KR20190043404A - Thermoplastic resin composition and thermoplastic resin molded article prepared by using the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition and a molded article manufactured from the same. More specifically, the present invention relates to: the thermoplastic resin composition having excellent heat resistance and scratch resistance at the same time by comprising a methyl methacrylate-methylene butyrolactone copolymer; and the molded article manufactured from the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition and a molded article obtained from the thermoplastic resin composition.

More particularly, the present invention relates to a weather resistant thermoplastic resin composition having excellent heat resistance and excellent scratch resistance, and a molded article produced therefrom.

Acrylonitrile-butadiene-styrene (hereinafter abbreviated as "ABS") resin, which is produced by emulsion polymerization using styrene as a main raw material, is excellent in rigidity, chemical resistance, impact resistance and workability, and has impact strength and mechanical properties, It has excellent secondary processing characteristics such as gloss, plating, printing, and painting, and has advantages of being able to produce products in various colors. In recent years, there has been a lot of research for use as an automobile interior material by imparting heat resistance to an ABS resin excellent in impact resistance, chemical resistance and processability due to the necessity of lightening automobiles. However, ABS resin has a problem that weatherability and aging resistance are comparatively low. Therefore, when not only the impact strength is high but also the product having excellent weatherability and aging resistance is to be produced, the ethylenically unsaturated polymer should not be present in the resin, and ASA resin using a crosslinked alkyl acrylate rubber polymer is suitable And is widely used in automobile parts, construction materials and sporting goods by rapidly replacing paint-coated products used in existing outdoor applications.

However, there is a problem that the above-described scratch resistance, color, gloss and the like are lowered when compared with appearance characteristics of a paint product coated with an existing paint, resulting in lower product value. To improve the appearance properties of such ASA resins, the most popular method is to blend with acrylate-styrene-acrylonitrile copolymers.

The methyl methacrylate resin is widely used as an outdoor product because of its excellent weather resistance, good mechanical properties, and excellent scratch resistance on the surface. The blend resin of ASA resin and methyl methacrylate resin has already been commercialized, but it is difficult to use it for automobile parts due to lack of heat resistance. As a conventional method for imparting heat resistance to a resin, there is a method of preparing an alpha methyl styrene-acrylonitrile heat resistant copolymer and kneading it with a resin. U.S. Patent Nos. 3,010,936 and 4,659,790 disclose a method for producing a heat resistant copolymer Discloses a method for replacing part or all of styrene with alpha methyl styrene.

However, the resin produced by this method has a problem that the heat resistance is excellent, but the impact strength is greatly deteriorated, and the colorability is deteriorated due to the color of the heat-resistant copolymer itself.

Therefore, there is a demand for a weather resistant resin which satisfies both of the conventional impact resistance and heat resistance and is excellent in scratch resistance. U.S. Patent No. 6,476,126 and U.S. Patent No. 4,579,909 disclose a method for producing a thermoplastic resin having excellent physical properties, weather resistance, and excellent appearance characteristics through an acrylate-styrene-acrylonitrile resin, methyl methacrylate, and polycarbonate resin through a three- However, the above-mentioned manufacturing method satisfies all of the above-mentioned appearance characteristics, but it has a problem that the molding processability is poor due to a decrease in flow characteristics and the economical efficiency is poor.

U.S. Patent No. 6,476,126 U.S. Patent No. 4,579,909

The present invention provides a thermoplastic resin composition having excellent heat resistance and scratch resistance by including an alkyl (meth) acrylate-methylenebutyrolactone copolymer and a molded article produced therefrom in order to solve the problems of the prior art as described above .

The present invention has been made to solve the above problems,

(A) an alkyl (meth) acrylate-styrene-acrylonitrile copolymer;

(B) an alkyl (meth) acrylate-methylenebutyrolactone copolymer; And

(C) an alkyl (meth) acrylate-styrene-acrylonitrile copolymer.

The present invention also provides a thermoplastic resin molded article produced from the thermoplastic resin composition, wherein the thermoplastic resin molded article has a heat distortion temperature of 95 ° C or more and an air resistance of 1.5 or less when the thickness is 1/4 ".

