KR20200076338A - Thermoplastic resin composition, method for preparing the thermoplastic resin composition and molding products thereof - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded product comprising the same and, more particularly, to a thermoplastic resin composition, a method for preparing the same, and a molded product comprising the same, which comprises: (A) a graft copolymer obtained by graft copolymerization including at least one of a (meth)acrylate alkyl ester compound, an aromatic vinyl compound, and a vinylcyan compound in a conjugated diene rubber; 100 parts by weight of a base resin including (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinylcyan compound non-grafted copolymer; (C) 0.1 to 4 parts by weight of a conductive polymer antistatic agent; and (D) 0.1 to 3 parts by weight of a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol, thereby providing more compatibility, excellent mechanical properties such as impact resistance, etc., while showing excellent antistatic property, processibility and transparency.

Description

THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE THERMOPLASTIC RESIN COMPOSITION AND MOLDING PRODUCTS THEREOF}

The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article containing the same, and more specifically, to increase the compatibility, excellent in impact resistance and the like, but excellent in antistatic property, processability, and transparency. Method and a molded article comprising the same.

In general, transparent ABS resins are widely used in various fields because of their extremely high light transmittance, excellent transparency, excellent impact resistance, processability, and excellent mechanical properties. Specifically, the transparent ABS resin is a housing for household appliances including air conditioners, vacuum cleaners, washing machines, etc., OA devices such as facsimile machines, computers, telephone housings, automobile parts, toys, leisure products, and indoor decorations. It is utilized for the purpose of.

However, since the transparent ABS resin has excellent electrical insulation properties of about 10 ¹⁵ to 10 ²⁰ Ωcm and is easily charged, it often causes serious problems due to charged static electricity. As an example, when friction or peeling of an overlapping film, charging of up to tens of thousands of volts can easily occur, sometimes giving an electric shock to an operator or sometimes causing a fire due to flammable gas or liquid ignition and explosion. As another example, in the case of an injection product manufactured using the transparent ABS resin, dust adheres to the exterior of the product and frequently damages the appearance, so that the product must be wiped again due to the dust attached to the surface of the product during long-term storage. There is this.

In order to prevent such a problem, attempts have been made to use a film with antistatic properties on the product or to transport the product in a transport container with antistatic properties, but this creates a new problem that is cumbersome.

Meanwhile, examples of the antistatic agent used for the purpose of preventing static electricity include conductive carbon black, surfactant type antistatic agent, ionic liquid, inherently conductive polymer (ICP), and metal salt compounds.

However, when a surfactant such as a fatty acid ester is added, the surfactant does not chemically bond with the resin, and thus, the antistatic property is easily lost due to friction or washing. As the amount of the surfactant added increases, the physical properties of the resin decrease. The surfactant exposed on the surface imparted tackiness to the resin surface, and thus dust or impurities were more easily adhered, thereby deteriorating the appearance.

In addition, when the conductive carbon black was added, it was easy to secure antistatic properties, but it was difficult to implement various colors, so there were limitations in the field of application.

In addition, when a metal salt compound was added, it had to be excessively administered in order to realize a desired level of surface resistance, and in this case, it was inevitably limited due to considerable difficulty in the extrusion and injection processes as well as maintaining the properties of the resin itself.

On the other hand, a plasticizer selected when manufacturing a thermoplastic resin composition requires proper compatibility with a transparent ABS resin. In addition, the formulation and economics of additives such as stabilizers, fillers, pigments, etc. are also factors to be considered in plasticizer selection.

In addition, the choice of plasticizer further affects the properties of the final product, namely color, odor, hardness, flexibility, cold resistance (flowability at low temperature, impact resistance), tensile strength, tear strength, heat resistance, electrical insulation, wear resistance, non-toxicity , Flame retardancy, slip resistance, mutual application with pigment and migration resistance. As such, it is not easy to select a plasticizer that satisfies all of the desired characteristics, and usually trade-off relationships between the characteristics are established, and it is inevitable that some of the desired characteristics are reduced.

Accordingly, there is a need to develop a transparent thermoplastic resin composition having excellent compatibility with ABS resins and other additives, and providing a high level of antistatic properties by a processing method that does not significantly increase manufacturing cost and excellent mechanical properties.

Korean Registered Patent No. 10-0226458

In order to solve the problems of the prior art as described above, the present invention is a thermoplastic resin composition having excellent mechanical properties such as impact resistance and improved antistatic property, processability and transparency due to increased compatibility, a method for manufacturing the same, and a molded article containing the same It aims to provide.

