KR20100067198A - Thermoplastic resin composition having improved impact strength - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition is provided to improve shock resistance, to maintain impact strength when the thermoplastic resin composition is molded at a high temperature, and to be used as exterior materials of electronic products. CONSTITUTION: A thermoplastic resin composition having improved shock resistance comprises: 30~99 parts by weight of a styrene-based polymer with an epoxy group; 1~70 parts by weight of a polyester resin; 0.1~5 parts by weight of a polyamide resin based on 100.0 parts by weight of the styrene-based polymer and the polyester resin; 1~30 parts by weight of bromine-containing flame retardant; and 0.1~10 parts by weight of a flame-retardant adjuvant.

Description

Thermoplastic Resin Composition Having Improved Impact Strength

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition excellent in impact resistance. More specifically, the present invention relates to a thermoplastic resin composition in which impact resistance is remarkably improved by adding a polyamide resin to a base resin comprising a styrene-based polymer and an polyester resin containing an epoxy group.

Background of the Invention

In general, styrene resins are excellent in transparency, thermal stability and mechanical properties. Such styrene resins are used alone or as high impact polystyrene (HIPS) copolymerized with rubber and styrene, or ABS resins copolymerized with acrylonitrile, rubber and styrene, and are used in various fields. . In particular, rubber-reinforced styrene resins are widely used as exterior materials for electrical and electronic products because of their excellent physical properties.

However, styrene-based resins do not have a resistance to combustion, and when a spark is ignited by an external ignition factor, the resin itself acts as an energy to help combustion, thereby continuously spreading fire. Accordingly, studies have been made to impart flame retardancy to styrene resins, and a method of adding a flame retardant to styrene resins has been proposed.

On the other hand, since the polyester resin has a short molecular chain length and poor structure, the polyester resin has good rigidity, electrical properties, weather resistance, heat resistance, and the like, and even when exposed at a high temperature for a long time, the tensile strength is considerably reduced. In addition, since it belongs to crystalline plastics, resistance to oils such as diesel oil is good.

However, polyester resins have an ester bond in the molecular chain, so that physical properties of the polyester resin are easily changed when contacted with an acid or an alkali for a high temperature and a long time. In addition, the impact resistance is difficult to use as a structural material. In order to use such a polyester resin as a structural material, a reinforcing agent such as glass fiber should be added. In addition, unless a mechanical reinforcing agent is used, the use as a structural material through injection molding in a general composition is limited.

In addition, since polyester resins have a disadvantage of easy combustion, various methods for imparting flame retardance to polyether resins have been studied. Japanese Patent Application No. 2004-056837 discloses a halogen flame retardant, an antimony oxide, potassium dihydrogen phosphate (KH ₂ PO ₄ ) or lithium dihydrosium phosphate (LiH ₂ PO ₄ ) in a resin containing polyethylene terephthalate (PET) and other polyesters. And a thermoplastic material to which a drip prevention agent is added are illustrated. In addition, Japanese Patent Application No. 1992-330430 discloses a flame-retardant resin composition composed of a polyethylene terephthalate (PET), a brominated bisphenol compound (TBBA), a glass fiber, an inorganic filler, and a polyolefin containing a glycidyl group.

Unlike the method of mixing the flame retardant with the polyester resin as described above, a method of adding a flame retardant such as a halogen or a phosphorus compound when synthesizing the polymer has been proposed. However, as proposed in Japanese Patent Application Laid-Open No. 48-52843, the method of adding a halogen-containing compound is provided with flame retardancy, but addition of a large amount of flame retardant not only results in deterioration of mechanical properties but also severely degrades weather resistance and yellow color. There are drawbacks such as coloring. In addition, since phosphorus-containing compounds are inherently poor in thermal stability and have low reactivity with polyesters, it is very difficult to contain a sufficient amount of flame retardant in the polymer.

In order to solve these drawbacks, the organic phosphorus compounds are disclosed in Japanese Patent Laid-Open No. 52-10351, Japanese Patent Laid-Open No. 59-191716, Japanese Patent Laid-Open No. 36-20771, US Patent No. 3,941,752, US Patent No. 4,033,936, and the like. After adding the polycondensation catalyst, the polycondensation catalyst is added while the polycondensation reaction proceeds to a certain degree, or the method of imparting flame retardancy by polycondensing phenylphosphonic acid dialkyl ester or phenylphosphonic acid aliphatic glycol ester as the reaction component of polyester. And the like. However, these techniques are complex or substantially low in the residual ratio of the phosphorus compound does not show a satisfactory flame retardancy.

