WO2015064859A1 - Thermoplastic resin composition having excellent chemical resistance and boss hardness - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition which can innovatively improve mechanical properties including flame retardancy, chemical resistance and boss hardness by comprising an aromatic copolymer resin, a polycarbonate resin, an amorphous polyester resin, a halogen-based compound and an aromatic phosphate ester-based compound.

Description

Thermoplastic resin composition excellent in chemical resistance and boss rigidity

The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition having excellent flame retardancy, chemical resistance, and boss rigidity, and a molded article manufactured using the same.

Rubber-modified styrene-based copolymer resins are widely used as interior and exterior materials for electrical and electronic products because of their excellent mechanical rigidity and processability and good appearance characteristics. However, the rubber-modified styrene-based copolymer resin itself is not resistant to combustion, and it helps to burn when ignited, so it is important to secure fire safety since it can continuously spread fire.

In general, the flame retardant method applied to the rubber-modified styrenic copolymer resin includes a flame retardant such as a halogen flame retardant, a phosphorus flame retardant, an inorganic flame retardant, or a flame retardant aid. Among them, a combination of a halogen compound and an antimony compound is mainly used. For example, a halogen flame retardant and an antimony compound are added to an acrylonitrile / butadiene / styrene (ABS) resin or an impact resistant polystyrene (HIPS) resin to impart a flame retardant effect.

At this time, the antimony trioxide used as the antimony compound is a white inorganic material, the colorability of the resin composition is lowered, the color implementation is limited. In particular, high black color is difficult to implement. In addition, when using an antimony-based compound, there is a problem that the discoloration and gas generation is deepened at a high injection temperature by reaction with the halogen-based flame retardant.

On the other hand, when the antimony-based compound is not used, the same flame retardance can be obtained only by using about 2-3 times the halogen-based flame retardant than when the halogen-based flame retardant and the antimony-based compound are mixed. However, mechanical properties such as impact strength, tensile strength, flexural strength, heat resistance, heat deformation temperature, and the like of the resin composition are degraded, and thus there is a problem that it is difficult to apply to electrical and electronic products.

On the other hand, as a known flame retardant method of the rubber-modified aromatic vinyl copolymer resin, there is a method using an antidropping agent. This is a method of reducing the use of antimony compounds by using a small amount of anti-dropping agent, it is possible to reduce the use of antimony-based compounds by using the anti-dropping properties of the resin and the phenomenon that the thickness of the resin thickens during the combustion process. Polytetrafluoroethylene (PTFE) can be used as anti-dripping agent. However, even when the anti-drip agent is used, the antimony-based compound should be used, which causes problems.

Korean Patent No. 10-0150766 (Patent Document 1) discloses that a rubber-modified styrenic copolymer resin is mixed with a polycarbonate resin and a phosphate ester compound which are easily formed in char to give flame retardancy. In this case, the fluidity is lowered, which requires a high temperature during injection processing, and there is a problem in that the impact is reduced, such as decomposition of the resin due to high temperature injection or phase separation of the polycarbonate and the rubber-modified styrene copolymer.

The present invention has been made to solve the above problems, and an object thereof is to provide a thermoplastic resin composition excellent in thermal stability and flame retardancy.

An object of the present invention is to provide a thermoplastic resin composition capable of improving mechanical properties such as impact resistance and boss rigidity.

An object of the present invention is to provide a thermoplastic resin composition capable of improving chemical resistance.

An object of the present invention is to provide a thermoplastic resin composition excellent in colorability and appearance characteristics.

In addition, an object of the present invention is to provide a molded article excellent in thermal stability, flame retardancy, mechanical properties, chemical resistance and appearance properties produced from a thermoplastic resin composition.

In order to achieve the above object, the present invention can provide a thermoplastic resin composition comprising an aromatic copolymer resin, a polycarbonate resin, an amorphous polyester resin, a halogen compound and an aromatic phosphate ester compound.

Thermoplastic resin composition according to an embodiment of the present invention is based on (A) 100 parts by weight of the base resin consisting of (a1) aromatic copolymer resin, (a2) polycarbonate resin, (a3) amorphous polyester resin, (B ) 1 to 10 parts by weight of the halogen compound and 5 to 30 parts by weight of the (C) aromatic phosphate ester compound.

In the thermoplastic resin composition according to the exemplary embodiment of the present invention, the weight mixing ratio (a1 / a2) of the aromatic copolymer resin (a1) and the polycarbonate resin (a2) may be 0.5 to 1.8.

