KR100830418B1 - Thermoplastic resin composition having improved impact strength - Google Patents

Abstract

A thermoplastic resin composition suitable for the external material of an electrical product or an electronic product is provided to improve impact resistance remarkably. A thermoplastic resin composition comprises 30-99 parts by weight of a styrene-based polymer containing an epoxy group which comprises 5-100 wt% of a vinyl copolymer containing an epoxy group, and 0-95 wt% of a rubber reinforced styrene-based copolymer resin; and 1-70 parts by weight of a polyester resin. Preferably the vinyl copolymer containing an epoxy group is prepared by copolymerizing 0.001-5.0 mol% of an unsaturated epoxy-based compound containing an epoxy group and 95-99.999 mol% of a vinyl-based compound; and the styrene-based polymer contains 0.001-5.0 mo% of an epoxy group.

Description

Thermoplastic Resin Composition Having Improved Impact Strength

Field of invention

The present invention relates to a thermoplastic flame retardant resin excellent in impact resistance. More specifically, the present invention relates to a thermoplastic resin composition in which an styrene-based polymer containing an epoxy group and a polyester resin are alloyed to have a significantly improved impact resistance.

Background of the Invention

In general, styrene resins are excellent in transparency, thermal stability and mechanical properties. Styrene-based resin is used as styrene-based copolymer alone or rubber-modified styrene-based copolymer and used as resin such as high impact polystyrene (HIPS), acrylonitrile, rubber and ABS copolymerized with styrene. have. In particular, styrene-based thermoplastic resins are widely used as exterior materials for electrical and electronic products because of their excellent physical properties.

In order to improve the impact resistance of the styrene resin, it is common to adjust the content or size of the rubber phase applied to the inside of the styrene resin and to improve dispersibility.

In order to express the excellent impact resistance properties of the styrene resin, the rubber-like component to be added is determined according to the impact strength required for the styrene resin, and 8 to 20 depending on the shape and size of the rubber phase in the styrene polymer. It will have a content of about%.

Since polyester has a short molecular chain length and is difficult to bend, it has good rigidity, electrical properties, weather resistance, and heat resistance, and has a small drop in tensile strength even when exposed at high temperatures for a long time. 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 particular, the impact resistance is low, it is difficult to use as a structural material. In order to use the polyester resin as a structural material, a reinforcing agent such as glass fiber had to be included. 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 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 in polyester. The technique of mix | blending the acrylonitrile- ethylene propylene rubber styrene copolymer (AES) resin which is a graft copolymer obtained by grafting is disclosed. However, the above technique is effective only when the content of polyester 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 when the injection or extrusion process at a high temperature, the compatibility between ABS and PET is lowered and the viscosity of each phase is lowered, so that phase separation is promoted, and a difference in impact resistance in a molding direction and a right angle direction of molding is very large. . In addition, when the resin stays in the molding machine for a long time there is a problem that the difference in physical properties due to the phase change 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.

US patent application Ser. No. 07 / 500,462 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 the adhesiveness in the laminated film, and when molding a large injection molding by injection molding, polyester and g-ABS or MBS agglomerates with each other to show the instability of the physical properties, especially low polyester content In this case, there is a drawback that the effect is large.

U.S. Patent Application No. 06 / 354,468 discloses a technique for commercializing a styrene-based resin including polyester and acrylic acid to improve heat resistance. However, due to the influence of the acid remaining at a high temperature, there is a disadvantage in that the physical properties are greatly reduced after molding and processing.

As described above, the conventional technology uses a styrene resin to improve the disadvantages of the low impact resistance of the polyester resin, but it is difficult to find a prior art that attempts to commercialize by applying a styrene resin containing an epoxy group.

Accordingly, the present inventors have studied and researched to solve the conventional problems. As a result, in order to improve the impact strength of the styrene resin, the present inventors have proposed a method of alloying a polyester resin having a low impact strength. In particular, the use of a styrene resin having an epoxy group introduced therein with polyester has led to the development of a thermoplastic resin composition with markedly improved impact resistance.

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 excellent in impact resistance and suitable for exterior materials of electric and electronic products.

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

Summary of the Invention

The improved impact resistance of thermoplastic resin composition of the present invention (A) (A ₁₎ epoxy group-containing vinyl copolymer contains 5 to 100% by weight of an epoxy group consisting of and (A ₂₎ rubber-reinforced styrene-based copolymer resin 0~95% by weight 30 to 99 parts by weight of styrene polymer; And (B) 1 to 70 parts by weight of polyester resin.