On the other hand, in order to improve the impact resistance of polyester, Japanese Patent Application No. 2003-140617 discloses that styrene and acrylonitrile are grafted to a rubber made of ethylene, propylene, and diene in which acid-modified low molecular weight α-olefin copolymer is uniformly dispersed. The technique which mix | blends the acrylonitrile ethylene propylene rubber styrene copolymer (AES) resin which is a graft copolymer obtained by copolymerization to a polyester resin is disclosed. However, the above technique is effective only when the content of the polyester resin is more than 60%, there is a disadvantage in that the effect of the impact modifier is less than the content.

Japanese Patent Application No. 2002-224941 discloses a technique for selectively including polycarbonate (PC) in a composition consisting of a polyethylene terephthalate (PET) recycling material, g-ABS, and a SAN resin. However, since the above technique basically uses recycled polyester resin, there is a limit in obtaining a high impact stable thermoplastic resin composition that can be used as a structural material. In addition, the thermoplastic resin composition has a disadvantage in that color development is very different depending on the size of the product due to a phase problem between ABS and PET when injection or extrusion processing at a high temperature. In addition, particularly when the resin stays in the molding machine for a long time, the difference in physical properties is large.

Japanese Patent Application No. 1991-283787 discloses a technique in which warpage of molded articles is reduced, dimensional stability is improved, and moldability is improved when PET, polybutylene terephthalate (PBT) and SAN resin are added. However, when glass fiber reinforcement is not made, it is difficult to greatly improve impact resistance.

U.S. Patent Application No. 1999-500462 discloses a technique for resin compositions having improved impact resistance by using g-ABS or methacrylate-butadiene-styrene (MBS) in PET. However, this is a technique for improving adhesion in a laminated film, and when molding a large injection molding by injection molding, polyester and g-ABS or MBS agglomerate with each other, resulting in instability of physical properties, especially low polyester content In this case, there is a drawback that the effect is large.

US Patent Application No. 1982-354468 illustrates a technique for improving the heat resistance by commercializing with a styrene-based resin containing polyester and acrylic acid. However, there is a disadvantage in that the physical properties are greatly reduced after molding and processing due to the influence of the residue remaining at high temperature.

As described above, there are many known prior arts for alloying polyester resins and styrene-based resins. However, prior arts attempting to commercialize by applying styrene-based polymers containing epoxy groups are difficult to find.

Accordingly, the present inventors have made an effort to solve the conventional problems, and as a result, by adding a polyamide resin to a base resin blended with a styrene-based polymer containing an epoxy group in a polyester resin, impact resistance is greatly improved and impact strength even when molded at a high temperature. It is to develop a thermoplastic resin composition which does not fall.

An object of the present invention is to provide a thermoplastic resin composition with improved impact resistance.

Another object of the present invention is to provide a thermoplastic resin composition which is excellent in impact resistance and can be applied as a structural material.

Still another object of the present invention is to provide a thermoplastic resin composition which is excellent in impact resistance and suitable as a packaging material for electrical and electronic products.

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

Summary of the Invention

The present invention provides a thermoplastic resin composition having improved impact resistance. The thermoplastic resin composition is a styrene polymer containing an epoxy group consisting of 5 to 100% by weight of (A) (A ₁ ) epoxy group-containing vinyl copolymer and 0 to 95% by weight of (A ₂ ) rubber-reinforced styrene-based copolymer resin 30 to 99 Parts by weight; (B) 1 to 70 parts by weight of polyester resin; 0.1-5 weight part of (C) polyamide resins with respect to 100 weight part of said (A) + (B); (D) 1 to 30 parts by weight of bromine-containing flame retardant; And (E) 0.1 to 10 parts by weight of a flame retardant aid.

The epoxy group-containing vinyl copolymer (A ₁ ) is a copolymer of a monomer mixture composed of 0.001 to 5 mol% of an unsaturated epoxy compound containing (A ₁₁ ) epoxy group and 95 to 99.999 mol% of (A ₁₂ ) vinyl compound.

The rubber-reinforced styrenic copolymer resin (A ₂ ) is composed of 20 to 100% by weight of the (A ₂₁ ) graft copolymer resin and 0 to 80% by weight of the (A ₂₂ ) copolymer resin.

Inorganic particles may be mixed in the polyester resin (B).

It is preferable that the said polyamide resin (C) is an aliphatic or aromatic-aliphatic polyamide resin.

It is preferable that the said flame retardant adjuvant (E) is antimony oxide.

Hereinafter, specific contents of the present invention will be described in detail below.