As described above, the thermoplastic resin composition according to the present invention has an effect of providing a weather resistant thermoplastic resin composition having excellent heat resistance and scratch resistance and a molded article produced from the composition.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention. Herein, terms and words used in the present specification and claims should not be construed to be limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of the term to describe its own invention in the best way. It should be construed as meaning and concept consistent with the technical idea of the present invention.

In the thermoplastic resin composition according to one embodiment of the present invention,

(A) an alkyl (meth) acrylate-styrene-acrylonitrile copolymer;

(B) an alkyl (meth) acrylate-methylenebutyrolactone copolymer; And

(C) an alkyl (meth) acrylate-styrene-acrylonitrile copolymer.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising an alkyl (meth) acrylate-styrene-acrylonitrile resin (ASA resin), a scratch resistant alkyl (meth) acrylate-methylenebutyrolactone copolymer in heat resistance and a methyl methacrylate- A weather resistant thermoplastic resin composition excellent in heat resistance and excellent in scratch resistance through blending with an acrylonitrile resin (MSAN resin) is provided.

The present inventors have found that when an heat resistant scratch resistant alkyl (meth) acrylate-methylene butyrolactone copolymer is used together with an ASA resin, the heat resistance is excellent and heat resistance can be imparted even when the kneaded material is kneaded, , And the heat resistance is controlled according to the content of the methylene butyrolactone compound and the scratch resistance is controlled according to the alkyl (meth) acrylate content, thereby completing the present invention.

Each component constituting the thermoplastic resin composition of the present invention will be described in detail as follows.

(A) an alkyl (meth) acrylate-styrene-acrylonitrile copolymer (ASA copolymer)

The ASA copolymer of the present invention is produced by forming in the order of (i) a polymeric seed, (ii) an alkyl (meth) acrylate based polymer core, and (iii) a graft shell.

Specifically, the ASA copolymer has a core-shell structure including an alkyl (meth) acrylate-based polymer core and a shell containing a styrene-based monomer-derived unit and an acrylonitrile-based monomer- .

(i) 5 to 25 parts by weight of at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds and alkyl (meth) acrylate compounds, 0.05 to 0.3 parts by weight of an electrolyte, 0.01 to 0.5 parts by weight of a crosslinking agent 0.04 to 0.5 part by weight of a grafting agent, 0.05 to 4 parts by weight of a surfactant, 0.01 to 0.3 part by weight of a polymerization initiator, and distilled water.

As the aromatic vinyl compound, it is preferable to use a styrene derivative. Specifically, styrene, alphamethylstyrene, paramethylstyrene, vinyltoluene, or a substituent thereof may be used.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile or ethacrylonitrile may be used.

As the alkyl (meth) acrylate compound, alkyl methacrylates having 1 to 4 carbon atoms in the alkyl moiety may be used alone or in admixture of two or more, preferably methyl methacrylate having 1 to 2 carbon atoms in the alkyl moiety Acrylate or ethyl methacrylate.

As the alkyl (meth) acrylate compounds, alkyl acrylates having 1 to 4 carbon atoms in the alkyl moiety may be used alone or in admixture of two or more. Preferably, alkyl (meth) acrylate compounds having 4 to 8 carbon atoms in the alkyl moiety Acrylate, more preferably butyl acrylate or ethylhexyl acrylate.

As the electrolyte, NaHCO ₃ , Na ₂ S ₂ O ₇ or K ₂ CO ₃ can be used, and NaHCO ₃ is preferably used.

Examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl Glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, and the like can be used.

As the grafting agent, aryl methacrylate (AMA), triarylisocyanurate (TAIC), triarylamine (TAA) or diarylamine (DAA) may be used.

Examples of the surfactant include, but are not limited to, a fatty acid soap system represented by oleic acid, stearic acid, lauric acid, a sodium or potassium salt of a mixed fatty acid, or a rosin soap system represented by abietic acid salt. They may be used alone or in combination of two or more.

As the polymerization initiator, an inorganic or organic peroxide initiator may be used. Specifically, a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate, or an initiator such as cumene hydroperoxide or benzoyl peroxide may be used have.

