KR20020054692A - Flame Retardant Glass Reinforced Styrenic Thermoplastic Composition - Google Patents

Abstract

PURPOSE: Provided is a styrene-based thermoplastic composite material with improved impact strength and flame retardancy, which contains a rubber modified styrene-based graft copolymer and a styrene-based copolymer. CONSTITUTION: The styrene-based thermoplastic composite material comprises: (A) 5-95pts.wt. of the rubber modified styrene-based graft copolymer obtained by graft-polymerizing (a1) 5-95pts.wt. of a monomer mixture comprising 50-95wt% of styrene, alpha-methyl styrene, halogen or alkyl substituted styrene and 50-5wt% of acrylonitrile, methacrylonitrile, C1-C8 methacrylic acid alkyl ester, maleic anhydride, and etc. and (a2) 95-5pts.wt. of a polymer selected from butadiene rubber, acryl rubber, ethylene/propylene rubber, styrene/ butadiene rubber, and etc.; (B) 95-5pts.wt. of the styrene-based copolymer, obtained by copolymerizing (b1) 50-95wt% of styrene, alpha-methyl styrene, halogen or alkyl substituted styrene and (b2) 5-50wt% of acrylonitrile, methacrylonitrile, C1-C8 methacrylic acid alkyl ester, maleic anhydride, and etc., or a mixture thereof; (C) 5-50pts.wt.(based on the (A)+(B) of 100pts.wt.) of glass fiber treated by a silane-based coupling agent; (D) 0.05-5pts.wt.(based on the (A)+(B) of 100pts.wt.) of an amino silane-based coupling agent; (E) 5-30pts.wt.(based on the (A)+(B) of 100pts.wt.) of a fused halogen compound; 1-10pts.wt.(based on the (A)+(B) of 100pts.wt.) of antimony trioxide.

Description

Styrene-based thermoplastic composite with improved impact strength and flame retardancy {Flame Retardant Glass Reinforced Styrenic Thermoplastic Composition}

Field of invention

The present invention relates to glass fiber reinforced styrenic thermoplastic composites. More specifically, the present invention relates to a styrene-based thermoplastic composite material having improved impact strength and flame retardancy made of a rubber-modified styrenic graft copolymer (hereinafter referred to as ABS), a flame retardant, a glass fiber, and a coupling agent.

Background of the Invention

In general, styrene-based resins have good processability and mechanical strength, and are mainly used as exterior materials for electrical and electronic products. However, the resin itself does not have a resistance to flame and when the spark is ignited by an external ignition source, the resin itself acts as an energy to assist combustion and continuously spreads the fire. .

In view of this, in order to guarantee the safety of electronic products, only USA and Europe have legalized to use only flame-retardant resins in the manufacture of molded parts of electronic products.

The method of imparting flame retardancy to a thermoplastic resin can be divided 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 by using a special monomer containing a flame retardant atom during polymerization. Among them, the polymerization type flame retardant method has been studied in the pilot scale stage, but due to the high cost and difficulty of achieving flame retardancy, commercialized products have not been released. Therefore, most commercialized flame retardant resins have been prepared by an additive flame retardant method in which a flame retardant containing halogen or phosphorus, which is an inactive element, is added during compounding.

The additive flame retardant method is mainly 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 highly flame retardant when added to styrene-based resins, but seriously deteriorate overall physical properties such as impact strength, weather stability, heat resistance and processability of the resin itself. Therefore, in manufacturing a flame retardant resin, it is very important to maintain a good flame retardancy while minimizing side effects such as deterioration of physical properties and processability, appearance defects.

In addition to the flame retardancy described above, in order to use as a material for parts requiring high strength and precision, there are disadvantages in that dimensional stability, creep resistance, heat resistance, and rigidity are unsuitable. In order to solve this problem, it is known to use an inorganic filler such as glass fiber.

By the way, in manufacturing such a thermoplastic composite material, it is very important to increase the interfacial bonding force between the reinforcing material and the resin in order to have good physical properties. This is because when the interfacial bonding force between the resin and the reinforcing material is lowered, the stress applied to the thermoplastic composite material acts on the interface between the resin and the reinforcing material, and the fracture proceeds around the interface, so that the effect of increasing the target rigidity cannot be obtained. to be.

