KR20140080354A - Flame retardant thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The flame retardant thermoplastic resin composition of the present invention comprises (A) 100 parts by weight of a polycarbonate resin; (B) 5 to 30 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; (C) 10 to 30 parts by weight of an aromatic phosphate ester compound; (D) 0.1 to 5 parts by weight of a halosite tube; And (E) 5 to 50 parts by weight of a filler. The flame retardant thermoplastic resin composition can improve the flame retardancy without lowering rigidity such as flexural modulus by applying a halloysite tube.

Description

TECHNICAL FIELD [0001] The present invention relates to a flame retardant thermoplastic resin composition and a molded article formed from the same. BACKGROUND ART [0002]

The present invention relates to a flame-retardant thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a flame retardant thermoplastic resin composition and a molded article comprising the flame retardant thermoplastic resin composition, which can improve the flame retardancy without lowering rigidity such as flexural modulus by applying a halloysite tube.

Polycarbonate resin is an engineering plastic having excellent mechanical strength, high heat resistance and transparency, and is used in various fields such as office automation equipment, electric / electronic parts, and building materials. Especially in the field of electric / electronic parts, resins used as exterior materials for notebook PCs are required to have high flame retardancy and high rigidity, and are required to have high fluidity due to slimming and thinning of products such as televisions, monitors and notebooks.

In general, the rubber-modified aromatic vinyl copolymer resin is used for electric / electronic products together with a thermoplastic polycarbonate resin because of good workability, excellent impact strength and excellent appearance, and particularly, Resin.

In order to impart flame retardancy to such a resin composition, a halogen-based flame retardant and an antimony compound or a phosphorus compound have conventionally been used. However, halogen-containing compounds may damage the mold due to hydrogen halide gas generated during processing and may have a fatal effect on the human body. In addition, since polybrominated diphenyl ethers, which are main components of halogen-based flame retardants, are highly likely to generate highly toxic gases such as dioxins and furans during combustion, there is a growing interest in a method of preventing flame retardancy that does not employ halogen-based compounds.

As such an erosion resistance method, a method of imparting flame retardancy to a resin composition by adding phosphorus or a compound containing nitrogen has been studied. Particularly, many methods of burnout using a phosphorus compound have been studied. Among the phosphorus compounds, phosphorus ester flame retardants are typically used as the flame retardant, and in the resin compositions using the phosphate flame retardants, so-called " juicing "phenomenon occurs in which the flame retardant migrates to the surface of the molding during molding, There is also a problem of degradation. In order to solve the above problems, a filler may be added, but when a filler is added, the rigidity, particularly the flexural modulus, is lowered.

An object of the present invention is to provide a flame retardant thermoplastic resin composition and a molded article formed therefrom which can improve flame retardancy without deteriorating rigidity such as flexural modulus in a thermoplastic resin composition using a flame retardant and a filler.

Another object of the present invention is to provide an environmentally friendly flame retardant thermoplastic resin composition without using a halogen-based flame retardant and a molded article formed therefrom.

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

One aspect of the present invention relates to a flame retardant thermoplastic resin composition. The flame-retardant thermoplastic resin composition comprises (A) 100 parts by weight of a polycarbonate resin; (B) 5 to 30 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; (C) 10 to 30 parts by weight of an aromatic phosphate ester compound; (D) 0.1 to 5 parts by weight of a halosite tube; And (E) 5 to 50 parts by weight of a filler.

In an embodiment, the rubber-modified aromatic vinyl-based graft copolymer resin (B) comprises (B1) 5 to 65 wt% of a rubbery polymer, 15 to 94 wt% of an aromatic vinyl monomer, and 1 to 50 wt% From 10 to 100% by weight of a graft copolymer resin; And (B2) 0 to 90% by weight of an aromatic vinyl-based copolymer resin containing 50 to 95% by weight of an aromatic vinyl-based monomer and 5 to 50% by weight of a vinyl cyanide-based compound.

In an embodiment, the rubber-modified aromatic vinyl copolymer resin (B) is at least one selected from the group consisting of an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), an acrylonitrile-ethylene propylene rubber-styrene copolymer resin (AES resin) Nitrile-acrylic rubber-styrene copolymer resin (AAS resin).