The epoxy group-containing vinyl copolymer (A ₁ ) is a copolymer of a monomer mixture composed of 0.001 to 5.0 mol% of an unsaturated epoxy compound (A ₁₁ ) containing an epoxy group and 99.999 to 95 mol% of a vinyl compound (A ₁₂ ). .

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.

The polyester resin (B) may be 0.3 to 1.0 g / dL intrinsic viscosity.

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

The resin composition of the present invention may further include an additive made of a flame retardant, an impact modifier, a heat stabilizer, a dye, a pigment, a lubricant, a mold release agent, a dispersant, an antidropping agent, a weather stabilizer, an inorganic filler, an inorganic fiber, and a mixture thereof.

Detailed Description of the Invention

(A) Styrene-Based Polymer Containing Epoxy Group

Styrene-based polymer (A) containing an epoxy group in the present invention comprises (A ₁ ) 5 to 100% by weight of an epoxy group-containing vinyl copolymer and (A ₂ ) rubber-reinforced styrene-based copolymer resin 0 to 95% by weight. In the styrene-based polymer (A) containing the epoxy group, it is preferable that the epoxy group contains 0.001 to 5.0 mol% epoxy group.

(A ₁ ) Epoxy group-containing vinyl copolymer

The vinyl copolymer including the epoxy group of the present invention is prepared by polymerizing a monomer mixture composed of an unsaturated epoxy compound (A ₁₁ ) and a vinyl compound (A ₁₂ ) containing an epoxy group so that the unsaturated epoxy group is present in the styrene copolymer. Resin. The monomer mixture is preferably composed of 0.001 to 5.0 mol% of an unsaturated epoxy compound (A ₁₁ ) containing an epoxy group and 99.999 to 95 mol% of a vinyl compound (A ₁₂ ).

(A ₁₁ ) Epoxy Compound

The epoxy compound used for the styrene resin containing an epoxy group is represented by following formula (1).

[Formula 1]

In the above, R ₁ , R ₂ , R ₃ , R ₆ , R ₇ and R ₈ are each H, C ₁ -C ₁₂ alkyl group or unsaturated alkyl group, C ₆ -C ₁₄ aryl group, alkyl substituted aryl group, unsaturated alkyl a substituted aryl group, and, Y is an ether group (-O-), carboxyl group (-O- [C = O] - , - [O = C] -O-), alkylene group of C ₁ ~C _12, C ₆ ~ When C ₁₄ arylene group or alkyl is substituted arylene group, and Y is ether (-O-) or carboxyl (-O- [C = O]-,-[O = C] -O-), R ₄ and R ₅ each have C _{1 to} C ₁₂ alkylene, C _{6 to} C ₁₄ arylene group or an alkyl substituted arylene group, and Y is C ₁ to C ₁₂ alkylene, or C ₆ When an arylene group of -C ₁₄ or an alkyl is substituted arylene group, Y represents (R ₄ -YR ₅ ).

Representative examples of the compound include epoxy alkyl acrylate, allyl glycidyl ester, aryl glycidyl ester, glycidyl methacrylate, glycidyl acrylate, butadiene monooxide, vinyl glycidyl ether, glycidyl itaco Nate and the like, but is not necessarily limited thereto. The epoxy compound may be used alone or in combination of two or more thereof.

The above compound is added in an amount of 0.001 to 5 mol% in the form of a copolymerization monomer. If it is less than 0.001 mol%, the impact strength improvement effect is small, and if it exceeds 5 mol%, there is a problem that a gelation phenomenon occurs during extrusion.

(A ₁₂ ) Vinyl Compound

The vinyl compound used for the epoxy group containing vinyl copolymer of this invention contains an aromatic vinyl monomer and the monomer copolymerizable with the said aromatic vinyl monomer.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinyl naphthalene. And the like, but are not necessarily limited thereto. Of these, styrene is most preferred. The styrene compounds may be used alone or in combination.

One or more monomers copolymerizable with the aromatic vinyl monomer may be introduced, and as the monomer capable of being introduced, unsaturated nitrile monomers such as acrylonitrile, methacrylonitrile, and ethacrylonitrile are preferred. It is not limited. Preferred is acrylonitrile.