Several other documents, including US Pat. No. 3,671,378, disclose a method of coating the surface of a reinforcement with a material comprising a reactive group capable of reacting with the resin in order to always maintain the interfacial adhesion between the resin and the reinforcement.

In International Publication No. 86/05445, the reinforcement is coated with a rubbery intermediate layer containing a reactor capable of reacting the reinforcement glass fibers with the reinforcing glass fibers and having compatibility with the resin forming the matrix, thereby improving the interfacial bonding force between the resin and the reinforcing material. An example is disclosed.

However, the above-described methods are excellent in the case where the matrix resin is a polyamide-based resin, a polyester-based resin, or a polycarbonate resin containing reactivity, whereas the mechanical properties when the inactive styrene-based resin is used as a matrix It is hard to expect improvement.

In addition, the method disclosed in International Publication No. 86/05445 has a hassle to coat the glass fiber with a rubbery polymer through a separate process.

European Patent No. 485793 (92.05.20) discloses a method of improving the interfacial adhesion between styrene resin and the reinforcing material without coating the surface of the reinforcing material through a separate process. No. 485793 improves the interfacial adhesion between the resin and the glass fiber by adding a rubber graft copolymer containing a tertiary alkyl ester group in a composite material based on ABS (acrylonitrile-butadiene-styrene copolymer) resin. The impact strength is improved.

U.S. Patent No. 5,304,591 blends styrene-methyl methacrylate-maleic anhydride terpolymer together with SAN copolymer to improve interfacial adhesion between matrix resin and glass fiber The technology which improved the performance and mechanical properties is disclosed.

In addition, US Patent No. 5,426,149 discloses a technique for improving the interfacial adhesion between the matrix resin and the glass fiber by introducing an epoxy group in the SAN copolymer.

In US Pat. No. 5,656,684, a silane compound having a phthalimide group was used to improve the interfacial adhesion between the resin and the glass fiber in a glass fiber reinforced resin of polycarbonate.

In addition, research is being conducted to improve the physical properties of the resin composition by improving the interfacial adhesion between the resin and the reinforcing material.

On the other hand, the present inventors improve the flame retardancy by adding a flame retardant to the rubber-modified styrenic copolymer, and improves the interfacial bonding force between the resin constituting the flame retardant-added matrix and the glass fiber as a reinforcing material, and mechanical strength including impact strength The development of styrenic thermoplastic composites with further improved flame retardancy has begun.

An object of the present invention is to provide a styrene-based thermoplastic composite material with improved mechanical strength, including impact strength.

Another object of the present invention is to provide a styrenic thermoplastic composite having excellent flame retardancy.

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

Styrene-based thermoplastic composite material of the present invention is (A) 5 to 95 parts by weight of rubber-modified styrene-based graft copolymer (B) 100 to 50 parts by weight of the base resin (A) + (B) consisting of styrene-based copolymers (C) 5 to 50 parts by weight of the glass fiber and (D) 0.05 to 5 parts by weight of the coupling agent (E) 5 to 30 parts by weight of the molten halogen compound (F) 1 to 10 parts by weight of antimony trioxide Characterized in that, the detailed description of each of these components is as follows.

(A) Rubber modified styrene graft copolymer resin

The rubber-modified graft copolymer resin used in the present invention is 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, or mixtures thereof and acrylonitrile, methacrylonitrile, C _1-8 meta Mixture with 5-50% by weight of alkyl acrylate esters, C _1-8 acrylic acid alkyl esters, maleic anhydride, C _1-4 alkyl or phenyl N-substituted maleimides, or mixtures thereof (a ₁ ) 5-95 weight Butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), and polyorganosiloxane / polyalkyl (meth) acrylic It is a copolymer grafted to 5-95 weight part of ₁ or mixtures (a2) selected from the group which consists of a latex rubber composite.

The C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms as esters of methacrylic acid or acrylic acid, respectively. As these specific examples, methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, or methacrylic acid propyl ester is mentioned, Among these, methacrylic acid methyl ester is especially preferable.

Preferred examples of the rubber-modified styrenic graft copolymer (A) include graft copolymerization of butadiene rubber, acrylic rubber, or styrene / butadiene rubber in the form of a mixture of styrene, acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers. It can be mentioned. Among the above, the rubber modified styrene graft copolymer (A) is most preferably ABS graft copolymer.