In an embodiment, the aromatic phosphoric ester compound (C) may be represented by the following formula (2):

(2)

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a C 6 -C 20 aryl group, or a C 6 -C 20 aryl group substituted with a C 1 -C 10 alkyl group, and R ₃ is A C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group, and n is an integer of 0 to 4;

In an embodiment, the haloisite tube (D) may have a diameter of 1 to 500 nm and a length of 100 to 40,000 nm.

In an embodiment, the filler (E) may be selected from carbon fibers, glass fibers, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica, calcium carbonate and mixtures thereof.

In an embodiment, the content ratio (C :( D), weight ratio) of the aromatic phosphate ester compound (C) and the halosite tube (D) is 5: 1 to 150: D) and the filler (E) (D :( E), weight ratio) may be from 1: 5 to 1: 250.

In an embodiment, the flame-retardant thermoplastic resin composition may further include at least one of an ultraviolet stabilizer, a fluorescent whitening agent, a lubricant, a releasing agent, an antistatic agent, a stabilizer, a reinforcing material, a pigment, and a dye.

In the specific examples, the flame retardant thermoplastic resin composition has a flame retardancy measured by UL-94 vertical test method of V-0 or more and a flexural modulus of 35,000 to 45,000 kgf / cm ² measured according to ASTM D790, The Izod impact strength measured according to the following formula can be 10 to 16 kgf · cm / cm.

Another aspect of the present invention relates to a molded article. The molded article is formed from the flame retardant thermoplastic resin composition.

An object of the present invention is to provide an environmentally friendly flame retardant thermoplastic resin composition which can improve flame retardancy without deteriorating rigidity such as flexural modulus and which is not used in a thermoplastic resin composition using a flame retardant and a filler, And has the effect of the invention provided.

Hereinafter, the present invention will be described in detail.

The flame retardant thermoplastic resin composition according to the present invention comprises 100 parts by weight of a polycarbonate resin (A), 5 to 30 parts by weight of a rubber-modified aromatic vinyl copolymer resin (B), 10 to 30 parts by weight of an aromatic phosphate ester compound (C) (D) 0.1 to 5 parts by weight of a halosite tube, and (E) 5 to 50 parts by weight of a filler.

(A) Polycarbonate resin

The polycarbonate resin (A) used in the present invention is a thermoplastic polycarbonate resin. For example, an aromatic polycarbonate resin prepared by reacting a diphenol represented by the following formula (1) with phosgene, halogenformate or carbonic acid diester Can be used.

[Chemical Formula 1]

In Formula 1, A represents a single bond, a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 5 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 6 carbon atoms , A substituted or unsubstituted cycloalkylidene group having 5 to 6 carbon atoms, -CO-, -S-, and -SO ₂ -, R ₁ and R ₂ are each independently a substituted or unsubstituted An alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and n ₁ and n ₂ are each independently an integer of 0 to 4.

The term "substituted" means that the hydrogen atom is replaced by a halogen atom, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, and a combination thereof.

Specific examples of the diphenols include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4- Methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2- -Dichloro-4-hydroxyphenyl) -propane, and the like. Preferably, the diphenols include 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro- Bis- (4-hydroxyphenyl) -cyclohexane, and more preferably 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as bisphenol-A.

The weight average molecular weight (Mw) of the polycarbonate resin may be 10,000 to 200,000 g / mol, for example, 15,000 to 80,000 g / mol, but is not limited thereto.

The polycarbonate resin may be used in the presence of a branched chain, and preferably 0.05 to 2 mol% of a trifunctional or higher polyfunctional compound, such as trivalent or more, A phenol group-containing compound may be added.

The polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin or a blend thereof.

The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as a bifunctional carboxylic acid.

(B) a rubber-modified aromatic vinyl-based copolymer resin

The rubber-modified aromatic vinyl-based copolymer resin (B) used in the present invention is a polymer in which a rubbery polymer is dispersed in the form of particles in a matrix (continuous phase) composed of an aromatic vinyl-based polymer. For example, the rubber-modified aromatic vinyl-based copolymer resin (B) can be polymerized by adding an aromatic vinyl-based monomer, and optionally a monomer copolymerizable with the aromatic vinyl-based monomer, to the rubbery polymer.