The ratio of the monomer copolymerizable with the aromatic vinyl monomer and the aromatic vinyl monomer is determined according to the ratio and compatibility of the monomer except rubber in the rubber-reinforced styrene-based copolymer resin (A ₂ ). Preferably it is 40-90 weight% of aromatic vinylic monomers, and 10-60 weight% of monomers copolymerizable with the said aromatic vinylic monomer. More preferably, they are 50 to 80 weight% of aromatic vinylic monomers, and 20 to 50 weight% of monomers copolymerizable with the said aromatic vinylic monomers. When the content of the aromatic vinyl monomer is less than 40% by weight, the viscosity is sharply increased to reduce the processability of the final product, when the content is more than 90% by weight is not suitable for the present invention because the strength is lowered.

The vinyl compound (A ₁₂ ) of the present invention may optionally contain acrylic acid and methacrylic acid; Methyl methacrylate, C ₁ -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; 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 workability and heat resistance. The monomer for imparting the processability and heat resistance may be added in 0 to 30% by weight, preferably 1 to 20% by weight, more preferably 2 to 15% by weight of the total vinyl compound (A ₁₂ ). .

(A ₂ ) Rubber reinforced styrene copolymer resin

The rubber-reinforced styrenic copolymer resin according to 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 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 resins can be produced by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, and graft copolymer resins and copolymer resins are usually produced by mixed extrusion. In the case of bulk polymerization, the grafted rubber content from the copolymer resin and a copolymer resin without producing a separate one-step reaction one producing the rubber-reinforced styrene-based resin only processes either case, the final rubber-reinforced styrene-based resin (A ₂₎ component 5-30% by weight is most suitable.

In the present invention, the particle size of the rubber phase to exhibit proper physical properties in the alloying of the rubber-reinforced styrenic copolymer resin and the polyester resin is Z-average of 0.1 to 6.0 μm, and in order to obtain desirable physical properties, the particle size of the rubber phase is Z-average. It is preferable that it is 0.25-3.5 micrometers.

The rubber-reinforced styrenic resins 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 are preferably blended in consideration of their compatibility.

(A ₂₁ ) graft copolymer resin

The graft copolymer resin (A ₂₁ ) of 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 selectively gives workability and heat resistance.

Examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), saturated rubbers hydrogenated with the diene rubber, isoprene rubber, polybutylacrylic acid, and the like. And acrylic rubbers and ethylene-propylene-diene monomer terpolymers (EPDM). Among these, especially diene rubber is preferable and butadiene rubber is more preferable. The content of the rubbery polymer is suitably 5 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 ㎛ in consideration of impact strength and appearance.

The aromatic vinyl monomer in the graft copolymerizable monomer mixture may include styrene, α-methylstyrene, β-methyl styrene, p-methyl styrene, para t-butyl styrene, ethyl styrene, vinyl xylene, monochloro styrene, dichloro styrene, Dibromostyrene, vinyl naphthalene, or the like may be used, but is not necessarily limited thereto. Of these, styrene is most preferred. The aromatic vinyl monomer is subjected to graft copolymerization using 35 to 95 parts by weight of the total weight of the graft copolymer resin (A ₂₁ ).

The graft copolymer resin (A ₂₁ ) of the present invention can introduce at least one monomer copolymerizable with an aromatic vinyl monomer. As the monomer to be introduced, vinyl cyanide such as acrylonitrile and unsaturated nitrile based compounds such as ethacrylonitrile and methacrylonitrile are preferable, and may be used alone or in combination of two or more thereof. The monomer is copolymerized using 1 to 20 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 0 to 15 parts by weight of the total weight of the graft copolymer resin (A ₂₁ ).

(A ₂₂ ) Copolymer Resin

The copolymer resin of the present invention is prepared according to the monomer ratio and compatibility of the components of the graft copolymer resin (A ₂₁ ) except rubber, monomers copolymerizable with aromatic vinyl monomers, aromatic vinyl monomers, and optionally processability And copolymerization by adding a monomer to impart heat resistance.