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

In order to achieve the above object, the present invention is (A) a conjugated diene rubber (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and at least one of a vinyl cyan compound graft copolymer graft copolymer and ( B) 100 parts by weight of a base resin comprising a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound non-graft copolymer; (C) 0.1 to 4 parts by weight of a conductive polymer antistatic agent; And (D) 0.1 to 3 parts by weight of a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol.

In addition, the present invention (A) a conjugated diene rubber (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and a graft copolymer comprising at least one of a vinyl cyan compound and (B) (meth) acrylic acid 100 parts by weight of a base resin comprising an alkyl ester compound-aromatic vinyl compound-vinyl cyan compound non-graft copolymer; (C) 0.1 to 4 parts by weight of a conductive polymer antistatic agent; And (D) 0.1 to 3 parts by weight of a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol, kneading and extruding under conditions of 200 to 330° C. and 100 to 500 rpm, and extruding the thermoplastic resin composition. Provide a manufacturing method.

In addition, the present invention provides a molded article characterized in that it is made of a thermoplastic resin composition of the present substrate.

According to the present invention, there is an effect of providing a transparent thermoplastic resin composition having excellent mechanical properties such as impact resistance and excellent antistatic property and processability by increasing compatibility, a manufacturing method thereof, and a molded article containing the same.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method for manufacturing the same, and a molded article containing the same will be described in detail.

When the present inventors mix a graft copolymer and a non-graft copolymer, and when adding a conductive polymer as an antistatic agent and a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol in a specific content, compatibility between components It has been confirmed that the mechanical properties such as impact resistance are improved as well as anti-static properties, processability and transparency are all improved, and based on this, more research has been conducted to complete the present invention.

The thermoplastic resin composition of the present invention comprises (A) a graft copolymer copolymerized with a graft copolymer comprising at least one of an (meth)acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubber and (B) (meth ) Acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound 100 parts by weight of a base resin comprising a non-graft copolymer; (C) 0.1 to 4 parts by weight of a conductive polymer antistatic agent; And (D) 0.1 to 3 parts by weight of a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol. In this case, mechanical properties such as impact resistance are excellent, but antistatic property, processability, and transparency are all excellent. It works.

The (A) graft copolymer of the present disclosure is, for example, 30 to 85% by weight of a (meth)acrylic acid alkyl ester compound, 1 to 30% by weight of an aromatic vinyl compound, and 1 to 20% of a vinyl cyan compound in 10 to 60% by weight of a conjugated diene rubber. It may be to include a weight%, there is an effect of excellent impact resistance and transparency within this range.

The (A) graft copolymer may include, for example, 10 to 60% by weight, 30 to 60% by weight, or 40 to 60% by weight of conjugated diene rubber, in which case impact resistance and transparency are improved. .

The conjugated diene rubber means, for example, a polymer or copolymer comprising a conjugated diene-based compound having a structure in which double bonds and single bonds are arranged over one another, and as a specific example, a butadiene polymer, butadiene-styrene It may be at least one selected from the group consisting of a copolymer and a butadiene-acrylonitrile copolymer, preferably a butadiene copolymer, and in this case, excellent mechanical properties, processability, etc. of the composition.

The conjugated diene rubber may have, for example, a weight average particle diameter of 800 to 3,500 Å, 1,200 to 3,500 Å, or 2,000 to 3,500 Å, preferably 2,800 to 3,200 ,, and mechanical properties and processability within this range. There is an effect to be improved.

In the present description, the weight average particle diameter is measured by using an intensity gaussian distribution (Nicomp 380), for example, by dynamic laser light scattering.

The conjugated diene rubber may have, for example, a gel content of 50 to 95% by weight, 60 to 90% by weight, or 65 to 80% by weight, and within this range, mechanical strength and transparency are excellent, but fluidity is adequate, and processability is excellent. It works.

The conjugated diene rubber may have, for example, a swelling index of 10 to 20, or 15 to 20, and has excellent effects in physical properties such as impact resistance and transparency within this range.

The gel content and swelling index of the conjugated diene rubber in this base material are, for example, solidified conjugated diene rubber using dilute acid or metal salt, washed, dried in a vacuum oven at 60° C. for 24 hours, and the obtained rubber mass is finely cut with scissors. Then, 1 g of the rubber section was put in 100 g of toluene, stored in a dark room at room temperature for 48 hours, and then separated into sol and gel, and calculated through Equations 1 and 2 below.