In order to improve the impact strength and the surface properties of the molded article, the rubber particle diameter preferably has a diameter of 0.05 to 4 µm.

The method for preparing the graft copolymer is well known to those skilled in the art, and any one of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used, and a preferred manufacturing method For example, the above-mentioned aromatic vinyl monomer is introduced in the presence of a rubbery polymer, followed by emulsion polymerization or bulk polymerization using a polymerization initiator.

(B) Styrene Copolymer

Styrene-based copolymers used in the present invention are 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene or mixtures thereof (b ₁ ) and acrylonitrile, methacrylonitrile, C _1-8 meta Styrene-based air obtained by copolymerizing 5-50% by weight of alkyl acrylate esters, C _1-8 acrylic acid alkyl esters, maleic anhydride, C _1-4 alkyl or phenyl N-substituted maleimides or mixtures thereof (b ₂ ) Copolymers or mixtures of these copolymers. The styrene copolymer resin is used in the range of 95-5 parts by weight.

The C _1-8 methacrylic acid alkyl esters or C _1-8 acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1-8 carbon atoms as esters of methacrylic acid or acrylic acid, respectively. As these specific examples, methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, or methacrylic acid propyl ester is mentioned, Among these, methacrylic acid methyl ester is especially preferable.

Preferred embodiments of the styrene copolymer (B) include a monomer mixture of styrene and acrylonitrile and optionally methyl methacrylate, a monomer mixture or styrene of α-methylstyrene and acrylonitrile and optionally methyl methacrylate. , prepared from monomer mixtures of α-methylstyrene and acrylonitrile and optionally methacrylic acid methyl ester. The styrene / acrylonitrile copolymer as component (B) may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, and it is preferable to use those having a weight average molecular weight of 15,000-200,000.

Another preferable styrene-based copolymer (B) is a copolymer of styrene and maleic anhydride, which can be produced using a continuous bulk polymerization method and a solution polymerization method. The composition ratio of the two monomer components can be varied in a wide range, preferably, the content of maleic anhydride is 5 to 25% by weight. The molecular weight of the styrene / maleic anhydride copolymer may also be used in a wide range, but it is preferable to use those having a weight average molecular weight of 20,000 to 200,000 and intrinsic viscosity of 0.3 to 0.9.

The styrene monomers used in the preparation of the vinyl copolymer (B) used in the preparation of the resin composition of the present invention are other substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and α-methylstyrene. It can be used instead of the monomer.

Styrene-based copolymers used in the production of the resin composition of the present invention described above may be used alone or in the form of a mixture of two or more thereof.

Vinyl copolymers or modified vinyl aromatic graft copolymers can be used in the present invention. The modified vinyl aromatic graft copolymer is a copolymer obtained by graft polymerization of 20-99 parts by weight of an aromatic vinyl monomer to 1-80 parts by weight of a rubbery polymer. Rubbery polymers include diene rubbers, ethylene rubbers and ternary copolymer rubbers of ethylene / propylene / diene monomers.

The average particle diameter of the rubber particles of the rubbery polymer may be used to 1.0 μm or less, preferably in the range of 0.05-0.5 μm.

Aromatic vinyl monomers include styrene, para t-butylstyrene, α-methylstyrene, β-methyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, chlorostyrene, ethyl styrene, vinyl naphthalene and divinyl. Benzene and the like, of which styrene and α-methylstyrene are preferable.

The method for preparing the graft copolymer is well known to those skilled in the art, and any one of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used, and preferable preparation is possible. As the method, it is preferable to add the aromatic vinyl monomer described above in the presence of a rubbery polymer, and to perform emulsion polymerization or bulk polymerization with a polymerization initiator.

Organic peroxides used in the preparation of the modified vinyl aromatic copolymers of the present invention include diisopropylbenzenehydroperoxide, di-t-butylperoxide, p-ethane hydroperoxide, t-butylcumyl peroxide and dicumyl. Peroxide, 2,5-dimethyl 2,5-di (t-butylperoxy) hexane, di-t-butyldiperoxyphthalate, succinic acid peroxide, t-butyldiperoxybenzoate, t-butylperoxymaleic acid , t-butylperoxyisopropylcarbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide and the like may be used, and these may be used alone or in combination of two or more thereof. Preferably, dicumyl peroxide is used.