The aromatic vinyl monomers include styrene, α-methylstyrene, β-methyl styrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinyl naphthalene. And the like, but are not necessarily limited thereto. Of these, styrene is most preferred. In the present invention, the aromatic vinyl monomer is 60 to 90 parts by weight of the total weight of the copolymer resin (A ₂₂ ) to obtain a copolymer resin.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include a vinyl cyanide compound such as acrylonitrile or an unsaturated nitrile compound such as ethacrylonitrile or methacrylonitrile, and may be used alone or in combination of two or more thereof. have. The content of the monomer copolymerizable with the aromatic vinyl monomer is 10 to 40 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 added at the time of copolymerization in order to impart processability and heat resistance is 0 to 30 parts by weight of the total weight of the copolymer resin (A ₂₂ ).

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) etc. are mentioned.

The rubber-reinforced styrenic copolymer resin (A ₂ ) used in the present invention is a mixture of 20 to 100% by weight of the graft copolymer resin (A ₂₁ ) and 0 to 80% by weight of the copolymer resin (A ₂₂ ). use.

(B) polyester

The polyester used in the present invention is a polyester resin having a intrinsic viscosity of 0.3 to 1.0 g / dL or a copolymer thereof. If the intrinsic viscosity is less than 0.3, the impact strength is weak, and if it exceeds 1.0, it is difficult to prepare the resin composition according to the present invention.

The polyester resin is generally terephthalic acid (TPA), isophthalic acid (Isophthalic acid, IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalene dica Leric 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 Carboxylic acid, 2,7-naphthalenedicarboxylic acid, dimethyl terephthalate (DMT), an aromatic dicarboxylate substituted with a dimethyl group, and dimethyl isophthalate (dimethyl isophthalate), naphthalene Alkyl esters of dicarboxylic acids 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, 1,5-pentanediol, 1,6-hexanediol, 1,3 It can be obtained by polycondensation of -cyclohexane dimethanol, 1,4-cyclohexane dimethanol or mixtures thereof and the like, which can be easily carried out by those skilled in the art.

The said polyester can mix | blend an inorganic particle with a conventional method according to a use. As examples of the inorganic particles, titanium dioxide (TiO ₂ ), silicon dioxide (SiO ₂ ), aluminum hydroxide (Al (OH) ₂ ), or the like may be used.

Polyester in the present invention constitutes a base resin, it is used in 1 to 70 parts by weight. If it is out of the above range, the impact strength is lowered and is not suitable for the present invention.

In the present invention, if necessary, at least one additive selected from the group consisting of flame retardants, impact modifiers, heat stabilizers, dyes, pigments, lubricants, mold release agents, dispersants, anti-drip agents, weather stabilizers, inorganic fillers, inorganic fibers, and mixtures thereof is conventional. It may further include a range.

The resin composition of this invention can be manufactured by a well-known method. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.

The composition of the present invention can be used for molding a variety of products, and in particular, it is widely applicable to exterior materials, computer housings or other office equipment housings of electrical and electronic products.

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) Vinyl copolymer containing an epoxy group

(A _1-1 ) Epoxy group-containing vinyl copolymer (GMA 0.3mol%-SAN)

Azobisisobuty, an additive necessary for a mixture of 100 parts by weight of a monomer mixture composed of 9 mol mol of a vinyl compound consisting of 0.3 mol% of glycidyl methacrylate, 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 _1-2 ) Epoxy group-containing vinyl copolymer (GMA 0.5mol%-SAN)

Prepared in the same manner as in (A1-1), except that 100 parts by weight of a monomer mixture composed of 0.5 mol% of glycidyl methacrylate, 70 parts by weight of styrene, and 30 parts by weight of acrylonitrile was used. It was.

(A _1-3 ) Epoxy group-containing vinyl copolymer (GMA 0.7mol%-SAN)

Prepared in the same manner as in (A1-1), except that 0.7 parts by weight of glycidyl methacrylate, 70 parts by weight of styrene and 99.3 mol% of vinyl compound consisting of 30 parts by weight of acrylonitrile were used. It was.

(A _1-4 ) Epoxy group-containing vinyl copolymer (GMA 2.0mol%-SAN)

Prepared in the same manner as in (A1-1), except that 2.0 parts by weight of glycidyl methacrylate, 70 parts by weight of styrene and 30 parts by weight of acrylonitrile were used in an amount of 100 parts by weight of a monomer mixture consisting of 98.0 mol% of a vinyl compound. It was.

(A ₂ ) rubber reinforced styrene 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 a polyester resin having an intrinsic viscosity of 0.8 g / dL.