Detailed Description of the Invention

(A) Styrene-Based Polymer Containing Epoxy Group

The styrene-based polymer that contains an epoxy group used in the present invention (A) is composed of (A ₁₎ epoxy group-containing vinyl copolymer, and (A ₂₎ rubber-reinforced styrene-based copolymer resin. Preferably, (A ₁₎ made of an epoxy group containing 5-100% by weight of a vinyl copolymer and (A ₂₎ in the rubber-reinforced styrene-based copolymer resin 0~95% by weight. Styrene-based polymer (A) containing the epoxy group is composed of 30 to 99 parts by weight, preferably 50 to 90 parts by weight of the base resin together with the polyester resin (B).

(A ₁ ) Epoxy group-containing vinyl copolymer

The vinyl copolymer (A ₁ ) containing an epoxy group used in the present invention polymerizes a monomer mixture composed of an unsaturated epoxy compound (A ₁₁ ) and a vinyl compound (A ₁₂ ) containing an epoxy group to form an unsaturated epoxy group in the vinyl copolymer. It is a resin prepared by polymerization to be present. Preferably, the monomer mixture is composed of 0.001 to 5.0 mol% of unsaturated epoxy compound (A ₁₁ ) containing epoxy group and 95 to 99.999 mol% of vinyl compound (A ₁₂ ), more preferably unsaturated containing epoxy group. an epoxy compound (a ₁₁₎ 0.05~5.0 mol% and a vinyl-based compound (a ₁₂₎ comprises a 95~99.95 mol%.

(A ₁₁ ) unsaturated epoxy compound

The unsaturated epoxy compound used for the epoxy group-containing vinyl copolymer (A ₁ ) is represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₆ , R ₇ and R ₈ are each H, C ₁ -C ₁₂ alkyl or unsaturated alkyl group, or C ₆ -C ₁₄ aryl group or C ₁ An aryl group substituted with -C ₁₂ alkyl, an unsaturated alkyl having a substituted aryl group, X is 0 or 1, Y is an ether group (-O-), a carboxyl group (-O- [C = O]-,-[O = C] -O-), C ₁ -C ₁₂ alkylene, C ₆ -C ₁₄ arylene group or C ₁ -C ₁₂ alkyl substituted arylene group, wherein Y is ether (-O-) or carbon In the case of a compound (-O- [C = O]-,-[O = C] -O-), R ₄ and R ₅ are each C _{1 to} C ₁₂ alkylene or C _{6 to} C ₁₄ arylene group Or an arylene group substituted with C _{1 to} C ₁₂ alkyl, wherein Y is C ₁ to C ₁₂ alkylene, or C _{6 to} C ₁₄ arylene group or C _{1 to} C ₁₂ alkyl substituted arylene group. , Y represents (R ₄ -YR ₅ ).

Representative examples of the unsaturated epoxy compound (A ₁₁ ) are epoxy alkyl acrylate, allyl glycidyl ester, aryl glycidyl ester, glycidyl methacrylate, glycidyl acrylate, butadiene monooxide, vinyl glycidyl Dill ethers, glycidyl itaconate, and the like, but are not necessarily limited thereto. The unsaturated epoxy compounds may be used alone or in combination of two or more thereof.

Preferably, the unsaturated epoxy compound (A ₁₁ ) is added at 0.001 to 5 mol% in the form of a copolymerized monomer, more preferably at 0.05 to 5.0 mol%. When the content of the unsaturated epoxy compound (A ₁₁ ) is less than 0.001 mol%, the effect of improving impact strength is small, and when it exceeds 5 mol%, gelation may occur during extrusion, which is not preferable.

(A ₁₂ ) Vinyl Compound

The vinyl compound (A ₁₂ ) used in the epoxy copolymer-containing vinyl copolymer (A ₁ ) may include an aromatic vinyl monomer and optionally further include a monomer copolymerizable with the aromatic vinyl monomer. Preferably, the vinyl compound (A ₁₂ ) comprises 40 to 100% by weight of an aromatic vinyl monomer and 0 to 60% by weight of a monomer copolymerizable with the aromatic vinyl monomer.

The aromatic vinyl monomer is represented by the following formula (2).

[Formula 2]

In Formula 2, R ₉ is hydrogen or a methyl group, R ₁₀ is a phenyl group, halophenyl group, alkylphenyl group, alkylhalophenyl group, naphthalene group or alkylnaphthalene group, preferably a phenyl group. The halophenyl group is substituted with one or two halogen compounds in the phenyl group, the alkylphenyl group is substituted with one or two alkyl groups in the phenyl group, and the alkylhalophenyl group is an alkyl group containing a halogen compound or a halogen and an alkyl group together with the phenyl group. The substituted alkylnaphthalene group refers to a substituted one to four alkyl groups in the naphthalene group. R ₁₁ is hydrogen or a methyl group.