Generally, the rubber-modified aromatic vinyl copolymer resin can be produced by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, and the like. Usually, the (B1) graft copolymer resin alone or (B1) The copolymer resin and the aromatic vinyl copolymer resin (B2) are used together, for example, in the form of mixing and extruding. Here, it is preferable to blend the components (B1) and (B2) in consideration of their compatibility. In the case of the above-mentioned bulk polymerization, the rubber-modified aromatic vinyl copolymer resin (B) is produced only by a one-step reaction process without separately preparing the graft copolymer resin (B1) and the aromatic vinyl copolymer resin (B2) However, in either case, the rubber (rubbery polymer) content in the final rubber-modified aromatic vinyl-based copolymer resin (B) is preferably 5 to 50% by weight. In addition, the particle size of the rubber may be 0.05 to 6.0 탆 in Z-average. In the above range, physical properties such as impact resistance are excellent.

(B1) graft copolymer resin

The graft copolymer resin (B1) can be obtained by graft copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer to a rubbery polymer, and if necessary, further includes a monomer which imparts processability and heat resistance .

Specific examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene) and saturated rubbers hydrogenated with the diene rubbers, isoprene rubber, polybutylacrylic acid Acrylic rubber, ethylene-propylene-diene monomer terpolymer (EPDM), and the like. Of these, a diene rubber is preferable, and a butadiene rubber is more preferable. The content of the rubbery polymer may be 5 to 65% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight in the total weight of the graft copolymer resin (B1). It is possible to obtain a good balance of impact strength and mechanical properties in the above range. The average particle size (Z-average) of the rubbery polymer (rubber particles) may be 0.05 to 6 mu m, preferably 0.15 to 4 mu m, more preferably 0.25 to 3.5 mu m. In the above range, the impact strength and appearance are excellent.

The aromatic vinyl monomer may be graft-copolymerized with the rubbery copolymer. Examples of the aromatic vinyl monomer include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, Xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like, but the present invention is not limited thereto. Of these, styrene is preferable. The content of the aromatic vinyl monomer may be 15 to 94% by weight, preferably 20 to 80% by weight, more preferably 30 to 60% by weight in the total weight of the graft copolymer resin (B1). It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as ethacrylonitrile and methacrylonitrile. Or more. The content of the monomer copolymerizable with the aromatic vinyl monomer may be 1 to 50% by weight, preferably 5 to 45% by weight, more preferably 10 to 30% by weight, based on the total weight of the graft copolymer resin (B1) . It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

Examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like. The content of the monomer for imparting processability and heat resistance may be 0 to 15% by weight, preferably 0.1 to 10% by weight, based on the total weight of the graft copolymer resin (B1). The workability and heat resistance can be imparted without deteriorating the other properties within the above range.

(B2) an aromatic vinyl-based copolymer resin

The aromatic vinyl-based copolymer resin (B2) used in the present invention can be prepared by using a monomer mixture excluding the rubber (rubbery polymer) among the components of the graft copolymer resin (B1) And the like. For example, the copolymer resin (B2) can be obtained by copolymerizing the aromatic vinyl-based monomer and the monomer copolymerizable with the aromatic vinyl-based monomer.

Examples of the aromatic vinyl monomers include aromatic vinyl monomers such as styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, para-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, Naphthalene, mystyrene, vinylnaphthalene, and the like can be used, but the present invention is not limited thereto. Of these, styrene is preferable.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide compounds such as acrylonitrile and unsaturated nitrile compounds such as ethacrylonitrile and methacrylonitrile. Two or more of them may be used in combination.

The aromatic vinyl-based copolymer resin (B2) may further comprise a monomer which imparts the above processability and heat resistance, if necessary. Examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like.

In the aromatic vinyl-based copolymer resin (B2), the content of the aromatic vinyl-based monomer is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, May be 70 to 80% by weight. It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

The content of the copolymerizable monomer with the aromatic vinyl-based monomer may be 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 20 to 30% by weight, based on the total weight of the aromatic vinyl-based copolymer resin (B2) have. It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

The content of the monomer for imparting the above processability and heat resistance may be 0 to 30% by weight, preferably 0.1 to 20% by weight, based on the total weight of the aromatic vinyl-based copolymer resin (B2). The workability and heat resistance can be imparted without deteriorating the other properties within the above range.