(C) glass fiber

Glass fiber used in the present invention is a kind used commercially. For example, it refers to chopped glass fiber having a length of about 3-6 mm. The glass fiber used in the injection molded product is E-glass and the diameter of the glass fiber generally used is 8-20 μm. In the present invention, it is used in 5-50 parts by weight based on 100 parts by weight of (A) + (B).

Glass fiber sizing compositions are generally treated during or after the fiber manufacture. Lubricating agents, coupling agents, surfactants and the like are used as the glass fiber treatment agent.

Lubricants use suitable additives to form good strands in the manufacture of glass fibers. The coupling agent serves to give good adhesion between the glass fiber and the resin. When various glass fiber treatment agents are developed and properly selected and used according to the type of resin and glass fiber used, the glass fiber reinforcing material is given good physical properties.

In general, the coupling agent treated on the glass fiber has a structural formula such as YRSiX3 as the silane coupling agent.

Y is an organic functional group that can react with the matrix resin. Organic functional groups are generally a vinyl group, an epoxy group, a merketane group, an amine group, and an acryl group.

X is composed of an ethoxy group, a halogen group and the like, and combines with water in air or an inorganic material to form hydrolyzed silanol. This silanol is combined with an inorganic filler. Therefore, the silane coupling agent has a structure capable of binding by reacting with the dendritic and inorganic filler.

The treatment of the silane coupling agent on the glass fibers is produced in a general manner without particular limitation.

Glass fibers usable in this experiment are amine-, acryl-, and epoxy-based γ-amino propyltriethoxy silane, γ-amino propyltrimethoxy silane, N- ( Beta-aminoethyl) γ-amino propyltriethoxy silane (N- (β-amino ethyl) γ-amino propyltriethoxy silane), γ-methacryloxy propyltriethoxy silane, γ-methoxy Γ-methacryloxy propyltrimethoxy silane, γ-glycidoxy propyltrimethoxy silane, β (3,4-epoxyethyl) γ-amino propyltrimethoxy silane It is treated with a coupling agent such as (3,4-epoxyethyl) γ-amino propyltrimethoxy silane. Among them, the glass fiber treated with the γ-methoxy propyltriethoxy silane coupling agent which is an acrylic coupling agent is the most favorable.

(D) coupling agent

In the present invention, the coupling agent is used in the range of 0.05-5 parts by weight based on 100 parts by weight of (A) + (B).

In the present invention, in addition to the coupling agent treated on the glass fiber, a separate coupling agent is further used in the compounding step. As the coupling agent added as described above, an amino silane coupling agent is most preferable.

Specific examples of the coupling agent include γ-amino propyltriethoxy silane, γ-amino propyltrimethoxy silane, γ-aminopropyl-tris (2-methoxy Γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N- (beta-aminoethyl) γ-amino propyltriethoxy silane (N- (β-amino ethyl) γ-amino propyltrimethoxy silane), N- (beta-aminoethyl) γ-amino propyl triethoxy silane (N- (β-amino ethyl) γ-amino propyltriethoxy silane), β (3,4-epoxyethyl) γ-amino propyl trimeth Methoxy silane (β (3,4-epoxyethyl) γ-amino propyltrimethoxy silane).

In the present invention, in order to reduce the cleavage of the glass fiber, a rubber-modified styrene-based graft copolymer (A), a rubber-modified copolymer (B), a coupling agent (D), a molten halogen-based flame retardant (E) and antimony trioxide, which are matrix resins (F) is mixed with a mixer and melted using an extruder, and the glass fiber (C) is added to the middle of the extruder for processing. The coupling agent of this invention is used in 0.05-5 weight part with respect to 100 weight part of (A) + (B).

(E) Melt Halogen Compound

The halogen compound used as a flame retardant in this invention is represented by following formula (1) and (2).

Formula (1)

N is an integer of 0 or more.

Formula (2)

Wherein n is an integer of 0 or more, and R ₁ is to be. (X is an integer between 1 and 5)

The molten halogen compound is preferably used 5 to 30 parts by weight based on 100 parts by weight of (A) + (B). When 5 parts by weight or less of the molten halogen compound is added, a flame retardant effect is not observed, and when 30 parts by weight or more is used, thermal stability is deteriorated.