[Equation 1]

Gel content (% by weight) = (weight of insoluble matter (gel) / weight of sample) X 100

[Equation 2]

Swelling index = weight of swollen gel / weight of gel

The (A) graft copolymer may include, for example, 30 to 85% by weight, 30 to 75% by weight, or 30 to 60% by weight of the (meth)acrylic acid alkyl ester compound based on 100% by weight of the graft copolymer, , In this case, while having excellent transparency, fluidity is appropriate and antistatic properties are excellent.

The (meth) acrylic acid alkyl ester compound is (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester and ( Meta) may be one or more selected from the group consisting of acrylic acid lauryl ester, preferably methyl methacrylate, and in this case, there is an effect of improving transparency.

The (A) graft copolymer may include, for example, 1 to 30 wt%, 5 to 20 wt%, or 7 to 15 wt% of an aromatic vinyl compound relative to 100 wt% of the graft copolymer, in this case transparency It is excellent in fluidity and has an excellent antistatic effect.

The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, preferably styrene, and in this case, fluidity is appropriate, and thus processability It has an excellent effect and excellent mechanical properties such as impact resistance.

The (A) graft copolymer may include, for example, 1 to 20% by weight, 1 to 18% by weight, or 1 to 10% by weight of a vinyl cyan compound relative to 100% by weight of the graft copolymer, in this case Impact, transparency and processability are all excellent effects.

The vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, preferably containing acrylonitrile, and in this case, impact resistance, Both transparency and processability have excellent effects.

The (A) graft copolymer may have a weight-average molecular weight of 80,000 to 300,000 g/mol, 80,000 to 250,000 g/mol, or 80,000 to 180,000 g/mol, and fluidity within this range is appropriate, thereby providing excellent processability It has an excellent impact resistance effect.

The (A) the weight average molecular weight of the graft copolymer can be easily controlled by adding a molecular weight modifier during polymerization of the graft copolymer, for example, the tertiary dodecyl mercaptan (TDDM), n- Dodecyl mercaptan (NDDM), n-octyl mercaptan and carbon tetrachloride may be at least one selected from the group consisting of, in this case, the effect of improving the transparency and processability of the composition by adjusting the weight average molecular weight of the graft copolymer have.

The weight average molecular weight in the present description can be measured using gel chromatography (GPC) filled with porous silica after dissolving 1 g of resin in tetrahydrofuran (THF) at a temperature of 40° C., unless otherwise defined. have. At this time, the molecular weight is measured after calibration using polymethyl methacrylate (PMMA) as a standard material.

The (A) graft copolymer may be, for example, produced by emulsion polymerization, and in this case, it has excellent grafting efficiency and thus has excellent physical properties such as impact resistance.

The (A) graft copolymer may have, for example, a refractive index of 1.49 to 1.55, 1.5 to 1.54, or 1.51 to 1.53, and has an excellent transparency effect within this range.

In this description, the refractive index is calculated as in Equation 3 below unless otherwise defined.

[Equation 3]

Refractive Index (RI) = ∑ Wti * RIi

(Wti = weight fraction of each component in the copolymer (%))

(RIi = polymer refractive index of each component in the copolymer)

The non-grafted copolymer (B) of the present disclosure may include, for example, 40 to 90% by weight of the (meth)acrylic acid alkyl ester compound, 1 to 50% by weight of the aromatic vinyl compound, and 1 to 30% by weight of the vinyl cyan compound, Within this range, fluidity is appropriate, so that it is easy to process, but has excellent mechanical strength, transparency, and antistatic properties.

The (meth)acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyan compound included in the non-graft copolymer (B) are (meth)acrylic acid alkyl ester compounds and aromatic vinyl compounds included in the graft copolymer of the present disclosure. And the vinyl cyan compound.

The (B) non-graft copolymer may be a methyl methacrylate-styrene-acrylonitrile (MSAN) copolymer as a preferred example, in which case the fluidity of the composition is appropriate, easy to process, transparency, mechanical strength, discoloration It has excellent effects such as sex.

The (B) non-graft copolymer may include, for example, 40 to 90% by weight, 50 to 80% by weight, or 60 to 75% by weight of the (meth)acrylic acid alkyl ester compound based on 100% by weight of the non-graft copolymer, , In this case, it has an excellent effect of transparency and antistatic properties.

The (B) non-graft copolymer may include, for example, 1 to 50% by weight, 5 to 40% by weight, or 15 to 30% by weight of an aromatic vinyl compound relative to 100% by weight of the non-graft copolymer, in this case It has excellent impact and transparency effects.