The weight average molecular weight of the aromatic vinyl-based copolymer resin (B2) may be 50,000 to 500,000 g / mol, but is not limited thereto.

Nonlimiting examples of the rubber-modified aromatic vinyl copolymer resin (B) used in the present invention include acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer resin AES resin), acrylonitrile-acrylic rubber-styrene copolymer resin (AAS resin), and the like. Here, the ABS resin is a copolymer (g-1) obtained by grafting an acrylonitrile monomer, which is an aromatic vinyl compound, and an unsaturated nitrile compound, to the core butadiene rubber-like polymer as the graft copolymer resin (B1) ABS) as the aromatic vinyl-based copolymer resin (B2) may be dispersed in a styrene-acrylonitrile copolymer resin (SAN resin).

In the rubber-modified aromatic vinyl copolymer resin (B), the content of the graft copolymer resin (B1) is 10 to 100% by weight, preferably 15 to 90% by weight, The content of the coalescing resin (B2) is 0 to 90% by weight, preferably 10 to 85% by weight. It is possible to obtain a good balance of impact strength and mechanical properties in the above range.

The rubber-modified aromatic vinyl-based copolymer resin (B) is used in an amount of 5 to 30 parts by weight, preferably 10 to 25 parts by weight, more preferably 15 to 20 parts by weight, per 100 parts by weight of the polycarbonate resin (A) . If the content of the rubber-modified aromatic vinyl copolymer resin (B) is less than 5 parts by weight based on 100 parts by weight of the polycarbonate resin (A), there is a disadvantage in that the impact is lowered. The polycarbonate resin (A) 100 When the amount is more than 30 parts by weight, the flame retardancy is deteriorated.

(C) an aromatic phosphoric ester compound

As the aromatic phosphate ester compound (C) used in the present invention, an aromatic phosphate ester flame retardant used in a conventional flame retardant thermoplastic resin composition can be used. For example, an aromatic phosphate ester compound represented by the following formula .

(2)

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a C 6 -C 20 (C 6 -C 20) aryl group, or a C 6 -C 20 aryl R ₃ is a C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group and is an arylene group which is derived from a diol such as resorcinol, hydroquinol, bisphenol-A, bisphenol- And n is an integer of 0 to 4.

Non-limiting examples of the aromatic phosphoric acid ester compound represented by Formula 2 include a diarylphosphate such as diphenylphosphate, triphenylphosphate, tricresylphosphate, triazylenylphosphate, tri (2 (2,4,6-trimethylphenyl) phosphate, tri (2,4,6-trimethylphenyl) phosphate, tri (2,4,6-trimethylphenyl) (2, 6-dimethylphenyl) phosphate, resorcinolbis (2,4-ditertiarybutylphenyl) phosphate, hydroquinolbis (2,6-dimethylphenyl) phosphate, hydroquinolbis (2,4-ditertiarybutylphenyl) phosphate, and the like. The aromatic phosphoric acid ester compound may be used alone or in the form of a mixture of two or more thereof.

The aromatic phosphoric acid ester compound (C) may be contained in an amount of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). If the content of the aromatic phosphoric acid ester compound (C) is less than 10 parts by weight based on 100 parts by weight of the polycarbonate resin (A), the flame retardancy may be deteriorated. If the content is more than 30 parts by weight, have.

(D) Halloysite tube

The halosite tube (D) used in the present invention is used as an impact modifier in a thermoplastic resin composition using the aromatic phosphate ester compound (C) and the filler (E) as a flame retardant, , And the flame retardancy can be improved. The haloisite tube (D) is a kaolin-based aluminum silicate among minerals and is formed in the form of a tube. The haloisite tube (D) exists in the form of a nanotube which can secure dispersibility in a polymer matrix and has a hollow center.

The diameter of the halosite tube (D) may be 1 to 500 nm, preferably 300 to 500 nm, and the length may be 100 to 40,000 nm, preferably 500 to 40,000 nm. The rigidity can be improved in the above range.

