electronic product molded from the composition of any one of claims 1 to 3 and 9.