The (B) non-graft copolymer may include, for example, 1 to 30% by weight, 1 to 20% by weight, or 3 to 10% by weight of a vinyl cyan compound relative to 100% by weight of the non-graft copolymer, in this case transparency , Mechanical strength, discoloration resistance, and the like.

The (B) non-graft copolymer may have, for example, a weight average molecular weight of 50,000 to 110,000 g/mol, 70,000 to 110,000 g/mol, or 80,000 to 105,000 g/mol, and preferably 80,000 to 100,000 g/mol. In this range, the fluidity is appropriate within this range, so that it is easy to process and has excellent mechanical properties such as impact resistance.

The intermediate weight average molecular weight of the non-grafted copolymer (B) can be easily adjusted by adding a molecular weight modifier during polymerization of the non-grafted copolymer, for example, and the molecular weight modifier is, for example, tertiary dodecyl mercaptan (TDDM), n- Dodecyl mercaptan (NDDM), n-octyl mercaptan and carbon tetrachloride may be at least one selected from the group consisting of, in this case, the effect of improving the transparency and processability of the composition by adjusting the weight average molecular weight of the graft copolymer have.

The (B) non-graft copolymer may be prepared by, for example, suspension polymerization or bulk polymerization, preferably continuous bulk polymerization, and in this case, not only reduces manufacturing cost but also has excellent thermal stability and transparency.

The (B) non-graft copolymer may have, for example, a refractive index of 1.49 to 1.55, 1.5 to 1.54, or 1.51 to 1.53, and has an excellent transparency effect within this range.

The difference in refractive index between the (A) graft copolymer and the (B) non-graft copolymer may be, for example, 0.01 or less, or 0.005 or less, and within this range, transparency is very excellent.

For example, the base resin of the base material may include, for example, 20 to 80% by weight of the graft copolymer (B) and 20 to 80% by weight of the non-graft copolymer, based on 100% by weight of the total base resin, and this range It is excellent in transparency, yet easy to process and has excellent effects such as impact resistance.

In another example, the base resin may be to include (A) 30 to 60% by weight of the graft copolymer and (B) 40 to 70% by weight of the non-graft copolymer based on 100% by weight of the total base resin, and this range It has excellent workability, impact resistance, transparency and antistatic properties.

The conductive polymer antistatic agent (C) of the present disclosure may include, for example, a polythiophene antistatic agent, and in this case, it has an excellent antistatic effect while maintaining high transparency, impact resistance, and workability.

The polythiophene-based antistatic agent may be, for example, poly(alkylenedioxythiophene), and in this case, while maintaining high transparency, impact resistance, and workability, antistatic properties are very excellent.

The poly(alkylenedioxythiophene) may include, for example, poly(3,4-ethylenedioxythiophene) (PEDOT), and in this case, the manufacturing cost is reduced and the antistatic property and the transparency are very excellent. .

The poly(alkylenedioxythiophene) may be poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid (PEDOT:PSS) as another example, and in this case, an antistatic property is further improved.

The (C) conductive polymer antistatic agent may be included in an amount of 0.1 to 4 parts by weight, or 0.5 to 4 parts by weight based on 100 parts by weight of the base resin, for example, preferably 1 to 3 parts by weight. The improvement effect of prevention is weak, and if it is more than the above range, mechanical strength and transparency are lowered, and a problem that material cost increases may occur.

The (C) conductive polymer antistatic agent, for example, may be in the form of a powder or a pellet, and in this case, has excellent compatibility with a base resin, and can provide a high level of antistatic properties to an insulating resin through mechanical processing. There is an effect that can be reduced.

The (C) conductive polymer antistatic agent may have, for example, a surface resistance of 150 to 600 Ω/sq, or 200 to 450 Ω/sq, and in this case, an antistatic property is further improved.

The conductive polymer antistatic agent (C) may have, for example, a transmittance (Tt) of 80% or more, or 85 to 93%, and in this case, both transparency and antistatic properties are excellent.

The surface resistance of the conductive polymer antistatic agent in this substrate is prepared by dissolving the conductive polymer in water or ethanol, coating it with a thickness of 40 μm on the surface of polyethylene terephthalate (PET), and then heat-curing it at 130° C. for 6 minutes to prepare the specimen. It is measured by using, and the transmittance of the conductive polymer antistatic agent in the present substrate is measured according to ASTM D1003 after removing PET from the specimen prepared as described above.