In the thermoplastic resin composition according to an embodiment of the present invention, the aromatic copolymer resin (a1) may include a rubber-modified aromatic vinyl graft copolymer and an aromatic vinyl copolymer.

In the thermoplastic resin composition according to an embodiment of the present invention, the rubber-modified aromatic vinyl graft copolymer is copolymerizable with 20 to 94 wt% of the aromatic vinyl monomer and 5 to 65 wt% of the rubbery polymer. It may be a graft polymerized monomer of 1 to 40% by weight.

In the thermoplastic resin composition according to an embodiment of the present invention, the amorphous polyester resin may be any one selected from the group consisting of polyalkylene terephthalate, polyalkylene naphthalate, and mixtures thereof.

In the thermoplastic resin composition according to an embodiment of the present invention, the amorphous polyester resin may be poly (ethylene-1,4-cyclohexanedimethylene terephthalate).

In the thermoplastic resin composition according to the embodiment of the present invention, the halogen-based compound is decabromodiphenyl oxide, decabromodiphenylethane, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer , Brominated epoxy oligomer, octabromotrimethylphenylindane, ethylenebistetrabromophthalimide, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-tri Azine, 1,2,3,4,7,8,9,10,13,13,14-dodecachloro-1,4,4a, 5,6,6a, 7,10,10a, 11,12, 12a-dodecahydro-1,4,7,10-dimethanodibenzo (a, e) cyclooctene and mixtures thereof.

In the thermoplastic resin composition according to the embodiment of the present invention, the aromatic phosphate ester compound may be represented by the following Chemical Formula 1.

[Formula 1]

(In Formula 1, R ₁ , R ₂ , R ₄ and R ₅ are each independently an aryl group or alkyl-substituted aryl group of C6 ~ C20, R ₃ is resorcinol, hydroquinol, bisphenol-A and Any one selected from the group consisting of dialcohols of bisphenol-S, n is an integer from 0 to 5.)

In the thermoplastic resin composition according to an embodiment of the present invention, the weight mixing ratio of the halogen-based compound and the aromatic phosphate ester-based compound may be 1: 1 to 1: 8.

Thermoplastic resin composition according to an embodiment of the present invention is at least one selected from the group consisting of anti-dropping agent, impact modifier, antioxidant, plasticizer, thermal stabilizer, light stabilizer, compatibilizer, pigment, dye, inorganic additive, antibacterial agent and antistatic agent It may further include an additive.

The present invention provides a molded article prepared from the thermoplastic resin composition.

The thermoplastic resin composition according to the present invention has excellent mechanical properties and appearance characteristics, including dimensional stability, molding processability, impact resistance, and boss rigidity, and has an advantage of significantly improving thermal stability, flame retardancy, and chemical resistance.

Figure 1 shows a quarter elliptical jig model for measuring chemical resistance.

Figure 2 shows the insertion of the screw into the cylinder to measure the boss stiffness.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. The following embodiments are provided as examples to ensure that the spirit of the present invention can be fully conveyed to those skilled in the art. In addition, unless there is another definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and unnecessarily obscure the subject matter of the present invention in the following description. Description of known functions and configurations that may be omitted.

The inventors of the present invention have studied to develop a thermoplastic resin composition having excellent flame retardancy and excellent mechanical properties such as chemical resistance and boss stiffness, and as a result, a thermoplastic resin comprising an aromatic copolymer resin, a polycarbonate resin, and an amorphous polyester resin. The present invention was found to be surprisingly excellent in thermal stability and flame retardancy, and at the same time significantly improved chemical resistance and boss stiffness by using the base resin, the base resin, the halogen compound and the aromatic phosphate ester compound at the same time. Completed.

In one aspect, the thermoplastic resin composition of the present invention is based on (A) 100 parts by weight of a base resin composed of (a1) aromatic copolymer resin, (a2) polycarbonate resin, and (a3) amorphous polyester resin, (B) It may include 1 to 10 parts by weight of the halogen compound and 5 to 30 parts by weight of the (C) aromatic phosphate ester compound.

Hereinafter, each component is demonstrated in detail.

(A) basic resin

(a1) aromatic copolymer resin

In the present invention, the aromatic copolymer resin may include a copolymer of an aromatic monomer and a monomer copolymerizable with the aromatic monomer. It may be selected from block copolymers, random copolymers, alternating copolymers, graft copolymers, and mixtures thereof, but is not necessarily limited thereto.