(F) antimony trioxide

Antimony trioxide (F) added in order to impart proper flame retardancy is preferably used in an amount of 1 to 10 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the base resin (A) + (B) of the present invention. . In the case where antimony trioxide (F) is used in less than 1 part by weight, sufficient flame retardant effect cannot be obtained, and when used in excess of 10 parts by weight, the balance of the physical properties of the resin composition is not preferable.

Flame retardant styrenic thermoplastic composite material of the present invention may be added to the general ingredients such as antioxidants or lubricants in addition to the above components according to each application.

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

(A) Rubber modified styrene graft copolymer, (B) Styrene copolymer resin, (C) Glass fiber (D) Coupling agent (E) Halogen compound and (F) used in the following Examples and Comparative Examples ) The specifications of antimony trioxide are as follows.

(A) Rubber modified styrene graft copolymer resin

Butadiene rubber latex was added so that the butadiene content was 45 parts by weight based on the total amount of the monomers, 1.0 parts by weight of potassium oleate, cumene hydroperoxide, an additive necessary for a mixture of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water. A graft resin prepared by adding 0.4 parts by weight and 0.3 parts by weight of mercaptan-based chain transfer agent and reacting was maintained at 75 ° C. for 5 hours.

(B) Styrene Copolymer Resin

The content of acrylonitrile was 28% and a styrene / acrylonitrile copolymer having a weight average molecular weight of 120,000 was used.

(C) glass fiber

The inorganic reinforcing material was 13 micron in diameter and 3 mm in chop length of Owens Corning of Korea, and glass fiber treated with coupling agent such as amino silane and methoxy silane, lubricant and binding agent was used. .

(D) coupling agent

KBM603, a Shinetsu Silicon Co. amino silane system, was used.

(E) halogenated compounds

As the halogen compound used in the present invention, a molten halogen compound represented by the general formula (1) or (2) was used.

(F) antimony trioxide

Antimony trioxide was added as shown in parts by weight in order for the halogen compound to express proper flame retardancy.

Example

In order to reduce the cutting of glass fibers, first, the component rubber-modified styrenic graft copolymer resin (A), styrene copolymer resin (B), amino silane coupling agent (D), halogenated compound (E) and antimony trioxide ( F) was mixed with a mixer, and the glass fiber (C) was melted at an extrusion temperature of 220 to 280 ° C. and a screw speed of 200 rpm using a twin screw extruder having L / D = 34 and φ = 40 mm. Pellet was prepared in. The pellet was dried at 80 ° C. for 3 hours, and then injected into a 10 Oz injection machine under a molding temperature of 220-280 ° C. and a mold temperature of 40-80 ° C. to prepare a physical specimen.

Comparative Example

Comparative Example was prepared in the same manner as in Example except that no coupling agent was used.

Table 1 shows the components and compositions of Examples and Comparative Examples.

Parts by weight (phr) Example Comparative Example ABS resin (A) 23 23 SAN resin (B) 53.5 53.5 Glass fiber (C) 23.5 23.5 Coupling Agent (D) 0.3 - Flame Retardant (E) 13 13 Antimony Trioxide (F) 4.0 4.0

From the pellets prepared in Examples and Comparative Examples, a specimen of 1/12 "thickness was prepared by injection molding, and tested for flame retardancy according to the UL-94 determination test method, and mechanical properties of the molded specimen were measured.

Izod notch impact strength was measured according to ASTM D256 standard, tensile strength was measured according to ASTM D638, flexural strength and flexural modulus were measured according to ASTM D790. The impact strength measured not only the Izod impact strength but also the height at which 50% fracture occurred when 20 specimens were tested using a 1 kg weight using the Dupont Drop test method.

In addition, according to ASTM D648, ASTM D792 and ASTM D785 measured the heat deformation temperature, specific gravity and hardness are shown in Table 2. The measurement results are shown in Table 2.