In the present description, the polymer plasticizer means that the weight average molecular weight is 1,000 g/mol or more unless otherwise defined, and the low molecular weight plasticizer means that the weight average molecular weight is less than 1,000 g/mol unless otherwise defined.

The polymer plasticizer (D) of the present disclosure may have, for example, a weight average molecular weight of 1,000 to 40,000 g/mol, 1,000 to 30,000 g/mol, or 2,000 to 10,000, preferably 2,000 to 7,000 g/mol, In this case, compatibility increases, and mechanical properties such as impact resistance are excellent, while antistatic properties, processability, and transparency are all excellent.

The polymer plasticizer (D) may be, for example, a polyester plasticizer, a ethylene-vinyl acetate, a vinyl ether, and a ternary-copolymer resin resin plasticizer of carbon monoxide, or a mixture thereof, preferably a polyester plasticizer. It may be a plasticizer, and in this case, compatibility increases, and thus mechanical properties such as impact resistance and antistatic properties are excellent.

The polyester plasticizer may be, for example, at least one selected from the group consisting of poly-2-ethylhexyl glycol adipate, adipic acid polyester, citric acid polyester, sebacic acid polyester, azelaic acid polyester, and phthalic acid polyester. In this case, the fluidity is appropriate, and the workability is excellent, but the impact resistance, transparency, and antistatic property are excellent.

The alkyl acrylate is, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, methyl Butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenylacrylic It may be at least one selected from the group consisting of acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate and allyl acrylate.

The polymer plasticizer (D) may be, for example, 0.1 to 3 parts by weight, or 0.5 to 3 parts by weight with respect to 100 parts by weight of the base resin, preferably 1 to 2.5 parts by weight, and if it is less than the above range, compatibility is poor And, if it exceeds the above range, there is a problem that impact resistance and transparency are lowered and there is also no economical efficiency.

The thermoplastic resin composition of the present disclosure is, for example, UV stabilizers, fluorescent brighteners, lubricants, chain extenders, mold release agents, pigments, dyes, antibacterial agents, processing aids, metal deactivators, smoke suppressants, inorganic fillers, glass fibers, anti-friction agents, and It may further include one or more additives selected from the group consisting of anti-wear agents, the additive may be, for example, 0.1 to 5 parts by weight, or 0.1 to 3 parts by weight with respect to 100 parts by weight of the base resin, in which case the physical properties are improved And the manufacturing cost is low, it has the effect of excellent economics.

The thermoplastic resin composition of the present disclosure is measured by applying a voltage of 250 V to a square specimen of 4.0 cm X 8.0 cm X 0.3 cm at 23 °C and 50% RH condition using VMG-1000 HIGHMEGOHM METER (Ando) as an example. One surface resistance may be 1.5 X 10 ¹⁰ or less, or 1.0 X 10 ⁷ to 1.0 X 10 ¹⁰ , preferably 1.0 X 10 ⁸ to 3.5 X 10 ⁹ , and an antistatic property is excellent in this range.

The thermoplastic resin composition of the present disclosure may have, for example, a transmittance (Tt) of a 3 mm sheet measured according to ASTM D1003 of 80% or more, 85% or more, or 85 to 95%, and transparency (Haze) of 10 or less, It may be 5.5 or less, or 3.0 to 5.0, and has an excellent transparency effect within this range.

For example, the thermoplastic resin composition of the present disclosure has an Izod impact strength (1/4'', 23°C) of 16 kgf·cm/cm ² or more, 16 to 25 kgf·cm/cm ² , measured according to ASTM D256, or It may be 17 to 23 kgf·cm/cm ² , and an impact resistance effect is excellent within this range.

The thermoplastic resin composition of the present disclosure may have, for example, a melt index (220° C., 10 kg) measured according to ASTM D1238 of 15 to 40 g/10min, preferably 20 to 35 g/10min, and in this case, fluidity There is an advantage that it is suitable and easy to process.

Hereinafter, a method for manufacturing the thermoplastic resin composition of the present invention and a molded article containing the composition will be described. In the description of the method for manufacturing the thermoplastic resin composition of the present invention and the molded article containing the composition, all of the contents of the thermoplastic resin composition described above are included.