The aromatic copolymer resin (a1) may be contained 35 to 60% by weight relative to the total weight of the base resin consisting of the polycarbonate resin (a2) and the amorphous polyester resin (a3) to be described later.

In the thermoplastic resin composition according to an embodiment of the present invention, the aromatic copolymer (a1) may include a rubber-modified aromatic vinyl graft copolymer and an aromatic vinyl copolymer.

(a11) Rubber-modified aromatic vinyl graft copolymer

In the present invention, the rubber-modified aromatic vinyl graft copolymer may be prepared by graft copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer to a rubbery polymer. At this time, the graft copolymerization of the monomer which can provide workability and heat resistance can be carried out as needed.

The rubber-modified aromatic vinyl graft copolymer is, in one embodiment, graft 5 to 65% by weight rubbery polymer, 20 to 94% by weight aromatic vinyl monomer and 1 to 40% by weight monomer copolymerizable with the aromatic vinyl monomer It may be polymerized.

Examples of the rubbery polymers include diene rubbers, saturated rubbers in which hydrogen is added to the diene rubbers, acrylate rubbers, ethylene-propylene rubbers, ethylene-propylene-diene terpolymers, silicone rubbers, and the like. Any one or a mixture of two or more of these may be used, but is not necessarily limited thereto.

The diene rubber may be any one selected from polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), polyisoprene, and mixtures thereof, but is not necessarily limited thereto.

The acrylate rubbers are polymethyl acrylate, polyethyl acrylate, poly (n-propyl acrylate), poly (n-butyl acrylate), poly (2-ethylhexyl acrylate), polyhexyl methacrylate, Any one selected from poly (2-ethylhexyl methacrylate) and mixtures thereof may be used, but is not necessarily limited thereto.

The silicone rubbers include polyhexamethyl cyclotrisiloxane, polyoctamethyl cyclosiloxane, polydecamethyl cyclosiloxane, polydodecamethyl cyclosiloxane, polytrimethyltriphenyl cyclosiloxane, polytetramethyltetrapetyl cyclotetrasiloxane, polyoctaphenyl cyclo Any one selected from the group consisting of tetrasiloxanes and mixtures thereof can be used, but is not necessarily limited thereto.

The rubbery polymer may be any one selected from the group consisting of ethylene-propylene rubber, terpolymer of ethylene-propylene-diene, and mixtures thereof, but is not limited thereto.

The rubbery polymer may be preferably a diene rubber, more preferably a polybutadiene rubber.

The particle size of the rubbery polymer may be 0.05 to 4.0 μm in Z-average, and preferably 0.1 to 3.0 μm. When the particle size of the rubbery polymer is included in the above range, impact resistance and appearance characteristics may be improved.

(a12) Aromatic vinyl copolymer

In the present invention, the aromatic vinyl copolymer may be obtained by polymerizing 60 to 90% by weight of an aromatic vinyl monomer and 10 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer.

The aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p- (tert-butyl) styrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, Vinyl naphthalene and mixtures thereof, but is not limited thereto.

The monomer copolymerizable with the aromatic vinyl monomer may be any one selected from unsaturated nitrile monomers, acrylic monomers, and mixtures thereof, but is not necessarily limited thereto.

The nitrile-based monomer may be any one selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof, but is not necessarily limited thereto.

The acrylic monomer may be any one selected from methyl acrylate, methyl methacrylate, and mixtures thereof, but is not necessarily limited thereto.

The rubber-modified aromatic vinyl graft copolymer may further include any monomer selected from unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimide monomers, and mixtures thereof in the rubbery polymer to impart heat resistance and processability. It may be graft polymerized.

The unsaturated carboxylic acid may include acrylic acid or methacrylic acid, but is not necessarily limited thereto.

The unsaturated carboxylic anhydride may include maleic anhydride, but is not necessarily limited thereto.

The maleimide monomer may include alkyl or nuclear substituted maleimide, but is not necessarily limited thereto.

 (a2) polycarbonate resin

In the present invention, the polycarbonate resin is combined with the aromatic copolymer resin (a1) and the amorphous polyester resin (a3) described later to improve mechanical properties such as boss stiffness and impact resistance, and at the same time, flame retardancy, chemical resistance and appearance characteristics. Can produce a synergistic effect.

In this case, the polycarbonate resin (a2) may have a weight mixing ratio ((a1 / a2) of 0.5 to 1.8 with the aromatic copolymer resin (a1). Preferably, the aromatic copolymer resin (a1) and the polycarbonate resin (a2) The weight mixing ratio may be 35: 60 to 65: 30. If the weight mixing ratio is out of the range, flame retardancy or chemical resistance may be lowered.