The haloisotube (D) may be contained in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). If the content of the haloisotube (D) is less than 0.1 parts by weight based on 100 parts by weight of the polycarbonate resin (A), the flame retardancy may be deteriorated. If the content is more than 5 parts by weight, .

In an embodiment, the content ratio ((C) :( D), weight ratio) of the aromatic phosphate ester compound (C) and the halosite tube (D) may be 5: 1 to 150: 1. The flame retardancy can be further improved without lowering the flexural modulus of the thermoplastic composition within the above range.

(E) filler

The filler (E) used in the present invention is added to increase the mechanical properties, heat resistance and dimensional stability of the flame retardant thermoplastic resin composition. As the filler (E), typical organic and / or inorganic fillers having various particle shapes such as spherical shape, plate shape, cylindrical shape and needle shape can be used. Specific examples thereof include carbon fiber, glass fiber, glass bead, , Carbon black, talc, clay, kaolin, talc, mica, calcium carbonate, and mixtures thereof. Preferably, glass fibers, talc or talc can be used, more preferably glass fibers or talc can be used. The filler E may have a longest length (long diameter) of 5 to 20 탆, but the present invention is not limited thereto.

The filler (E) may be included in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). If the content of the filler (E) is less than 5 parts by weight based on 100 parts by weight of the polycarbonate resin (A), the mechanical properties, heat resistance and dimensional stability may be deteriorated. If the content is more than 50 parts by weight, .

In an embodiment, the content ratio (D :( E), weight ratio) of the haloisotube (D) and the filler (E) may be from 1: 5 to 1: 250. The flame retardancy can be further improved without lowering the flexural modulus of the thermoplastic composition within the above range.

The flame-retardant thermoplastic resin composition according to the present invention may further contain additives such as ultraviolet stabilizer, fluorescent whitening agent, lubricant, releasing agent, antistatic agent, stabilizer, reinforcing material, coloring agent such as pigment or dye depending on each use . For example, the additive may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin (A), but is not limited thereto.

The ultraviolet stabilizer serves to suppress the color change of the resin composition and the deterioration of light reflectivity upon UV irradiation, and compounds such as benzotriazole-based, benzophenone-based, and triazine-based compounds can be used.

The fluorescent whitening agent serves to improve the light reflectance of the polycarbonate resin composition. It is preferable that the fluorescent whitening agent is 4- (benzoxazol-2-yl) -4'- (5-methylbenzoxazol-2-yl) Stibenz-bisbenzoxazole derivatives such as 4,4'-bis (benzoxazol-2-yl) stilbene and the like can be used.

As the release agent, a fluorine-containing polymer, a silicone oil, a metal salt of stearic acid, a metal salt of montanic acid, a montanic ester wax or a polyethylene wax may be used.

The flame retardant thermoplastic resin composition according to the present invention can improve the flame retardancy without lowering the stiffness such as the flexural modulus of elasticity. A specimen having a thickness of 1.2 mm is prepared, and the flame retardancy measured by the UL-94 vertical test method is V- 0 or more and a thickness of 6.4 mm, and the flexural modulus measured according to ASTM D790 may be 35,000 to 45,000 kgf / cm ² , preferably 37,000 to 45,000 kgf / cm ² .

The flame-retardant thermoplastic resin composition may be melt-extruded in an extruder after the components and other additives are mixed at the same time, and may be produced in the form of pellets. The produced pellets can be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding.

Another aspect of the present invention provides a molded article formed from the thermoplastic resin composition. The molded article is excellent in both rigidity and flame retardancy, and can be widely applied to parts, exterior materials, automobile parts, sundry goods, and structural materials of electric and electronic products.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example

The specifications of each component used in the following examples and comparative examples are as follows:

(A) Polycarbonate resin

A bisphenol-A type polycarbonate having a weight average molecular weight (Mw) of 25,000 g / mol was used.

(B) a rubber-modified aromatic vinyl-based copolymer resin

A resin prepared by kneading 40% by weight of the styrene-based graft copolymer resin (B-1) and 60% by weight of the styrene-containing copolymer resin (B-2) was used.