The manufacturing method of the thermoplastic resin composition of the present disclosure includes, for example, (A) a graft copolymer copolymerized with a graft copolymer comprising at least one of an (meth)acrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound in a conjugated diene rubber, and (B) 100 parts by weight of a base resin comprising a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound non-graft copolymer; (C) 0.1 to 4 parts by weight of a conductive polymer antistatic agent; And (D) 0.1 to 3 parts by weight of a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol, kneading and extruding under conditions of 200 to 330°C and 100 to 500 rpm, and in this case, compatibility By increasing, it has excellent mechanical properties such as impact resistance, but has an excellent antistatic property, processability, and transparency.

The kneading may be, for example, first mixing the graft copolymer and the non-graft copolymer, and then kneading by introducing the conductive polymer antistatic agent and the polymer plasticizer, and as another example, the graft copolymer and the non-graft copolymer. , A conductive polymer antistatic agent and a polymer plasticizer may be kneaded at once.

The kneading and extrusion may be performed, for example, through a single-screw extruder, a twin-screw extruder, or a Benbury mixer, in which case the composition is uniformly dispersed to have excellent compatibility.

The kneading and extrusion may be performed within a range in which the barrel temperature is 200 to 330°C, 250 to 320°C, 280 to 310°C, or 290 to 310°C, for example, in this case, sufficient and sufficient melt kneading in throughput per unit time. This may be possible, there is an effect that does not cause problems such as thermal decomposition of the resin component.

The kneading and extrusion may be performed under the conditions that the screw rotation speed is 100 to 500 rpm, 150 to 400 rpm, 100 to 350 rpm, 200 to 310 rpm, or 250 to 350 rpm, for example, and in this case, the throughput per unit time is appropriate. While excellent in process efficiency, it has the effect of suppressing excessive cutting.

The molded article of the present base material may be made of, for example, a thermoplastic resin composition of the present base material, and in this case, compatibility increases, and thus mechanical properties such as impact resistance are excellent, and antistatic properties, processability and transparency are excellent.

The molded article may include, for example, a housing of a household appliance such as an air conditioner, a vacuum cleaner, a washing machine, a refrigerator, and a TV back cover; Housings of OA devices such as computers, laptops, monitors, facsimiles, telephones, copiers and scanners; Automotive parts such as automotive interior and exterior materials; A toy member; Leisure goods; And interior decoration products.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

Materials used in Examples and Comparative Examples are as follows.

Preparation Example (A): Preparation of graft copolymer

100 parts by weight of ion-exchanged water, 1.0 part by weight of sodium oleate emulsifier, 35 parts by weight of methyl methacrylate, 50 parts by weight of a butadiene rubber latex (gel content 70% by weight, average particle size 0.3 µm) prepared by emulsion polymerization, Styrene 12 parts by weight, acrylonitrile 3 parts by weight, tertiary dodecyl mercaptan 0.5 parts by weight, sodium sulfoxylate formaldehyde 0.048 parts by weight, ethylenediaminetetraacetic acid 0.012 parts by weight, ferrous sulfide 0.001 parts by weight, cumene hydroper 0.08 parts by weight of oxide was reacted by continuously administering at 70° C. for 4 hours. After the reaction, the mixture was heated to 75°C, aged for 1 hour, and then the reaction was completed to prepare latex. At this time, the polymerization conversion rate was 98.0%, and solid coagulation was 0.3%. The prepared latex was coagulated with an aqueous calcium chloride solution and washed to obtain a powder.

Preparation Example (B-1): Preparation of non-graft copolymer

An average reaction time of 3 hours was obtained by mixing 70 parts by weight of methyl methacrylate, 23 parts by weight of styrene, and 7 parts by weight of acrylonitrile with 30 parts by weight of toluene as a solvent and 0.5 parts by weight of dicerary dodecyl mercaptan as a molecular weight regulator. When possible, the reaction tank was continuously charged, and the reaction temperature was maintained at 148°C to react. The polymerization solution discharged from the reaction tank was heated in a preliminary heating tank, and unreacted monomers were volatilized and removed from the volatilization tank. Thereafter, the polymer resin was processed into pellets using a polymer transfer pump extrusion machine at a temperature of 210°C. The prepared pellets were measured for weight average molecular weight using GPC (Gel Permeation Chromatography), wherein the weight average molecular weight was 100,000 g/mol.

Preparation Example (B-2): Preparation of non-graft copolymer

It was prepared in the same manner as in Preparation Example B-1, except that 0.15 parts by weight instead of 0.5 parts by weight of dietary dodecyl mercaptan, which is a molecular weight modifier, was prepared in Preparation Example B-1. At this time, the weight average molecular weight was 150,000 g/mol.

(C-1): Conductive polymer antistatic agent

Orgacon Dry powder from Agfa, Belgium, was used.