Specific examples of the aromatic vinyl monomer include styrene, para t-butyl styrene, α-methyl styrene, β-methyl styrene, p-methyl styrene, ethyl styrene, vinyl xylene, monochloro styrene, dichloro styrene, dibromostyrene, Vinylnaphthalene and the like, but are not necessarily limited thereto. These can be used individually or in mixture of 2 or more types. Of these, styrene is preferable.

One or more monomers copolymerizable with the aromatic vinyl monomer may be introduced, and as the monomer to be introduced, an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like is preferable, but is not limited thereto. It doesn't happen. Preferred of these is acrylonitrile. The monomer copolymerizable with the aromatic vinyl monomer may be added in an amount of 0 to 60 wt% based on the total weight of the vinyl compound (A ₁₂ ).

The vinyl compound (A ₁₂ ) used in the present invention may optionally contain acrylic acid, methacrylic acid and dicarboxylic acid; Methyl methacrylate, C _{1 to} C ₄ alkyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2 Phenoxyethyl acrylate and 2-phenoxyethyl methacrylate; N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexyl maleimide; Maleic acid, fumaric acid, itaconic acid and their anhydrides; Nitrogen-functional, such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinyl caprolactam, vinylcarbazole, vinylaniline, acrylamide and methacrylamide A monomer or the like may be added to impart properties such as processability and heat resistance to the copolymer. The monomer for imparting the processability and heat resistance may be used in the range of 0 to 30% by weight based on the total weight of the vinyl compound (A ₁₂ ).

Preferably, the vinyl compound (A ₁₂ ) is added in the form of a copolymerized monomer at 95 to 99.999 mol%, more preferably at 95 to 99.95 mol%.

(A ₂ ) Rubber reinforced styrene copolymer resin

The rubber-reinforced styrenic copolymer resin (A ₂ ) used in the present invention is a polymer in which a rubbery polymer is dispersed and present in the form of particles in a matrix (continuous phase) made of an aromatic vinyl polymer.

The rubber-reinforced styrene copolymer resin (A ₂ ) is polymerized by adding an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer selectively to the rubbery polymer.

Such rubber-reinforced styrenic copolymer resin (A ₂ ) can be produced by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization. In addition, the graft copolymer resin and the copolymer resin may be produced by mixing and extruding. In the case of the bulk polymerization, the rubber-reinforced styrene-based copolymer resin (A ₂ ) is produced by only one step reaction without producing graft copolymer resin and the copolymer resin separately. ₂ ) Among the components, the rubber content is most preferably 5 to 35% by weight.

The rubber-reinforced styrenic copolymer resin (A ₂ ) used in the present invention may be prepared by using graft copolymer resin alone or in combination with graft copolymer resin and copolymer resin, and blended in consideration of their compatibility. It is desirable to.

(A ₂₁ ) graft copolymer resin

The graft copolymer resin (A ₂₁ ) used in the present invention is obtained by graft copolymerization of a rubbery polymer, an aromatic vinyl monomer, a monomer copolymerizable with an aromatic vinyl monomer, and a monomer that optionally provides workability and heat resistance. .

Examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and saturated rubber, isoprene rubber, chloroprene rubber, and poly-hydrogenated diene rubber. Acrylic rubber, such as butyl acrylic acid, and ethylene-propylene-diene monomer terpolymer (EPDM), etc. are mentioned, It is not necessarily limited to this. Among these, especially diene rubber is preferable and butadiene rubber is more preferable. The content of the rubbery polymer is preferably 5 to 65 parts by weight, more preferably 30 to 65 parts by weight of the total weight of the graft copolymer resin (A ₂₁ ). The average size of the rubber particles is preferably in the range of 0.1 to 4 ㎛ considering the impact strength and appearance.

Aromatic vinyl monomers in the monomer mixture capable of graft copolymerization with the rubbery polymer include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, and monochlorostyrene. , Dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like may be used, but are not necessarily limited thereto. Of these, styrene is most preferred. The aromatic vinyl monomer is graft copolymerized using 20 to 95 parts by weight, preferably 20 to 60 parts by weight of the total weight of the graft copolymer resin (A ₂₁ ).

The graft copolymer resin (A ₂₁ ) may be introduced at least one monomer copolymerizable with an aromatic vinyl monomer. As the monomer which can be introduced, unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile and ethacrylonitrile are preferable, and these may be used alone or in combination of two or more thereof. The monomer is copolymerized using 0.1 to 20 parts by weight, preferably 10 to 18 parts by weight of the total weight of the graft copolymer resin (A ₂₁ ).

Examples of the monomer for imparting the processability and heat resistance include acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide. The content of the added monomer is preferably 0 to 40 parts by weight, more preferably 0.0001 to 15 parts by weight based on the total weight of the graft copolymer resin (A ₂₁ ).