The polycarbonate resin (a2) may be prepared by a conventional method. Preferably aromatic polycarbonate resins can be used without limitation.

For example, the polycarbonate resin may be an aliphatic polycarbonate resin, an aromatic polycarbonate resin, a copolycarbonate resin thereof, a copolycarbonate carbonate resin, a polycarbonate-polysiloxane copolymer resin, or a mixture thereof. In addition, the polycarbonate resin may have a linear or branched structure.

The polycarbonate resin of the present invention can be prepared by reacting an aromatic dihydroxy compound (a21) with a carbonate precursor (a22).

(a21) aromatic dihydroxy compound

The aromatic dihydroxy compound (a1) is a compound represented by the following formula (2) or a mixture thereof:

[Formula 2]

In Formula 2, R ₆ and R ₇ are each independently hydrogen, halogen, or an alkyl group of C1-C8; a and b are each independently an integer between 0 and 4, Z is a single bond, an alkylene group of C1-C8, an alkylidene group of C2-C8, a cycloalkylene group of C5-C15, a cycloalkyl of C5-C15 A den group, -S-, -SO-, SO _2- , -O-, or -CO-.

Examples of the aromatic dihydroxy compound (a21) represented by the formula (2) include bis (hydroxy aryl) alkane, bis (hydroxy aryl) cycloalkane, bis (hydroxy aryl) ether, bis (hydroxy aryl) sulfide, and bis (hydroxy Roxy aryl) sulfoxide, biphenyl compounds may be used, and these compounds may be used alone or in a mixture of two or more.

The bis (hydroxy aryl) alkanes include bis (4-hydroxy phenyl) methane, bis (3-methyl-4-hydroxy phenyl) methane, bis (3-chloro-4-hydroxy phenyl) methane, bis (3 , 5-dibromo-4-hydroxy phenyl) methane, 1,1-bis (4-hydroxy phenyl) ethane, 1,1-bis (2-tertiary-butyl-4-hydroxy-3-methyl Phenyl) ethane, 2,2-bis (4-hydroxy phenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxy phenyl) propane, 2,2-bis (2-methyl- 4-hydroxy phenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy phenyl) propane, 1,1-bis (2-tertiary-butyl-4-hydroxy-5-methyl phenyl Propane, 2,2-bis (3-chloro-4-hydroxy phenyl) propane, 2,2-bis (3-fluoro-4-hydroxy phenyl) propane, 2,2-bis (3-bromo 4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxy phenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxy phenyl) propane , 2,2-bis (3,5-dibromo-4-hydroxy phenyl) propane, 2,2- ratio S (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy phenyl) octane, 2,2-bis (4-hydroxy phenyl) phenyl methane, 2,2-bis (4-hydroxy- 1-methyl phenyl) propane, 1,1-bis (4-hydroxy-tertiary-butyl phenyl) propane, 2,2-bis (4-hydroxy-3-bromo phenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl phenyl) propane, 2,2-bis (4-hydroxy-3-chloro phenyl ) Propane, 2,2-bis (4-hydroxy-3,5-dichloro phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo phenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chloro phenyl) propane, 2,2-bis (3-phenyl- 4-hydroxy phenyl) propane, 2,2-bis (4-hydroxy phenyl) butane, 2,2-bis (3-methyl-4-hydroxy phenyl) butane, 1,1-bis (2-butyl- 4-hydroxy-5-methyl phenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) butane, 1,1-bis (2- Tert-butyl-4-hydroxy-5-methyl phenyl) isobutane, 1,1-bis (2-tertary-amyl-4-hydroxy-5-methyl phenyl) butane, 2,2-bis (3 , 5-dichloro-4-hydroxy phenyl) butane, 2,2-bis (3,5-dibromo-4-hydro phenyl) butane, 4,4-bis (4-hydroxy phenyl) heptane, 1, 1-bis (2-tert-butyl-4-hydroxy-5-methyl phenyl) heptane, 2,2-bis (4-hydroxy phenyl) octane, 1,1- (4-hydroxy phenyl) ethane and It may be any one selected from the group consisting of a mixture thereof, but is not necessarily limited thereto.