An activator may be used to accelerate the initiation reaction of the peroxide with the polymerization initiator. Examples of the activator include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate or sodium pyrophosphate Sodium sulfate and the like can be used alone or in admixture of two or more, and preferably 0.001 to 0.02 parts by weight of sodium formaldehyde, 0.001 to 0.02 parts by weight of sodium ethylenediaminetetraacetate, and 0.0001 to 0.002 parts by weight of ferrous sulfate can be used .

The above components may be polymerized by emulsion polymerization alone, or by a combination of emulsion polymerization and non-emulsion polymerization. In this case, the monomers may be added either singly or in combination. On the other hand, the prepared polymer seeds preferably have an average particle diameter of 80 to 250 nm.

(meth) acrylate based polymer core comprises 20 to 70 parts by weight of an alkyl (meth) acrylate compound, 0.05 to 0.3 parts by weight of an electrolyte, 0.1 to 1 part by weight of a crosslinking agent, 0.05 to 0.5 parts by weight of a grafting agent, 0.05 to 4 parts by weight of a surfactant, 0.01 to 0.3 parts by weight of a polymerization initiator, and distilled water.

The alkyl (meth) acrylate compound, the electrolyte, the crosslinking agent, the grafting agent, and the surfactant may be the same as those used in the production of the (i) polymeric seed.

The polymerization method may be the same method as used in the production of the (i) polymer seed.

The resulting alkyl (meth) acrylate cores have (i) an alkyl (meth) acrylate rubber polymer crosslinked on the surface of the polymeric seed, wherein the crosslinked alkyl (meth) acrylate rubber polymer has a glass transition temperature And more preferably, the glass transition temperature may be -20 to -70 占 폚.

The alkyl (meth) acrylate core preferably has an average particle diameter of 300 to 600 nm, more preferably 400 to 500 nm, in a latex state.

(Iii) The grafted shell is prepared by blending 10 to 50 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyan compound, (iii) an aromatic vinyl compound in the presence of 30 to 80 parts by weight (based on solids) 0.05 to 4 parts by weight of an activator, 0.01 to 0.3 parts by weight of a polymerization initiator, and a shell prepared by polymerizing distilled water.

The aromatic vinyl compound, the vinyl cyan compound, and the polymerization initiator may be the same as those used in the production of the (i) polymer seed.

The surfactant may be the same as that used in the production of the polymeric seed (i), and may be a derivative of an alkylsulfosuccinate metal salt having a pH of 3 to 9 and a carbon number of 12 to 18, an alkylsulfuric acid having a carbon number of 12 to 20 Esters, or derivatives of sulfonic acid metal salts.

Examples of the derivative of the alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms include dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate sodium salt , Dioctylsulfosuccinate sodium salt or dioctylsulfosuccinate potassium salt, and the like can be used.

Examples of the alkyl sulfates or sulfonic acid metal salt derivatives having 12 to 20 carbon atoms include sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfate, sodium octadecyl sulfate, sodium oleate sulfate, potassium dodecyl sulfate Or potassium octadecyl sulfate may be used.

The polymerization method is preferably an emulsion polymerization method, and the monomer addition method is preferably a continuous introduction method. If a monomer mixture containing a surfactant is added at a time during the production of the graft shell, the pH of the polymerization system is temporarily raised to make the grafting difficult, the stability of the particles is lowered, and the internal structure of the particles is not uniform. Method is preferable.

The ASA copolymer prepared from the above procedure is in a latex state and is stable at a total solid content of 35 wt% or more. In addition, the pH of the ASA copolymer latex is preferably 8 to 11, more preferably 9 to 10.5.

The latex-like ASA copolymer is formed into powder by agglomeration, aging, dehydration, washing, and drying as a well-known flocculant. As the coagulant, sulfuric acid, MgSO ₄ , CaCl ₂ , Al ₂ (SO ₄ ) ₃ and the like can be used, and CaCl ₂ can be preferably used. The ASA copolymer latex is aged at 80 ° C at atmospheric pressure using an aqueous solution of CaCl ₂ , aged at 95 ° C, dehydrated and washed, and dried in hot air at 90 ° C for 30 minutes to prepare a powder. The ASA copolymer is preferably contained in the thermoplastic resin composition of the present invention in an amount of 30 to 70 parts by weight, preferably 400 to 60 parts by weight.