(A ₂₂ ) Copolymer Resin

The copolymer resin (A ₂₂ ) used in the present invention is prepared according to the monomer ratio and compatibility of the components of the graft copolymer resin (A ₂₁ ) excluding rubber, and copolymerized with an aromatic vinyl monomer and the aromatic vinyl monomer. Possible monomers and optionally monomers which impart processability and heat resistance are added and copolymerized.

The aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene And mixtures thereof, and the like, but are not necessarily limited thereto. Of these, styrene is most preferred. In the present invention, the aromatic vinyl monomer is used in an amount of 60 to 95 parts by weight, preferably 65 to 90 parts by weight, based on the total weight of the copolymer resin (A ₂₂ ).

As an example of the monomer copolymerizable with the aromatic vinyl monomer, an unsaturated nitrile compound such as acrylonitrile, methacrylonitrile and ethacrylonitrile is preferable, and these may be used alone or in combination of two or more thereof. The content of the monomer copolymerizable with the aromatic vinyl monomer is preferably 5 to 40 parts by weight, more preferably 10 to 35 parts by weight of the total weight of the copolymer resin (A ₂₂ ).

Acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, etc. are mentioned as a monomer for providing the said processability and heat resistance. The content of the monomer to be added during the copolymerization in order to impart processability and heat resistance is preferred that the copolymer resin (A ₂₂₎ of the total weight of 0 to 40 parts by weight, more preferably 0.0001 to 15 wt denied.

Examples of the rubber-reinforced styrenic copolymer resin (A ₂ ) used in the present invention include acrylonitrile-butadiene-styrene copolymer resins (ABS resins), acrylonitrile-ethylenepropylene rubber-styrene copolymer resins (AES resins), Acrylonitrile-acryl rubber-styrene copolymer resin (AAS resin) and the like, but are not necessarily limited thereto.

Roneun the rubber-reinforced styrene-based copolymer resin (A _2), it is preferable to use a mixture of the graft copolymer resin (A ₂₁₎ 20~100% by weight of the copolymer resin (A ₂₂₎ 0~80% by weight.

(B) polyester resin

The polyester resin (B) used for this invention is a polyester resin or its copolymer whose intrinsic viscosity is 0.3-1.0 g / dL. If the intrinsic viscosity of the polyester resin is less than 0.3, the impact strength is low, and if it exceeds 1.0, the fluidity is greatly reduced, making it difficult to manufacture the thermoplastic resin composition according to the present invention.

The polyester resin (B) is generally a terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5 -Naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6 -Naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, Dimethyl Terephthalate (DMT), Dimethyl Isophthalate, which is an aromatic dicarboxylate substituted with a dimethyl group. Alkyl esters of naphthalene dicarboxylic acid or dimethyl-1,2-naphthalate, dimethyl-1,5-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1,7-naphthalate, dimethyl-1, 8-naphthalate, dimethyl-2,3-naphthalate, dimethyl-2,6-naphthalate, dimethyl- Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, having 2 to 12 carbon atoms as diols, such as 2,7-naphthalate or mixtures thereof, 2,2-dimethyl-1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-cyclohexane dimethanol, 1, 4-cyclohexane dimethanol or a mixture thereof may be obtained by polycondensation, which can be easily carried out by those skilled in the art.

In the polyester resin (B), inorganic particles may be mixed in a conventional manner depending on the purpose. Examples of the inorganic particles may include titanium dioxide (TiO ₂ ), silicon dioxide (SiO ₂ ), aluminum hydroxide (Al (OH) ₂ ), and the like, but are not limited thereto. These can be used individually or in mixture of 2 or more types.

In the present invention, the polyester resin (B) forms a basic resin together with the styrene-based polymer (A) containing an epoxy group, and is used in an amount of 1 to 70 parts by weight, preferably 10 to 50 parts by weight. When the content of the polyester resin (B) is less than 1 part by weight or exceeds 70 parts by weight, the impact strength is lowered and is not suitable for the present invention.

(C) polyamide resin

In the present invention, all conventional polyamide resins can be used, but more preferably, aliphatic or aromatic-aliphatic polyamide resins are used.

As the aliphatic polyamide resin, nylon 6, nylon 66, nylon 46, nylon 12 and the like and mixtures thereof may be freely used, but are not necessarily limited thereto. The aromatic-aliphatic polyamide resin is a polyamide resin having a partially aromatic polyamide resin such as nylon 6T, nylon 9T, etc., which may be implemented by introducing terephthalic acid during polymerization.