The bis (hydroxy aryl) cycloalkane is 1,1-bis (4-hydroxy phenyl) cyclopentane, 1,1-bis (4-hydroxy phenyl) cyclohexane, 1,1-bis (3-methyl- 4-hydroxy phenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxy phenyl) cyclohexane, 1,1-bis (3-phenyl-4-hydroxy phenyl) cyclohexane, 1, 1-bis (4-hydroxy phenyl) -3,5,5-trimethylcyclohexane and mixtures thereof, but is not limited thereto.

The bis (hydroxy aryl) ether may be any one selected from the group consisting of bis (4-hydroxy phenyl) ether, bis (4-hydroxy-3-methyl phenyl) ether, and mixtures thereof, and thus It is not limited.

The bis (hydroxy aryl) sulfide may be any one selected from the group consisting of bis (4-hydroxy phenyl) sulfide, bis (3-methyl-4-hydroxy phenyl) sulfide and mixtures thereof, and thus It is not limited.

The bis (hydroxy aryl) sulfoxides include bis (hydroxy phenyl) sulfoxide, bis (3-methyl-4-hydroxy phenyl) sulfoxide, bis (3-phenyl-4-hydroxy phenyl) sulfoxide and these It may be any one selected from the group consisting of, but is not necessarily limited thereto.

The biphenyl compound is bis (hydroxy aryl) such as bis (4-hydroxy phenyl) sulfone, bis (3-methyl-4- hydroxy phenyl) sulfone, bis (3-phenyl-4- hydroxy phenyl) sulfone Sulfone, 4,4'-dihydroxy biphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4 Can be any one selected from the group consisting of 4'-dihydroxy-3,3'-dicyclobiphenyl, 3,3-difluoro-4,4'-dihydroxy biphenyl, and mixtures thereof. It is not necessarily limited thereto.

Aromatic dihydroxy compounds (a21) that can be used in addition to the compound represented by the formula (2) include dihydroxy benzene, halogen or alkyl-substituted dihydroxy benzene. Specifically resorcinol, 3-methyl resorcinol, 3-ethyl resorcinol, 3-propy resorcinol, 3-butyl resorcinol, 3-tertiary-butyl resorcinol, 3-phenyl resorcinol , 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3 -Propylhydroquinone, 3-butylhydroquinone, 3-tertiary-butylhydroquinone, 3-phenylhydroquinone, 3-gyumilhydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetramethyl Hydroquinone, 2,3,5,6-tetra-tertiary-butylhydroquinone, 2,3,5,6-tetraprohydrohydroquinone, 2,3,5,6-tetrabromo hydroquinone, and the like. May be, but is not necessarily limited thereto.

The aromatic dihydroxy compound (a21) may be preferably 2,2-bis (4-hydroxy phenyl) propane (bisphenol A).

(a22) carbonate precursor

The carbonate precursors are dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) Carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, bishaloformate and the like. These compounds may be used alone or in mixture of two or more.

The carbonate precursor (a22) may be used in a molar ratio of 0.9 to 1.5 with respect to 1 mole of the aromatic dihydroxy compound (a21).

The polycarbonate resin (a2) of the present invention may have a weight average molecular weight of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol.

The polycarbonate resin (a2) may be contained 35 to 55% by weight relative to the total weight of the base resin. When the content of the polycarbonate resin (a2) is less than 35% by weight, impact resistance, thermal stability and molding processability may be lowered, and when it is more than 55% by weight, flame resistance and chemical resistance may be lowered.

(a3) amorphous polyester resin

In the present invention, the polyester resin may be preferably selected from polyalkylene terephthalate resin or polyalkylene naphthalate resin.

Preferably, the amorphous polyester resin may comprise 0.1 to 99 mol% of the cyclic alkyldiol derivatives relative to the acid component derivatives.

Examples of the polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexaneterephthalate (PCT), polyethylene naphthalate (PEN), and the like, but are not necessarily limited thereto. Do not.

Moreover, glycol modified polyethylene terephthalate can be used as needed.

The amorphous polyester may preferably be poly (ethylene-1,4-cyclohexanedimethylene terephthalate) (PETG).

The amorphous polyester may preferably have a viscosity of 0.6 to 0.8 dl / g.

The amorphous polyethylene terephthalate may be formed by polymerizing an acid component and a diol component. Terephthalic acid, isophthalic acid and other acid components may be used as the acid component, and ethylene glycol, 1,4-cyclohexadimethanol and other diol components may be used as the diol component.

The diol component may include 1,4-cyclohexadimethanol. In this case, 1,4-cyclohexadimethanol may be 0.1 to 99 mol%, preferably 20 to 60 mol%, relative to the acid derivative.