(B) a heat resistant scratch-resistant alkyl (meth) acrylate-methylenebutyrolactone copolymer

The copolymer may be copolymerized by, for example, an alkyl (meth) acrylate, a methylenebutyrolactone compound, an aromatic vinyl compound, and a vinyl cyan compound.

The copolymer is a copolymer comprising 50 to 75 parts by weight of an alkyl (meth) acrylate monomer-derived unit, 5 to 40 parts by weight of a methylenebutyrolactone monomer-derived monomer unit, 1 to 30 parts by weight of a styrene- , And 1 to 20 parts by weight of an acrylonitrile-based monomer-derived unit; Or an alkyl (meth) acrylate monomer unit, 55 to 70 parts by weight of an alkyl (meth) acrylate monomer unit, 10 to 35 parts by weight of a methylene butyrolactone monomer unit, 5 to 20 parts by weight of a styrene monomer unit, 1 to 15 parts by weight, and has an excellent heat resistance and scratch resistance within this range.

As the alkyl (meth) acrylate compounds, alkyl methacrylates having 1 to 4 carbon atoms in the alkyl moiety may be used alone or in admixture of two or more, preferably methyl methacrylate having 1 to 2 carbon atoms in the alkyl moiety Or ethyl methacrylate may be used.

The methylene butyrolactone compound is preferably selected from the group consisting of? -Methylene-? -Butyrolactone,? -Methyl-? -Methylene-? -Butyrolactone,? -Methyl-? -Methylene-? -Butyrolactone,? -Ethyl-? Methylene-γ-butyrolactone, and β-butyl-α-methylene-γ-butyrolactone.

As the aromatic vinyl compound, styrene, alphacetylstyrene, paramethylstyrene or vinyltoluene may be used, and styrene may be preferably used.

The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The copolymer may have a weight average molecular weight of 50,000 to 300,000 g / mol, 50,000 to 200,000 g / mol, or 70,000 to 150,000 g / mol, an excellent impact strength and a good flowability within this range, .

The polymerization method of the copolymer is not limited, but may be suspension polymerization or mass polymerization, preferably continuous mass polymerization, in which case the production cost is reduced.

In addition, the molecular weight can be adjusted by adding a molecular weight regulator during polymerization. The molecular weight regulator can be dodecyl mercaptan, and specific examples thereof include tertiary dodecyl mercaptan, n-dodecyl mercaptan, or a mixture thereof.

The heat resistant scratch resistant alkyl (meth) acrylate-methylene butyrolactone copolymer may have a glass transition temperature of 115 to 180 ° C, or 120 to 150 ° C, and an excellent balance of heat resistance and physical properties within this range have.

The heat resistant scratch resistant alkyl (meth) acrylate-methylene butyrolactone copolymer is preferably contained in the thermoplastic resin composition of the present invention in an amount of 20 to 70 parts by weight, preferably 20 to 60 parts by weight, based on the total weight of the thermoplastic resin composition Do.

(C) alkyl (meth) acrylate-styrene-acrylonitrile copolymer (MSAN copolymer)

The MSAN copolymer of the present invention is composed of a hard polymer-forming monomer having a glass transition temperature of at least 60 ° C or higher, and includes a styrene monomer unit, an acrylonitrile monomer unit, and an alkyl (meth) acrylate monomer unit ≪ / RTI >

The MSAN copolymer may contain 55 to 75 parts by weight of the alkyl (meth) acrylate monomer-derived unit based on the total weight of the MSAN copolymer, and has a weight average molecular weight (Mw) of 100,000 to 180,000 g / mol.

The MSAN copolymer is preferably contained in the thermoplastic resin composition of the present invention in an amount of 1 to 50 parts by weight based on the total weight of the thermoplastic resin composition.

The heat resistant scratch resistant thermoplastic resin composition comprising the components (A) to (C) as described above may be suitably used in the form of dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, , A foaming agent, a plasticizer or a low gloss agent.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. , And it is natural that such variations and modifications fall within the scope of the appended claims.