Example  1 to 8 and Comparative Example  1 to 4

Each of the components was added in the content as shown 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 250 ° C., a screw rotational speed of 250 rpm, and a composition feed rate of 60 kg / hr to prepare pellets. The prepared pellets were injected under conditions of a molding temperature of 250 ° C. and a mold temperature of 80 ° C. in a 10 Oz injection machine to prepare a physical specimen. The prepared specimens were left at 23 ° C. and 50% relative humidity for 40 hours, and then measured the Izod impact strength (1/4 ”notch, kgf · cm / cm) according to ASTM D-256. The results are shown in Table 1 below. It was.

As shown in Table 1, Comparative Examples 1, 3, and 4, which do not include the vinyl copolymer (A) containing epoxy groups according to the present invention, showed very low impact strength. In addition, (B) Comparative Example 2 that does not include a polyester resin can also be seen that the impact strength is very low. However, it can be seen that the compositions of Examples 1 to 8 consisting of the (A) epoxy group-containing vinyl copolymer and (B) polyester resin according to the present invention have a very high impact strength.

The present invention has the effect of providing a thermoplastic resin composition having improved impact resistance by using a vinyl copolymer having an epoxy group and polyester.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (12)

(A) (A ₁₎ epoxy group-containing vinyl copolymer and 5 to 100% by weight of (A ₂₎ a styrene-based polymer 30-99 parts by weight, which contains a rubber-reinforced styrene-based copolymer resin epoxy group consisting of 0-95% by weight; And (B) 1 to 70 parts by weight of polyester resin; The thermoplastic resin composition with improved impact resistance, characterized in that consisting of. According to claim 1, wherein the epoxy group-containing vinyl copolymer (A ₁ ) is composed of 0.001 to 5.0 mol% of unsaturated epoxy compound (A ₁₁ ) containing the epoxy group and 99.999 to 95 mol% of vinyl compound (A ₁₂ ) A thermoplastic resin composition characterized by copolymerizing a monomer mixture. The thermoplastic resin composition of claim 1, wherein the (A) styrene-based polymer contains 0.001 to 5.0 mol% of epoxy groups. The thermoplastic resin composition according to claim 1, wherein the polyester resin (B) has an intrinsic viscosity of 0.3 to 1.0 g / dL. The thermoplastic resin composition of claim 2, wherein the unsaturated epoxy compound (A ₁₁ ) is represented by the following Formula 1. [Formula 1]

In the above, R ₁ , R ₂ , R ₃ , R ₆ , R ₇ and R ₈ are each H, C ₁ -C ₁₂ alkyl group or unsaturated alkyl group, C ₆ -C ₁₄ aryl group, alkyl substituted aryl group, unsaturated alkyl a substituted aryl group, and, Y is an ether group (-O-), carboxyl group (-O- [C = O] - , - [O = C] -O-), alkylene group of C ₁ ~C _12, C ₆ ~ When C ₁₄ arylene group or alkyl is substituted arylene group, and Y is ether (-O-) or carboxyl (-O- [C = O]-,-[O = C] -O-), R ₄ and R ₅ each have C _{1 to} C ₁₂ alkylene, C _{6 to} C ₁₄ arylene group or an alkyl substituted arylene group, and Y is C ₁ to C ₁₂ alkylene, or C ₆ - when the arylene group an arylene group or a substituted alkyl of C _14, Y should represent a (R ₄ -YR _5). The method of claim 5, wherein the unsaturated epoxy compound (A ₁₁ ) is an epoxy alkyl acrylate, allyl glycidyl ester, aryl glycidyl ester, glycidyl methacrylate, glycidyl acrylate, butadiene monooxide, A thermoplastic resin composition selected from the group consisting of 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 90 wt% of an aromatic vinyl monomer and 10 to 60 wt% of a monomer copolymerizable with the aromatic vinyl monomer. 8. The thermoplastic resin composition of claim 7, 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. The thermoplastic resin composition according to claim 1, wherein the rubber-like particle size of the rubber-reinforced styrenic copolymer resin (A ₂ ) is 0.1 to 6.0 µm in Z-average. The thermoplastic resin composition according to claim 1, wherein the polyester resin (B) is a mixture of inorganic particles. The method of claim 1, wherein the resin composition further comprises at least one additive selected from the group consisting of flame retardants, heat stabilizers, dyes, pigments, lubricants, mold release agents, dispersants, anti-drip agents, weather stabilizers, inorganic fillers, inorganic fibers and mixtures thereof. Thermoplastic resin composition comprising a.