(D-1): Polymer plasticizer (polyester plasticizer)

Palamoll 652 (Polymeric plasticizer derived from adipic acid and polyhydric alcohols) having a weight average molecular weight of 3,300 g/mol was used.

(D-2): Low molecular weight plasticizer having a weight average molecular weight of 300 to 400 g/mol

Reaction product of disubstituted carbomonocycle, alkyl(C=1~3) alkanol(C=4~6) and alkanol(C=3~5) (LG Chem, LGflex GL500) were used.

(D-3): Diisodecyl phthalate (DIDP) was used as a phthalate plasticizer.

(D-4): Tri(2-ethylhexyl) trimellitate (TOTM) was used as a trimellitic acid plasticizer.

(D-5): 1,2-cyclohexane dicarboxylic acid diisononyl ester (1,2-cyclohexane dicarboxylic acid diisononyl ester) (Hexamoll DINCH) was used.

[Example]

Example 1

The prepared graft copolymer, non-graft copolymer, PEDOT as an antistatic agent and Palamoll 652 as a plasticizer were mixed in the contents shown in Table 1 below, and 0.3 parts by weight of lubricant and 0.3 parts by weight of antioxidant were added to obtain a cylinder temperature of 210°C. It was prepared in pellet form using a twin-screw extrusion kneader. After that, the specimen was prepared by injection into the prepared pellet.

Examples 2 to 4, Comparative Examples 1 to 8 and Reference Example 1

In Example 1, except for using the components and contents of Table 1, it was carried out in the same manner as in Example 1.

Graft copolymer Non-graft
Copolymer Antistatic agent Plasticizer A B-1 B-2 C-1 D-1 D-2 D-3 D-4 D-5 Example 1 40 60 One One Example 2 40 60 One 2.5 Example 3 40 60 3 One Example 4 40 60 3 2.5 Comparative Example 1 40 60 One Comparative Example 2 40 60 One 2.5 Comparative Example 3 40 60 One 2.5 Comparative Example 4 40 60 One 2.5 Comparative Example 5 40 60 One 2.5 Comparative Example 6 40 60 5 One Comparative Example 7 40 60 One 4 Comparative Example 8 40 60 One 5 Reference Example 1 40 60 One 2.5

(In the table above, the contents of each of (A) and (B) are weight% based on the total weight of (A) and (B), and the respective contents of (C) and (D) are (A) and ( B) parts by weight based on 100 parts by weight.)

[Test Example]

The properties of the specimens prepared in Examples 1 to 4, Comparative Examples 1 to 8 and Reference Example 1 were measured by the following method, and the results are shown in Table 2 below.

* Transparency: The transparency (Haze Value) and transmittance (Tt) of a 3 mm sheet were measured according to ASTM D1003, respectively.

* Izod impact strength (kgfcm/cm ² ): Measured according to standard measurement ASTM D256 at 23°C using a specimen of 1/4''.

* Melt Index (g/10min): measured at 220° C. and 10 kg using ASTM D1238.

* Surface resistance (Ω/sq): Using a VMG-1000 HIGHMEGOHM METER (Ando), the surface resistance value was measured by applying a voltage of 250 V to the specimen for 1 minute at 23°C and 50% RH. It shows that the antistatic property is excellent.

Transmittance
(%) transparency
(Haze value) Impact strength
(kgfcm/cm ² ) Melt Index
(g/10min) Surface resistance
(Ω/sq) Example 1 89.1 4.6 17.38 24.28 3.2 X 10 ⁹ Example 2 89.0 4.8 18.27 27.35 3.4 X 10 ⁹ Example 3 87.1 5.4 19.52 25.76 8.3 X 10 ⁸ Example 4 87.4 5.2 19.04 30.11 8.1 X 10 ⁸ Comparative Example 1 89.1 4.7 18.14 21.11 3.1 X 10 ⁹ Comparative Example 2 88.5 4.9 16.99 26.25 3.3 X 10 ⁹ Comparative Example 3 88.9 4.7 17.22 26.18 3.1 X 10 ⁹ Comparative Example 4 87.8 5.8 17.61 25.43 3.0 X 10 ⁹ Comparative Example 5 86.9 6.5 21.01 28.67 3.8 X 10 ⁹ Comparative Example 6 83.3 7.8 16.27 25.72 4.5 X 10 ⁸ Comparative Example 7 88.1 5.2 18.38 28.54 3.2 X 10 ⁹ Comparative Example 8 87.1 5.9 17.38 30.18 3.4 X 10 ⁹ Reference Example 1 89.0 4.7 18.02 20.04 3.2 X 10 ⁹

As shown in Table 2, it was confirmed that the thermoplastic resin compositions prepared by Examples 1 to 4 of the present invention had a proper melt index and excellent transparency, impact strength, and antistatic properties.