Manufacturing example

(A) Preparation of ASA Copolymer

(i) polymer seed

5 parts by weight of butyl acrylate, 0.15 part by weight of NaHCO ₃ , 0.4 part by weight of potassium rosinate, and 0.1 part by weight of ethylene glycol dimethacrylate were added to a polymerization reactor (autoclave) substituted with nitrogen, based on 100 parts by weight of the total monomers used for preparing the ASA copolymer. 0.05 part by weight of acrylate, and 60 parts by weight of distilled water. The temperature was raised to 70 DEG C, and 0.05 part by weight of potassium persulfate was added to initiate the reaction. The reaction was continued for 1 hour at 70 DEG C to prepare a polymer seed latex. The average particle size of the seed latex thus prepared was 182 nm.

(Ii) Preparation of alkyl acrylate cores

45 parts by weight of butyl acrylate, 0.15 part by weight of NaHCO ₃ , 0.5 part by weight of potassium rosinate and 0.5 part by weight of potassium oleate, 0.3 part by weight of ethylene glycol dimethacrylate, and 40 parts by weight of distilled water And 0.05 parts by weight of potassium persulfate was continuously added at 70 캜 for 3 hours, and further polymerization was carried out for 1 hour after completion of charging to prepare a butyl acrylate core latex. The average particle size of the prepared core latex was 385 nm.

(Iii) Preparation of graft shell

ASA copolymer, 37.5 parts by weight of styrene, 12.5 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosinate, 1.5 parts by weight of potassium persulfate in the presence of 50 parts by weight (solids basis) of butyl acrylate core latex based on 100 parts by weight of total monomers used in the production of ASA copolymer, 0.05 part by weight of sulfite, 0.1 part by weight of tertiary dodecylmercaptan and 60 parts by weight of distilled water was added to the mixture at 70 DEG C for 4 hours. After completion of the addition, the temperature was raised to 78 캜 so as to increase the polymerization conversion rate, and further reacted for 1 hour and cooled to 60 캜. The total solid content in the final ASA copolymer latex obtained after the completion of the reaction was 35%, and the polymerization conversion rate was 99.5%

The obtained ASA copolymer latex was subjected to atmospheric pressure agglomeration at 80 ° C using CaCl ₂ aqueous solution, aged at 95 ° C, dehydrated and washed, and dried with hot air at 90 ° C for 30 minutes to obtain ASA copolymer powder particles .

(B) Preparation of heat resistant scratch-resistant alkyl (meth) acrylate-methylenebutyrolactone copolymer

(B1): 52 parts by weight of methyl methacrylate, 10 parts by weight of? -Methyl-? -Methylene-? -Butyrolactone, 28 parts by weight of styrene and 25 parts by weight of ethylbenzene as a solvent in 10 parts by weight of acrylonitrile, 0.15 part by weight of ditearyldodecylmercaptan as a regulator and 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a radical initiator , And 3,5-trimethylcyclohexane) was continuously fed into the reactor so that the average reaction time was 3 hours, and the reaction temperature was maintained at 148 ° C. The polymer solution discharged from the reaction tank was heated in a preheating tank, and the unreacted monomers were volatilized in a volatilizing tank and the polymer temperature was kept at 210 ° C., and the copolymer resin was processed into a pellet using a polymer transfer pump extrusion machine. The weight average molecular weight of the copolymer obtained was 130,000 g / mol and the glass transition temperature was 130 ° C.

Except that 15 parts by weight of styrene, 10 parts by weight of acrylonitrile, 59 parts by weight of methyl methacrylate and 16 parts by weight of? -Methyl-? -Methylene-? -Butyrolactone were used in the production of (B2): (B1) , And the rest were prepared in the same manner. The heat resistant scratch resistant methyl methacrylate-methylenebutyrolactone copolymer thus prepared had a weight average molecular weight of 110,000 g / mol and a glass transition temperature of 142 占 폚.