In order to improve impact resistance, it is more preferable to apply a higher melting temperature among polyamide resins. In the case of each polyamide resin, there is no particular limitation on use, and polyamide resin having a number average molecular weight of 5,000 to 150,000 g / mol that can be used for injection is more preferable. When the number average molecular weight of the polyamide resin is out of the above range, it is difficult to prepare the thermoplastic resin composition according to the present invention.

The polyamide resin (C) is used in an amount of 0.1 to 5 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the base resin (A) + (B). When the polyamide resin (C) is used in less than 0.1 parts by weight, it is difficult to obtain a synergistic effect of impact resistance, and when used in excess of 5 parts by weight, the impact strength may be rather reduced, which is not preferable.

(D) bromine-containing flame retardants

The bromine-containing flame retardant (D) used in the present invention is a compound having a bromine content of 40 to 87% by weight in the flame retardant.

Examples of the bromine-containing flame retardant (D) are tetrabromo Bisphenol A, Decabromo Diphenyl Oxide, Decabrominated Diphenyl Ethane, 1,2- Bis (tribromophenyl) ethane (1,2-Bis (tribromophenyl) ethane), brominated epoxy oligomer with molecular weight of 600-8,000, octabromo trimethylphenyl Indane, bis (2 Bis (2,3-dibromopropyl) ether, Tris (tribromophenyl) triazine, Brominated Aliphatic or Aromatic Hydrocarbon Etc. may be used, but is not necessarily limited thereto. These may be used alone or in mixture of two or more thereof.

The bromine-containing flame retardant (D) is used in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the base resin (A) + (B). When the content of the bromine-containing flame retardant (D) is less than 1 part by weight, it is difficult to obtain a desired flame retardancy, and when it exceeds 30 parts by weight, physical properties may be lowered, which is not preferable.

(E) flame retardant supplements

The flame retardant aid (E) used in the present invention includes antimony and is a compound having an antimony content of 75 to 87% by weight in the flame retardant. Preferably the flame retardant aid (E) is antimony oxide, antimony trioxide, antimony pentoxide and mixtures thereof may be used, but is not necessarily limited thereto.

In the case of antimony trioxide, 50% particle size is appropriately 0.01 to 6 mu m, more preferably 0.02 to 3.0 mu m. In the case of antimony pentoxide, the particle size is appropriately 0.01 to 1.0 mu m, more preferably 0.02 to 0.5 mu m. When the 50% particle size of the antimony trioxide is outside the range of 0.01 to 6 μm, or the particle size of the antimony pentoxide is outside the range of 0.01 to 1.0 μm, mechanical strength is lowered due to the dispersibility, which is not preferable.

The flame retardant aid (E) is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the base resin (A) + (B). If the content of the flame retardant (E) is less than 0.1 parts by weight, it is difficult to obtain a flame retardancy improving effect, and when it exceeds 10 parts by weight, the physical properties may be lowered, which is not preferable.

The thermoplastic resin composition according to the present invention may further include an additive as necessary. The additive may be a heat stabilizer, dyes, pigments, lubricants, mold release agents, dispersants, anti-dropping agents, weather stabilizers, inorganic fillers, inorganic fibers, and the like, but is not limited thereto. These may be applied alone or in mixture of two or more. The additive is preferably used in an amount of 30 parts by weight or less, more preferably 0.0001 to 30 parts by weight based on 100 parts by weight of the base resin (A) + (B).

The thermoplastic resin composition of the present invention can be produced by a general method. For example, the above-described components and other additives may be mixed at the same time, and then melt-extruded in an extruder to produce pellets, or sheets, films, fibers, or the like.

Since the thermoplastic resin composition of the present invention has excellent impact resistance compared to the flame retardant resin generally used, it can be used for molding various products. In particular, the present invention can be widely applied to exterior materials for electrical and electronic products, computer housings or other office equipment housings, structural materials and the like.

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

The specification of each component used in the Example and comparative example of this invention is as follows.

(A) Styrene-Based Polymer Containing Epoxy Group

(A ₁ ) Epoxy group-containing vinyl copolymer (GMA 0.7 mol%-SAN)

Azobisisobuty, an additive necessary for a mixture of 100 parts by weight of a monomer mixture composed of 0.7 mol% of glycidyl methacrylate, 99.3 mol% of a vinyl compound composed of 70 parts by weight of styrene, and 30 parts by weight of acrylonitrile and 120 parts by weight of deionized water. After adding 0.2 parts by weight of ronitrile, 0.4 parts by weight of tricalcium phosphate, and 0.2 parts by weight of mercaptan-based chain transfer agent, the temperature was raised from room temperature to 80 ° C. for 60 minutes, and then maintained at this temperature for 180 minutes to provide styrene-acrylonitrile containing epoxy. Copolymer resin (GMA-SAN) was prepared. It was washed with water, dehydrated and dried to prepare a powdered epoxy-containing styrene-acrylonitrile copolymer resin (GMA-SAN).