(B-1) styrene-based graft copolymer resin (ABS graft copolymer resin)

50 parts by weight of butadiene rubber latex was added to the reactor, and then 36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water were added, and 1.0 part by weight of potassium oleate, 0.4 part by weight of an oxide, 0.2 part by weight of a mercaptan chain transfer agent, 0.4 part by weight of glucose, 0.01 part by weight of sulfuric acid iron hydrate and 0.3 part by weight of sodium pyrophosphate were added and reacted at 75 DEG C for 5 hours to obtain a graft copolymer latex . 0.4 part by weight of sulfuric acid was added to the prepared resin latex in relation to the solid content of the resin latex to solidify the resin latex to prepare a styrene-based graft copolymer resin in powder form.

(B-2) Styrene-containing copolymer resin (SAN copolymer resin)

72 parts by weight of styrene, 28 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.2 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate and 0.2 parts by weight of mercaptan chain transfer agent were fed into the reactor, The temperature was raised to 80 캜 for 90 minutes, and then maintained at this temperature for 240 minutes to prepare a styrene-acrylonitrile copolymer resin (SAN) having an acrylonitrile content of 25% by weight. The resultant was washed with water, dehydrated and dried to prepare a styrene-containing copolymer resin in powder form. The styrene-containing copolymer resin had a weight average molecular weight of 180,000 to 200,000 g / mol.

(C) aromatic phosphoric acid ester compound: diarylphosphate (trade name: PX-200, manufactured by DAIHACHI INC.) Was used.

(D) Impact reinforcement

(D-1) Halo site nanotube: Dragonite XR from Applied mineral was used.

(D-2) Polydimethylsiloxane rubber mixture: Metablene S-2001 manufactured by Mistubishi Rayon chemical Co., Ltd. was used.

(E) filler

Glass fiber (trade name: UPN HS-T 0.5, manufactured by HAYASHI) was used.

Example  1 to 3 and Comparative Example  1 to 10

According to the contents of the following Table 1, each component was added and melted and kneaded in a biaxial melt extruder heated to 240 to 280 캜 to prepare a resin composition in a chip state. The chips thus obtained were dried at a temperature of 80 캜 for 5 hours or more and then tested for flame retardancy and specimens for evaluation of mechanical properties by using a screw extruder heated to 240 to 280 캜. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Flame retardancy: Specimens having thicknesses of 1.5 mm and 1.2 mm were prepared and measured by UL-94 vertical test method.

(2) Vicat Softening Temperature (VST): Measured according to ASTM D1525 at a load of 5 kgf (unit: ° C).

(3) Izod Impact Strength: A notch was measured on a 3.2 mm thick Izod sample according to ASTM D256 (Unit: kgf · cm / cm).

(4) Flexural modulus: A specimen having a thickness of 6.4 mm was prepared and measured according to ASTM D790 (unit: kgf / cm ² ).

Example Comparative Example One 2 3 One 2 3 4 5 6 7 8 9 10 (A) 100 100 100 100 100 100 100 100 100 100 100 100 100 (B) 15 15 20 - 50 15 15 15 15 15 15 15 15 (C) 20 20 20 20 20 5 40 20 20 20 20 20 20 (D-1) 2 3 2 2 2 2 2 - 10 2 2 - 0.05 (D-2) - - - - - - - - - - - 2 - (E) 20 20 20 20 20 20 20 20 20 - 100 20 20 Flammability (1.5mm) V-0 V-0 V-0 V-0 Fail Fail V-0 V-0 V-0 V-0 V-0 V-0 V-0 Flammability (1.2mm) V-0 V-0 V-0 V-0 Fail Fail V-0 Fail V-1 Fail V-0 V-1 V-1 VST 95 95 93 105 85 110 80 94 90 80 97 95 90 Impact strength 11 12 15 3 19 20 3 9 4 25 3 10 4 curve
Elastic modulus 39,000 41,000 38,000 42,500 38,000 36,000 40,000 39,500 40,000 24,000 45,000 33,000 36,000

Content Unit: parts by weight

From the results of Table 1, it can be seen that the flame retardant thermoplastic resin compositions of Examples 1 to 3 according to the present invention are excellent in impact strength and flame retardancy without lowering the rigidity (flexural modulus).