Except that 16 parts by weight of styrene, 1 part by weight of acrylonitrile, 63 parts by weight of methyl methacrylate and 20 parts by weight of? -Methyl-? -Methylene-? -Butyrolactone were used in the production of (B3): (B1) , And the rest were prepared in the same manner. The prepared scratch resistant methyl methacrylate-methylenebutyrolactone copolymer in heat resistance had a weight average molecular weight of 110,000 g / mol and a glass transition temperature of 150 캜.

(C) Preparation of MSAN Copolymer

As the MSAN copolymer, a methyl methacrylate-styrene-acrylonitrile copolymer (XT510, manufactured by LG Chemical) having a weight average molecular weight of 130,000 g / mol was used.

≪ Preparation of heat resistant scratch resistant thermoplastic resin composition >

Example  One

40 parts by weight of the above-prepared (A) ASA copolymer, (B1) 40 parts by weight of a scratch resistant alkyl (meth) acrylate-methylenebutyrolactone copolymer in heat resistance and 20 parts by weight of an MSAN copolymer (C) , 1 part by weight of lubricant EBS (ethylene bis (stearamide)) and 0.5 parts by weight of an antioxidant Irganox 1076 were added to the mixture, and the resulting mixture was pelletized using a 40 psi extrusion kneader at a cylinder temperature of 250 캜. Specimens were prepared.

Example  2 and 3

A physical property specimen was prepared in the same manner as in Example 1, except that the components (A), (B) and (C) were added in the same manner as in Table 1 below.

Comparative Example  1 to 3

The components (A) and (C) were added in the same manner as in Example 1, and the polymethyl methacrylate resin (PMMA resin, LGMMA EH910, MFI Styrene-acrylonitrile copolymer (98 UHM, glass transition temperature: 122 占 폚, manufactured by LG Chemical Co., Ltd.) for increasing the heat resistance was added in the same composition as in Table 1, A physical property test piece was prepared in the same manner.

Comparative Example  4 and 5

A physical property specimen was prepared in the same manner as in Example 1, except that the components (A), (B) and (C) were added in the same manner as in Table 1 below.

(Parts by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (A)
ASA copolymer 40 40 40 40 40 40 40 28 (B) a methyl methacrylate-methylenebutyrolactone copolymer (B1) 40 - - - - - 15 71 (B2) - 40 - - - - - - (B3) - - 40 - - - - - (C) MSAN copolymer 20 20 20 - - 60 45 One PMMA resin - - - 20 40 - - - 98UHM - - - 40 20 - - -

Experimental Example

The physical properties of the thermoplastic resin composition specimens prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

1) Impact strength (impact resistance, kg.cm/cm)

Impact strength was measured by injection-molding the pellets of each of the thermoplastic resin compositions described above according to ASTM D256 (1/4 ", notched at 23, kg · cm / cm) into a 1/4" thick specimen.

2) Heat deformation temperature (캜)

(18.5 Kg / cm2) and under load (4.6 Kg / cm2) using a 1/4 "thick specimen according to ASTM D648.

3) Pencil hardness (scratch resistance, Pencil Hardness)

After the pencil was fixed with a load of 0.3 Kg at an angle of 45 °, the surface of the test piece was scratched by pencil hardness to judge whether or not it was scratched with the naked eye.

4) Weatherability (ΔE)

And measured with a weather resistance measuring device (QUV). The measurement conditions were the UV LAMP illumination of 0.77 W / m ² , the humidity of 50%, the Black Panel temperature of 60 ° C after 20 hours of stay, ΔE is the arithmetic average value of Hunter Lab values before and after stay, . ? E indicating weatherability is expressed by the following equation (1).

[Equation 1]

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Impact strength
(1/4 ", kg.cm/cm) 15 16 14 14 12 20 14 11 Heat distortion temperature
(1/4 ",) 97 99 95 95 91 90 90 98 Pencil hardness HB HB F 2B B HB F B Weatherability (ΔE) 1.5 1.5 1.3 2.7 2.1 1.9 1.5 1.4

As shown in Table 2, it was confirmed that the thermoplastic resin compositions of Examples 1 to 3 prepared according to the present invention had excellent impact resistance and heat resistance, and excellent scratch resistance and weather resistance.