The amorphous polyester resin used in the present invention may have an intrinsic viscosity of 0.5 to 1.0 dl / g, preferably 0.6 to 0.8 dl / g.

The polyester resin (a3) may be contained 5 to 15% by weight based on the total weight of the base resin. When the polyester resin (a3) content is less than 5% by weight, flame retardancy and mechanical properties may be lowered, and when it is more than 15% by weight, chemical resistance may be lowered.

(B) halogen-based compound

In the present invention, the halogen compound may use a conventional bromine compound or chlorine compound, but is not necessarily limited thereto. Preferably, a halogenated flame retardant having a bromine or chlorine content of 50% or more may be used in consideration of mechanical properties and flame retardancy.

Examples of the halogen-based compound include decabromodiphenyl oxide, decabromodiphenylethane, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, brominated epoxy oligomer, and octabromotri Methylphenyl indane, ethylenebistetrabromophthalimide, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, 1,2,3,4, 7,8,9,10,13,13,14-dodecachloro-1,4,4a, 5,6,6a, 7,10,10a, 11,12,12a-dodecahydro-1,4, It may be any one selected from the group consisting of 7,10-dimethanodibenzo (a, e) cyclooctene and mixtures thereof.

In the present invention, the halogen-based compound may be used in combination with the aromatic phosphate ester compound described below to improve flame retardancy and moldability without deteriorating mechanical properties including boss strength.

In the present invention, the halogen-based compound (B) may be included 1 to 30 parts by weight based on 100 parts by weight of the base resin (A). If the content of the halogen-based compound is less than 1 part by weight, flame retardancy may be lowered. If it is more than 30 parts by weight, moldability and boss strength may be reduced.

(C) Aromatic Phosphate Ester Compounds

In the present invention, the aromatic phosphate ester compound may be represented by Formula 1, but is not necessarily limited thereto.

The aromatic phosphate ester compound may be used to impart flame retardancy. At this time, the aromatic phosphate ester-based compound may be included 5 to 30 parts by weight based on 100 parts by weight of the base resin (A). Preferably 10 to 20 parts by weight may be included. Is suitable. If the aromatic phosphate ester compound content is less than 5 parts by weight, flame retardancy may be lowered, and if it is more than 30 parts by weight, chemical resistance and boss rigidity may be lowered.

[Formula 1]

In Chemical Formula 1, R ₁ , R ₂ , R _4, and R ₅ are each independently an aryl group or an alkyl substituted aryl group having 6 to 20 carbon atoms, and R ₃ is resorcinol, hydroquinol, bisphenol-A, and bisphenol. Any one selected from the group consisting of dial alcohols of -S, n is an integer from 0 to 5.

The aromatic phosphate ester compound is, for example, when n is 0, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trigylyl phosphate, tri (2, 4, 6-trimethylphenyl) phosphate, tri ( 2, 4-dibutyl butylphenyl) phosphate, a tri (2, 6-dibutyl butylphenyl) phosphate, etc. are mentioned. In addition, when n is 1, resorcinol bis (diphenyl phosphate), hydroquinol bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol bis (2,6-dibutyl butylphenyl) Phosphate), hydroquinolbis (2,6-dimethylphenylphosphate), and the like, but are not necessarily limited thereto. In addition, when n is 2 or more, it is present in the form of a mixture in oligomeric form, and a single or a mixture of two or more of the above-described compounds may be used.

The aromatic phosphate ester compound may be used simultaneously with other phosphorus-containing flame retardants such as phosphorus, phosphonate, phosphinate, and phosphazene, and may replace part or all.

In the present invention, the weight mixing ratio of the halogen-based compound and the aromatic phosphate ester-based compound may be 1: 1 to 1: 8. When the weight mixing ratio of the halogen-based compound and the aromatic phosphate ester-based compound is outside the above range, chemical resistance or boss stiffness may decrease.

The thermoplastic resin manufacturing method of the present invention may further include a dropping agent, an impact enhancer, an antioxidant, a plasticizer, a heat stabilizer, a light stabilizer, a compatibilizer, a weather stabilizer, a pigment, a dye, a colorant, an inorganic additive, and a mixture thereof. May be, but is not necessarily limited thereto. Examples of the inorganic additives include glass fibers, silica, talc, ceramics, and the like.

The additive may be included from 0 to 50 parts by weight based on 100 parts by weight of the base resin (A).