(A ₂ ) Rubber reinforced styrene copolymer resin

(A ₂₁ ) graft copolymer resin

In a mixture of 50 parts by weight of solid butadiene rubber latex, 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water, 1.0 part by weight of potassium oleate, 0.4 part by weight of cumene hydroperoxide, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of pyrophosphate sodium salt were added to maintain the reaction at 75 ° C. for 5 hours to obtain a graft copolymer (g- ABS) latex was prepared. 0.4 parts by weight of sulfuric acid was added to the resulting resin composition solids and solidified to prepare a graft copolymer resin (g-ABS) in powder form.

(A ₂₂ ) Copolymer Resin

Room temperature was added by adding 75 parts by weight of styrene, 25 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-based chain transfer agent. After raising the temperature to 80 ℃ for 90 minutes, and maintained at this temperature to 180 minutes to prepare a styrene / acrylonitrile copolymer resin (SAN). This was washed with water, dehydrated and dried to prepare a powdered styrene / acrylonitrile copolymer resin (SAN).

(B) polyester

Anychem's A1100 product was used as the polyester resin having an intrinsic viscosity of 0.76 g / dL.

(C) polyamide resin

Zytel 42A, Dupont, USA, was used as nylon 66 having a number average molecular weight of 20,000 to 30,000 g / mol.

(D) bromine-containing flame retardants

FR-245 was used as a flame retardant having a bromine content of 40 to 87 wt% in the flame retardant.

(E) flame retardant supplements

As a compound having an antimony content in the flame retardant aid of 75 to 87% by weight, ANTIS-W of Ilsan Antimony Co., Ltd., Korea was used.

(F) heat stabilizer

SONGSTAB TM-661 (POLY (DIBUTYL-TIN-MALEATE): ZEOLITE (CaO · Na ₂ O · Al ₂ O ₃ · SiO ₃ ) = 50: 50) manufactured by Songwon Industrial Co., Ltd. was used.

Examples 1-4 and Comparative Examples 1-2

Each of the components and additives were added in the amounts as listed in Table 1 below, followed by uniform mixing for 3 to 10 minutes in a Henschel mixer. The mixture was extruded in a conventional twin screw extruder at an extrusion temperature of 180 to 250 ° C., a screw rotational speed of 150 to 300 rpm, and a composition feed rate of 30 to 60 Kg / hr to prepare pellets. The prepared pellets were dried at 90 ° C. for 4 hours and then injected into a 6 Oz injection machine under conditions of a molding temperature of 250 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a specimen. After the prepared specimens were allowed to stand at 23 ° C. and 50% RH for 40 hours, the Izod impact strength (kgf · cm / cm) was measured at 1/4 ”and 1/8” thickness according to ASTM D256. It is shown in Table 1 below.

As shown in Table 1, Comparative Example 1 without the polyamide resin (C) was found to be low impact strength at 1/4 "and 1/8" thickness. In addition, Comparative Example 2 including the polyamide resin (C) outside the scope of the present invention was also confirmed that the impact strength is lowered. In contrast, Examples 1 to 4 containing the polyamide resin (C) within the scope of the present invention was found to be excellent in impact strength at both 1/4 "and 1/8" thickness, especially the base resin (A) In Examples 2 and 3 including 1 to 4 parts by weight of polyamide resin based on 100 parts by weight of + (B), it was confirmed that the impact strength was improved.

The present invention, by adding a polyamide resin to the base resin of the styrene-based polymer containing a polyester resin and an epoxy group, the impact resistance is greatly improved, and has an effect of providing a thermoplastic resin composition suitable as an exterior material or a structural material of electrical and electronic products.

Simple modifications and variations of the present invention can be easily made 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 (15)