Example Comparative Example Impact strength (kgcm / cm) 1/4 ″ 6.3 6.0 1/8 ″ 6.9 6.6 Tensile Strength (5mm / min, kg / cm ² ) 947 937 Flexural Strength (2.8mm / min, kg / cm ² ) 1192 1144 Flexural modulus (2.8mm / min, kg / cm ² ) 56,090 54,570 Heat Deflection Temperature (1/4 ″, ℃) 97.5 95.0 Hardness (R (M), R-scale) 113.2 112.7 MFI (220 ° C, 10Kg, g / 10min) 15.0 15.68 DuPont Drop Test (cm) 57 53 UL 94 flame retardant V-0 V-1 Glowing (seconds) 32 110 Dropping water 0 0

In the results of Table 2, when the coupling agent (D) is added to the glass fiber (C), the flexural strength and the flexural modulus were increased, and the height of the breakdown of the DuPont drop test was found to be improved. . In particular, even when the same weight part of the flame retardant and antimony trioxide were added, the UL grade was high as V-0 in the embodiment in which the coupling agent was added, and the glow time after the secondary combustion was significantly reduced, thereby improving the flame retardancy. there was.

The present invention improves flame retardancy and mechanical strength by adding a flame retardant and glass fibers to a rubber-modified styrene graft copolymer and a styrene copolymer, which is a matrix, and a coupling between the resin forming the matrix to which the flame retardant is added and the glass fiber which is a reinforcing material. By adding a ring agent to improve the interfacial bonding force, it has the effect of providing a styrene-based thermoplastic composite material having further improved flame retardancy as well as mechanical strength including impact strength.

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 (4)

(A) (a ₁ ) 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, or mixtures thereof and acrylonitrile, methacrylonitrile, C _1-8 methacrylic acid alkyl esters, 5-95 parts by weight of a monomer mixture consisting of C _1-8 acrylic acid alkyl esters, maleic anhydride, C _1-4 alkyl or phenyl N-substituted maleimide, or a mixture thereof 50-5% by weight (a ₂ ) butadiene rubber, In acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, terpolymer (EPDM) of ethylene-propylene-diene, polyorganosiloxane / polyalkyl (meth) acrylate rubber composite 5-95 parts by weight of rubber-modified styrenic graft copolymers obtained by graft polymerization on 95-5 parts by weight of a polymer selected from one or a mixture thereof; (B) 50-95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene or mixtures thereof (b ₁ ) and acrylonitrile, methacrylonitrile, C _1-8 methacrylic acid alkyl esters, C Styrene copolymer obtained by copolymerizing _1-8 acrylic acid alkyl esters, maleic anhydride, C _1-4 alkyl or phenyl N-substituted maleimide, or mixtures thereof (b ₂ ) 5-50% by weight 95- 5 parts by weight; (C) 5-50 parts by weight of glass fibers treated with a silane coupling agent based on 100 parts by weight of (A) + (B); (D) 0.05-5 parts by weight of an amino silane coupling agent based on 100 parts by weight of (A) + (B); (E) 5-30 parts by weight of a molten halogen compound based on 100 parts by weight of (A) + (B); And (F) 1-10 parts by weight of antimony trioxide based on 100 parts by weight of (A) + (B); Styrene-based thermoplastic composite material, characterized in that consisting of. The glass fiber reinforced styrene-based thermoplastic composite material according to claim 1, wherein the coupling agent treated on the glass fiber (C) is an acrylic coupling agent. According to claim 1, wherein the amino silane coupling agent (D) is γ-amino propyltriethoxy silane (γ-amino propyltriethoxy silane), γ-amino propyltrimethoxy silane (γ-amino propyltrimethoxy silane), γ- Γ-aminopropyl-tris (2-methoxy-ethoxy) silane, N- (beta-amino ethyl) γ-amino propyl trimethoxy silane (N- ( β-amino ethyl) γ-amino propyltrimethoxy silane), N- (beta-aminoethyl) γ-amino propyltriethoxy silane (N- (β-aminoethyl) γ-amino propyltriethoxy silane), and β (3,4- Epoxyethyl)? -Aminopropyl trimethoxy silane selected from the group consisting of styrene-based thermoplastic composite material. Rubber modified styrene graft copolymer (A), styrene copolymer (B), amino silane coupling agent (D), molten halogen compound (E) and antimony trioxide (F) are mixed in a mixer and extruder is used. Method of producing a styrene-based thermoplastic composite material characterized in that the glass fiber (C) in the molten state by the injection into the middle portion of the extruder.