KR20230034507A - 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. According to the present invention, a resin composition having excellent impact strength and wax resistance and implementing high blackness to satisfy consumer needs, a method for preparing the same, and a molded product comprising the same. To this end, the thermoplastic resin composition comprises (A) 55 to 86 wt% of a polymethacrylate resin; (B) 0.1 to 12 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 250 to 600 nm; and (C) 6 to 27 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 130 to 200 nm, wherein the weight ratio between the graft copolymer (B) and the graft copolymer (C) is 1:0.7 to 1:3.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded products including the same

The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded product including the same, and more particularly, excellent in impact strength and gloss resistance, and high blackness can be realized while providing economic advantages without increasing processing costs. It relates to a thermoplastic resin composition, a method for preparing the same, and a molded article including the same.

In general, ABS (acrylonitrile-butadiene-styrene) resin has excellent impact resistance and excellent processability, so it can be applied to various applications such as automobiles, electric and electronic devices, office equipment, home appliances, toys, and stationery, and is widely used.

However, ABS resin is easily oxidized by oxygen, ultraviolet rays, light and heat due to the double bond of butadiene rubber in the resin, resulting in discoloration of the resin, and thus has low weather resistance and chemical resistance. Accordingly, the exterior quality of interior and exterior materials to which the resin is applied is deteriorated. There was a problem that it was degraded and could not satisfy the level of demand of consumers.

In order to solve this problem, in the art, ASA (acrylonitrile-styrene-acrylate) resin was used instead of ABS resin to improve weather resistance and chemical resistance, which are the biggest drawbacks of ABS resin. However, this ASA resin has a problem in that the glossiness and blackness of the product decrease due to poor colorability.

Recently, automobile manufacturers are making efforts to improve the cost competitiveness of parts by using ASA resin and at the same time to realize a high-quality feeling of molded products by realizing high blackness.

Conventionally, gloss dyes were used to realize the gloss of ASA resin, and PMMA (polymethyl methacrylate), which has a relatively low refractive index, was used in combination to improve blackness, but there was a problem of discoloration.

In addition, black colorant must be used to realize a high level of blackness, but the representative black pigment had difficulty in realizing high blackness due to the difference in refractive index when PMMA and ASA resin were mixed.

Therefore, it is necessary to develop a thermoplastic resin composition capable of satisfying the needs of consumers by realizing high blackness as well as excellent impact strength and gloss resistance properties.

Chinese Patent Publication No. 110483932

In order to solve the problems of the prior art as described above, the present invention is excellent in impact strength and gloss resistance characteristics, and does not increase processing cost, providing economic advantages while providing a high level of blackness. It is an object of the present invention to provide a manufacturing method and a molded product comprising the same.

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

In order to achieve the above object, the present invention

(A) 55 to 86% by weight of a polymethacrylate resin;

(B) 0.1 to 12% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 250 to 600 nm; and

(C) 6 to 27% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 130 to 200 nm;

It provides a thermoplastic resin composition, characterized in that the weight ratio of the (B) graft copolymer and (C) graft copolymer is 1:0.7 to 1:3.

The (A) polymethacrylate resin may have a melt index (230 °C, 3.8 kg) of 2 to 6 g/10min and a Rockwell hardness of 93 to 102.

The (B) graft copolymer may include 45 to 55% by weight of acrylate rubber, 40 to 50% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound.

The (C) graft copolymer may include 45 to 55% by weight of acrylate rubber, 40 to 60% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound.

The thermoplastic resin composition may include at least one selected from the group consisting of a lubricant, an antioxidant, a UV stabilizer, a flame retardant, a release agent, a heat stabilizer, a plasticizer, an abrasion resistance agent, an antistatic agent, an inorganic filler, and a conductive filler.

The thermoplastic resin composition may have a heat distortion temperature (HDT) of 75 °C or higher.