On the other hand, Comparative Example 1, which did not contain the (meth) acrylate-methylenebutyrolactone copolymer (B), was found to be excellent in heat resistance but lowered in impact resistance and weatherability as a result of excessive use of 98 UHM as a heat- Example 2 shows that the PMMA resin which increases the scratch resistance enhances the scratch resistance and weatherability but the impact resistance and the heat resistance deteriorate. As in Comparative Example 3, the heat resistant copolymer and the scratch resistant copolymer When nothing is used, the impact resistance and scratch resistance are excellent, but the heat resistance is lowered.

On the other hand, even when the (B) methyl methacrylate-methylenebutyrolactone copolymer was contained, the heat resistance was not good when the amount of the copolymer (B) was too small as in Comparative Example 4. As in Comparative Example 5, (B) an excessive amount of the copolymer, it was confirmed that the physical properties such as impact resistance and pencil hardness were deteriorated although the heat resistance was excellent.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (13)

(A) an alkyl (meth) acrylate-styrene-acrylonitrile copolymer;
(B) an alkyl (meth) acrylate-methylenebutyrolactone copolymer; And
(C) an alkyl (meth) acrylate-styrene-acrylonitrile copolymer.
The method according to claim 1,
The thermoplastic resin composition preferably contains the thermoplastic resin composition
(A) 30 to 70 parts by weight of a copolymer,
(B) 20 to 70 parts by weight of a copolymer, and
(C) 1 to 50 parts by weight of a copolymer.
The method according to claim 1,
The above-mentioned (A) copolymer has a core-shell structure comprising an alkyl (meth) acrylate-based polymer core and a shell containing a styrene-based monomer-derived unit and an acrylonitrile-based monomer- Wherein the thermoplastic resin composition is a thermoplastic resin composition.
The method according to claim 1,
Wherein the alkyl (meth) acrylate monomer of the copolymer (A) is butyl acrylate or ethylhexyl acrylate.
The method according to claim 1,
The (B) copolymer is a copolymer of (B)
50 to 75 parts by weight of an alkyl (meth) acrylate monomer-derived unit and
And 5 to 40 parts by weight of a methylenebutyrolactone monomer-derived unit.
The method according to claim 1,
Wherein the alkyl (meth) acrylate monomer of the (B) copolymer is methyl methacrylate or ethyl methacrylate.
The method according to claim 1,
The methylene butyrolactone monomer of the (B) copolymer is preferably a copolymer of? -Methylene-? -Butyrolactone,? -Methyl-? -Methylene-? -Butyrolactone,? -Methyl-? Wherein the thermoplastic resin composition is at least one selected from the group consisting of lactone,? -Ethyl-? -Methylene-? -Butyrolactone, and? -Butyl-? -Methylene-? -Butyrolactone.
The method according to claim 1,
Wherein the (B) copolymer has a glass transition temperature of 115 to 180 ° C and a weight average molecular weight (Mw) of 70,000 to 150,000 g / mol.
The method according to claim 1,
Wherein the (B) copolymer further comprises a styrene-based monomer-derived unit and an acrylonitrile-based monomer-derived unit.
10. The method of claim 9,
The (B) copolymer is a copolymer of (B)
50 to 75 parts by weight of an alkyl (meth) acrylate monomer-derived unit,
5 to 40 parts by weight of a methylene butyrolactone monomer derived unit,
1 to 30 parts by weight of a styrene-based monomer-derived unit, and
And 1 to 20 parts by weight of an acrylonitrile-based monomer-derived unit.
The method according to claim 1,
Wherein the (C) copolymer comprises 55 to 75 parts by weight of an alkyl (meth) acrylate monomer-derived unit based on the total weight of the (C) copolymer.
The method according to claim 1,
Wherein the thermoplastic resin composition further comprises at least one additive selected from the group consisting of dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers and low- Composition.
A thermoplastic resin composition, which is produced from the thermoplastic resin composition according to any one of claims 1 to 12,
Wherein the thermoplastic resin molded article has a heat distortion temperature of 95 DEG C or more and an air resistance of 1.5 or less when the thickness is 1/4 ".