On the other hand, in Comparative Example 1 in which the rubber-modified aromatic vinyl copolymer resin (B) was not used, the impact strength was lowered. Comparative Example 2 in which the rubber-modified aromatic vinyl copolymer resin (B) was used in an excessive amount had a flame retardancy and heat resistance Comparative Example 3 in which the aromatic phosphate ester compound (C) was used in a small amount showed a decrease in flame retardancy and Comparative Example 4 in which the aromatic phosphate ester compound (C) was used in an excessive amount showed a decrease in impact strength and heat resistance (VST) Able to know. From the results of Comparative Example 5, it can be seen that when the impact modifier (D) such as the haloisotube (D-1) is not used, the flame retardancy and the impact strength are lowered and the haloisite tube (D- It can be seen from Comparative Examples 6 and 10 that the impact strength is rather lowered when a small amount is used. It was also found from Comparative Example 7 that the flame retardancy, heat resistance and flexural modulus were lowered when the filler (E) was not used. From Comparative Example 8, it was found that when the filler (E) Able to know. In particular, it was confirmed from Comparative Example 9 that when the polydimethylsiloxane rubber mixture (D-2) was used instead of the haloisotube (D-1) of the present invention as the impact modifier (D), the flame retardancy and the flexural modulus were lowered .

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

(A) 100 parts by weight of a polycarbonate resin;
(B) 5 to 30 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin;
(C) 10 to 30 parts by weight of an aromatic phosphate ester compound;
(D) 0.1 to 5 parts by weight of a halosite tube; And
(E) 5 to 50 parts by weight of a filler.
The rubber-modified aromatic vinyl-based graft copolymer resin (B) according to claim 1, wherein the rubber-modified aromatic vinyl-based graft copolymer resin (B) comprises 5 to 65% by weight of a rubbery polymer (B1), 15 to 94% by weight of an aromatic vinyl monomer, From 10 to 100% by weight of a graft copolymer resin comprising, by weight; And 0 to 90% by weight of an aromatic vinyl-based copolymer resin comprising (B2) 50 to 95% by weight of an aromatic vinyl monomer and 5 to 50% by weight of a vinyl cyanide compound.
The rubber-modified aromatic vinyl copolymer resin (B) according to claim 1, wherein the rubber-modified aromatic vinyl copolymer resin (B) is at least one selected from the group consisting of an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), an acrylonitrile-ethylene propylene rubber- Acrylonitrile-acryl rubber-styrene copolymer resin (AAS resin). The flame retardant thermoplastic resin composition according to claim 1,
The flame-retardant thermoplastic resin composition according to claim 1, wherein the aromatic phosphoric ester compound (C) is represented by the following formula (2):
(2)

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a C 6 -C 20 aryl group, or a C 6 -C 20 aryl group substituted with a C 1 -C 10 alkyl group, and R ₃ is A C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group, and n is an integer of 0 to 4;
The flame-retardant thermoplastic resin composition according to claim 1, wherein the haloisite tube (D) has a diameter of 1 to 500 nm and a length of 100 to 40,000 nm.
The method according to claim 1, wherein the filler (E) is selected from carbon fibers, glass fibers, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica, calcium carbonate and mixtures thereof Flame retardant thermoplastic resin composition.
The method according to claim 1, wherein the content ratio (C :( D), weight ratio) of the aromatic phosphate ester compound (C) and the halosite tube (D) is 5: 1 to 150: Wherein the content ratio (D :( E), weight ratio) of the tube (D) and the filler (E) is 1: 5 to 1: 250.
The flame-retardant thermoplastic resin composition according to claim 1, wherein the flame-retardant thermoplastic resin composition further comprises at least one of an ultraviolet light stabilizer, a fluorescent whitening agent, a lubricant, a releasing agent, an antistatic agent, a stabilizer, a reinforcing material, Composition.
The flame retardant thermoplastic resin composition according to claim 1, wherein the flame retardant thermoplastic resin composition has a flame retardancy of not less than V-0 and a flexural modulus of 35,000 to 45,000 kgf / cm ² measured according to ASTM D790, And the Izod impact strength measured based on D256 is 10 to 16 kgfcm / cm.
A molded article formed from the flame-retardant thermoplastic resin composition according to any one of claims 1 to 9.