The resin composition of the present invention may be prepared by a conventional method, and preferably, the components of the present invention and other additives may be mixed at the same time, and then melt-extruded in an extruder to prepare pellets or chips.

Thermoplastic resin composition according to the present invention is very excellent in flame retardancy, detergent resistance and boss rigidity can be applied to various fields including electrical and electronic products.

The thermoplastic resin composition of the present invention may preferably be used for chemical resistance and boss rigidity.

The present invention provides a molded article prepared from the thermoplastic resin composition.

Examples of the method for molding the molded article include extrusion, injection, compression or casting molding methods, but are not necessarily limited thereto.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Specifications of each component used in the following Examples and Comparative Examples are as follows.

(A) Basic resin

(a1) aromatic copolymer resin

(a11) Rubber modified aromatic vinyl graft copolymer: A graft acrylonitrile-butadiene-styrene graft copolymer (g-ABS) containing 58% by weight of a polybutadiene rubbery polymer manufactured by Cheil Industries was used. .

(a12) Aromatic vinyl copolymer: A styrene-acrylonitrile copolymer (SAN) having an acrylonitrile content of 28 wt% manufactured by Cheil Industries was used.

(a2) Polycarbonate resin: Panlite L-1225 Grade manufactured by Teijin, Japan was used.

(a31) Amorphous polyester resin: SKYGREEN PETG (S2008) Grade of SKC Corporation was used.

(a32) Crystalline polyester resin: A1100 manufactured by Amuchem was used.

(B) Halogen compound: Saytex 4010 manufactured by Albemarle, USA was used.

(C) Aromatic Phosphate Ester Compounds: CR-741 Grade, which is bisphenol-A bis (diphenylphosphate) manufactured by Daihachi Chemical Co., Ltd., was used.

(Example 1)

Each component was mixed in a mixer using the above-mentioned components in the composition shown in Table 1, and then introduced into a twin screw extruder (L / D = 35, ø = 45 mm). In Example 1, 2.5 parts by weight of the halogen-based compound and 20 parts by weight of the aromatic phosphate ester compound based on 100 parts by weight of the base resin consisting of 35% by weight of the aromatic copolymer resin, 60% of the polycarbonate resin and 5% by weight of the amorphous polyester resin. The mixture mixed in the mixer was prepared through pellet extruder thermoplastic resin composition. The composition was prepared in the specimen for evaluation of physical properties using a 15 oz injection machine at an injection temperature of 220 to 240 ℃. These specimens were measured for 48 hours at a temperature of 23 ° C. and a relative humidity of 50%, and then measured according to the following evaluation method. The results are shown in Table 1 below.

In Table 1, the contents of (a1), (a2) and (a3) are in weight%, and the contents of (B), (C), (D) and (E) are (a1) + (a2) + ( a3) = relative content (parts by weight) to 100 parts by weight.

(Example 2)

5 parts by weight of a halogen-based compound and aromatic phosphate ester based on 100 parts by weight of a base resin resin comprising 40% by weight of an aromatic copolymer resin, 50% of a polycarbonate resin and 10% by weight of an amorphous polyester resin. Except that 15 parts by weight of the compound was carried out in the same manner as in Example 1.

(Example 3)

It carried out by the same method as Example 1 except having used the base resin resin which consists of 45 weight% of aromatic copolymer resins, 45% of polycarbonate resins, and 10 weight% of amorphous polyester resins.

(Example 4)

It carried out by the same method as Example 1 except having used the base resin resin which consists of 50 weight% of aromatic copolymer resins, 35% of polycarbonate resins, and 15 weight% of amorphous polyester resins.

(Example 5)

It carried out by the same method as Example 2 except having used the base resin which consists of 55 weight% of aromatic copolymer resins, 40% of polycarbonate resins, and 5 weight% of amorphous polyester resins.

(Example 6)

It carried out by the same method as Example 1 except having used the base resin resin which consists of 60 weight% of aromatic copolymer resins, 35% of polycarbonate resins, and 5 weight% of amorphous polyester resins.

(Comparative Example 1)

It carried out by the same method as Example 1 except not using amorphous polyester resin and using the base resin resin which consists of 70 weight% of aromatic copolymer resins, and 30% of polycarbonate resins.

(Comparative Example 2)

It carried out by the same method as Example 1 except having used the base resin resin which consists of 60 weight% of aromatic copolymer resins, 30% of polycarbonate resins, and 10 weight% of crystalline polyester resins (a4).