On the other hand, when comparing Examples 1 and 2 of the present invention, and the Graft copolymer, the non-graft copolymer and the antistatic agent of the present invention are the same type and content, but do not include the polymer plasticizer of the present invention, Comparative Example 1, It was confirmed that Examples 1 and 2 had transparency, impact resistance, and antistatic properties equal to or greater than that of Comparative Example 1, but also had high fluidity.

In addition, if the conditions other than the polymer plasticizer of the present invention, except for the low molecular plasticizer, are all the same in Comparative Examples 2 to 5 and Comparative Example 2 of the present invention, Example 2 is not only a suitable melt index, but also transparency, It was confirmed that the impact strength and antistatic properties were excellent in all aspects.

Furthermore, in the case of Comparative Example 6 including the antistatic agent of the present invention in excess, it was confirmed that all conditions other than the antistatic agent content of the present invention were significantly lower in transparency and impact strength compared to Examples 1 and 3.

In addition, in the case of Comparative Examples 7 and 8 containing the polymer plasticizer of the present invention in excess, it was confirmed that all conditions other than the polymer plasticizer content were significantly lower in transparency than in Examples 1 and 2, and the melt index was also poor.

Claims (12)

(A) A graft copolymer copolymerized with at least one of a (meth)acrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound in a conjugated diene rubber, and (B) (meth)acrylic acid alkyl ester compound-aromatic 100 parts by weight of a base resin comprising a vinyl compound-vinyl cyan compound non-graft copolymer;
(C) 0.1 to 4 parts by weight of a conductive polymer antistatic agent; And
(D) characterized in that it comprises 0.1 to 3 parts by weight of a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol
Thermoplastic resin composition.
According to claim 1,
The (A) graft copolymer contains 30 to 85% by weight of the (meth)acrylic acid alkyl ester compound, 1 to 30% by weight of the aromatic vinyl compound and 1 to 20% by weight of the vinyl cyan compound in 10 to 60% by weight of the conjugated diene rubber. Characterized by
Thermoplastic resin composition.
According to claim 1,
The (B) non-graft copolymer is characterized in that it contains 40 to 90% by weight of the (meth) acrylic acid alkyl ester compound, 1 to 50% by weight of the aromatic vinyl compound and 1 to 30% by weight of the vinyl cyan compound
Thermoplastic resin composition.
According to claim 1,
The (B) non-graft copolymer is characterized in that the weight average molecular weight is 50,000 to 110,000 g/mol
Thermoplastic resin composition.
According to claim 1,
The base resin is characterized in that it comprises (A) 20 to 80% by weight of the graft copolymer and (B) 20 to 80% by weight of the non-graft copolymer.
Thermoplastic resin composition.
According to claim 1,
The (C) conductive polymer antistatic agent is characterized in that it comprises a polythiophene antistatic agent
Thermoplastic resin composition.
The method of claim 6,
The polythiophene-based antistatic agent is poly (alkylenedioxythiophene), characterized in that
Thermoplastic resin composition.
According to claim 1,
The polymer plasticizer (D) is characterized in that it is a polyester plasticizer
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that the Izod impact strength (1/4'', 23 ℃) measured in accordance with ASTM D256 is 16 kgf·cm/cm ² or more
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that the melt index (220 ℃, 10 kg) measured in accordance with ASTM D1238 is 15 to 40 g/10min
Thermoplastic resin composition.
(A) A graft copolymer copolymerized with at least one of a (meth)acrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound in a conjugated diene rubber, and (B) (meth)acrylic acid alkyl ester compound-aromatic 100 parts by weight of a base resin comprising a vinyl compound-vinyl cyan compound non-graft copolymer;
(C) 0.1 to 4 parts by weight of a conductive polymer antistatic agent; And
(D) 0.1 to 3 parts by weight of a polymer plasticizer having a weight average molecular weight of 1,000 to 40,000 g/mol, comprising kneading and extruding under conditions of 200 to 330°C and 100 to 500 rpm.
Method of manufacturing a thermoplastic resin composition.
It characterized in that it is made of a thermoplastic resin composition according to any one of claims 1 to 10
Molded article.