(A) (A ₁₎ epoxy group-containing vinyl copolymer and 5-100% (A ₂₎ 30-99 parts by weight of the styrene-based polymer include a rubber-reinforced styrene-based copolymer resin epoxy group consisting of 0-95% by weight; (B) 1 to 70 parts by weight of polyester resin; Based on 100 parts by weight of (A) + (B), (C) 0.1 to 5 parts by weight of polyamide resin; (D) 1 to 30 parts by weight of bromine-containing flame retardant; And (E) 0.1 to 10 parts by weight of flame retardant auxiliary; The thermoplastic resin composition with improved impact resistance, characterized in that consisting of. According to claim 1, wherein the epoxy-containing vinyl copolymer (A ₁ ) is a monomer consisting of 0.001 to 5 mol% of unsaturated epoxy compound containing (A ₁₁ ) epoxy group and 95 to 99.999 mol% of (A ₁₂ ) vinyl compound A thermoplastic resin composition characterized by copolymerizing a mixture. The thermoplastic resin composition of claim 2, wherein the unsaturated epoxy compound (A ₁₁ ) is represented by the following Formula 1. [Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₆ , R ₇ and R ₈ are each H, a C _{1 to} C ₁₂ alkyl group or an unsaturated alkyl group, or a C _{6 to} C ₁₄ aryl group or C ₁ to An aryl group substituted with C ₁₂ alkyl, an unsaturated alkyl having a substituted aryl group, X is 0 or 1, Y is an ether group (-O-), a carboxyl group (-O- [C = O]-,-[O = C] -O-), C ₁ -C ₁₂ alkylene, C ₆ -C ₁₄ arylene group or C ₁ -C ₁₂ alkyl substituted arylene group, wherein Y is ether (-O-) or carboxyl When (-O- [C = O]-,-[O = C] -O-), R ₄ and R ₅ are each C _{1 to} C ₁₂ alkylene, or C _{6 to} C ₁₄ arylene group or When C _{1 to} C ₁₂ alkyl has a substituted arylene group, and Y is C ₁ to C ₁₂ alkylene, C _{6 to} C ₁₄ arylene group or C _{1 to} C ₁₂ alkyl substituted arylene group, Y represents (R ₄ -YR ₅ ). The method of claim 3, wherein the unsaturated epoxy compound (A ₁₁ ) is an epoxy alkyl acrylate, allyl glycidyl ester, aryl glycidyl ester, glycidyl methacrylate, glycidyl acrylate, butadiene monooxide , Vinyl glycidyl ether, glycidyl itaconate, and mixtures thereof. The thermoplastic resin composition according to claim 2, wherein the vinyl compound (A ₁₂ ) comprises 40 to 100% by weight of an aromatic vinyl monomer and 0 to 60% by weight of a monomer copolymerizable with the aromatic vinyl monomer. The thermoplastic resin composition of claim 5, wherein the monomer copolymerizable with the aromatic vinyl monomer is an unsaturated nitrile monomer. The rubber-reinforced styrene-based copolymer resin (A ₂ ) is made of 20 to 100% by weight of the (A ₂₁ ) graft copolymer resin and 0 to 80% by weight of the (A ₂₂ ) copolymer resin. Thermoplastic resin composition. According to claim 7, wherein the graft copolymer resin (A ₂₁ ) is 5 to 65 parts by weight of rubbery polymer, 20 to 95 parts by weight of aromatic vinyl monomer and 0.1 to 20 parts by weight of monomer copolymerizable with the aromatic vinyl monomer The copolymer resin (A ₂₂ ) is graft copolymerized, the thermoplastic resin composition characterized in that the copolymerization of 60 to 95 parts by weight of the aromatic vinyl monomer and 5 to 40 parts by weight of monomer copolymerizable with the aromatic vinyl monomer. The thermoplastic resin composition according to claim 1, wherein the polyester resin (B) is a mixture of inorganic particles. The thermoplastic resin composition according to claim 1, wherein the polyamide resin (C) is an aliphatic or aromatic-aliphatic polyamide resin. The thermoplastic resin composition according to claim 10, wherein the polyamide resin (C) is selected from the group consisting of nylon 6, nylon 66, nylon 46, nylon 12, nylon 6T, nylon 9T, and mixtures thereof. The bromine-containing flame retardant (D) is tetrabromo bisphenol A, decabromo diphenyloxide, decabrominated diphenyl ethane, 1,2-bis (tribromophenyl) ethane, molecular weight From 600 to 8000 brominated epoxy oligomers, octabromo trimethylphenyl indane, bis (2,3-dibromopropyl) ethers, tris (tribromophenyl) triazines, brominated aliphatic or aromatic hydrocarbons and mixtures thereof Thermoplastic resin composition, characterized in that selected. The thermoplastic resin composition according to claim 1, wherein the flame retardant aid (E) is antimony oxide. The thermoplastic resin composition according to claim 13, wherein the antimony trioxide has a 50% particle size of 0.01 to 6 mu m, and the antimony pentoxide has a particle size of 0.01 to 1.0 mu m. The method of claim 1, wherein the resin composition further comprises an additive selected from the group consisting of heat stabilizers, dyes, pigments, lubricants, mold release agents, dispersants, anti-drip agents, weather stabilizers, inorganic fillers, inorganic fibers and mixtures thereof. Thermoplastic resin composition.