(Property evaluation)

(1) flame retardant

Flame retardancy was evaluated as pass or fail in accordance with UL94 for 1.5 mm thick specimens, and flame retardance was measured for the passed specimens.

 (2) chemical resistance

It was measured using a quarter elliptic jig model (length of long axis: 120 mm, length of short axis: 34 mm) as shown in FIG. A specimen having a thickness of 3.2 mm was injected, placed on a jig, and placed in a 50 ° C. oven for 12 hours, and evaluated for cracks. At this time, the specimen is coated with a 50% water dilution of Nanox (Lion, Japan) to 100㎛ thickness.

 (3) Boss Torque

As shown in FIG. 2, a cylinder having a diameter of 6 mm, an inner diameter of 3 mm, and a height of 2 cm was formed on the specimen of 4 cm × 2 cm, and a screw torque was inserted into the cylinder to evaluate boss torque as crack occurrence.

As can be seen in Table 1, Examples 1 to 6 according to the present invention was confirmed to exhibit excellent flame resistance, chemical resistance and boss stiffness compared to Comparative Examples 1 and 2.

As described above in the present invention has been described by a limited embodiment, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, the present invention is not limited to the common knowledge Those having a variety of modifications and variations are possible from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the claims as well as the following claims will belong to the scope of the present invention. .

Claims (12)

1. A thermoplastic resin composition comprising an aromatic copolymer resin, a polycarbonate resin, an amorphous polyester resin, a halogen compound and an aromatic phosphate ester compound.
2. The method of claim 1,

   The thermoplastic resin composition is based on (A) 100 parts by weight of the base resin consisting of (a1) aromatic copolymer resin, (a2) polycarbonate resin, and (a3) amorphous polyester resin, (B) halogenated compounds 1 to 10 A thermoplastic resin composition comprising 5 parts by weight and 5 to 30 parts by weight of the (C) aromatic phosphate ester compound.
3. The method of claim 2,

   The resin composition (A) wherein the base resin has a weight mixing ratio (a1 / a2) of the aromatic copolymer resin (a1) and the polycarbonate resin (a2) of 0.5 to 1.8.
4. The method of claim 1,

   The aromatic copolymer resin (a1) is a thermoplastic resin composition comprising a rubber-modified aromatic vinyl graft copolymer and an aromatic vinyl copolymer.
5. The method of claim 4, wherein

   The rubber-modified aromatic vinyl graft copolymer is a graft polymer of 20 to 94% by weight of an aromatic vinyl monomer and 1 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer to 5 to 65% by weight of a rubbery polymer. Thermoplastic resin composition.
6. The method of claim 1,

   The amorphous polyester resin is any one selected from the group consisting of polyalkylene terephthalate, polyalkylene naphthalate and mixtures thereof.
7. The method of claim 6,

   The amorphous polyester resin is a poly (ethylene-1,4-cyclohexanedimethylene terephthalate) thermoplastic resin composition.
8. The method of claim 1,

   The halogen-based compound is decabromodiphenyl oxide, decabromodiphenylethane, decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, brominated epoxy oligomer, octabromotrimethylphenyl indane, Ethylene bistetrabromophthalimide, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, 1,2,3,4,7,8 , 9,10,13,13,14-dodecachloro-1,4,4a, 5,6,6a, 7,10,10a, 11,12,12a-dodecahydro-1,4,7,10 A thermoplastic resin composition which is any one selected from the group consisting of dimethanodibenzo (a, e) cyclooctene and mixtures thereof.
9. The method of claim 1,

   The aromatic phosphate ester compound is a thermoplastic resin composition represented by the following formula (1).

   [Formula 1]

   

   (In Formula 1, R ₁ , R ₂ , R ₄ and R ₅ are each independently an aryl group or alkyl-substituted aryl group of C6 ~ C20, R ₃ is resorcinol, hydroquinol, bisphenol-A and Any one selected from the group consisting of dialcohols of bisphenol-S, n is an integer from 0 to 5.)
10. The method of claim 1,

    The weight ratio of the halogen-based compound and the aromatic phosphate ester-based compound is 1: 1 to 1: 8 thermoplastic resin composition.
11. The method of claim 1,

    A thermoplastic resin composition further comprising at least one additive selected from the group consisting of anti-dripping agents, impact modifiers, antioxidants, plasticizers, thermal stabilizers, light stabilizers, compatibilizers, pigments, dyes, inorganic additives, antibacterial agents and antistatic agents.
12. A molded article prepared from the composition of any one of claims 1 to 11.

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