The thermoplastic resin composition is prepared by dropping 0.2 ml of glossy wax on the surface of the specimen, leaving it at room temperature for 24 hours, and then sequentially placing it at 80 ± 2 ° C for 3 hours, 23 ± 2 ° C for 1 hour, 40 ± 2 ° C for 3 hours, After 1 hour at 23 ± 2 ℃, 7 hours at 90 % RH or higher, and 1 hour at 23 ± 2 ℃, the gloss resistance characteristics measured by the SCI measurement method using a colormeter device can have a Delta L value of 17 or less. there is.

The thermoplastic resin composition may have a blackness (L) of 10 or less as measured by SCI using a color meter.

In addition, the present invention

(A) 55 to 86% by weight of a polymethacrylate resin; (B) 0.1 to 12% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 250 to 600 nm; (C) 6 to 27% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 130 to 200 nm; (D) kneading and extruding the additive and (F) the colorant;

It provides a method for producing a thermoplastic resin composition, characterized in that the weight ratio of the (B) graft copolymer and (C) graft copolymer is 1:0.7 to 1:3.

In addition, the present invention

A molded article characterized by comprising the above-described thermoplastic resin composition is provided.

The molded article may be an automobile exterior material.

According to the present invention, there is an effect of providing a thermoplastic resin composition capable of realizing high blackness while providing an economical advantage because it has excellent impact strength and gloss resistance characteristics and does not increase processing cost, a method for manufacturing the same, and a molded product including the same. there is.

In particular, in the case of using conventional ASA resin, there is an advantage in effectively solving the problem of deterioration in gloss and blackness of a product due to poor colorability.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method for preparing the same, and a molded product including the same will be described in detail.

Terms or words used in this specification and claims should not be construed as being limited to their usual or dictionary meanings, and given that the inventors may appropriately define the concept of terms in order to best describe the invention. Therefore, it should be interpreted as meaning and concept consistent with the technical spirit of the present invention.

In the present description, the meaning of "comprising" may be defined as "containing and polymerizing", "including and polymerizing" or "including as a derived unit" unless otherwise defined.

In this description, the weight average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. It is a value obtained by applying the weight average molecular weight (Mw) in terms of polystyrene by permeation chromatography (GPC: gel permeation chromatography, PL GPC220, Agilent Technologies).

Specifically, the polymer to be measured was dissolved in tetrahydrofuran to a concentration of 1%, and 10 μl was injected into GPC, flowing at a flow rate of 0.3 mL/min, and 30 μl for a sample concentration of 2.0 mg/mL (100 μl injection). The assay can be performed at °C. Here, the column may be connected in series with two PLmixed B from Waters, and the detector may be measured at 40 ° C using an RI detector (2414, manufactured by Agilent Waters) and then processed using ChemStation.

In the present description, "property of resisting gloss wax" means a property that resists discoloration and deformation of the surface by gloss wax unless otherwise defined.

In the present description, the composition ratio of the (co)polymer may mean the amount of units constituting the (co)polymer, or the amount of units introduced during polymerization of the (co)polymer.

In this description, "content" means weight unless otherwise defined, and "%" means weight% unless otherwise defined.

When the present inventors include a resin with a relatively low refractive index and a specific content of two types of ASA resins with different average particle diameters, additional processing processes such as painting or plating process are omitted to increase economic efficiency while improving both mechanical properties and blackness In particular, it was confirmed that it can be applied in high quality with a luxurious feel to fields requiring high impact strength and glossy wax characteristics, such as automobile exterior materials, and based on this, further devoted to research and completed the present invention.

The thermoplastic resin composition of the present invention includes (A) 55 to 86% by weight of a polymethacrylate resin; (B) 0.1 to 12% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 250 to 600 nm; and (C) 6 to 27% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 130 to 200 nm. And it has an advantage of being able to implement high blackness while providing an economical advantage because it has excellent gloss resistance and does not increase processing cost.

In the present description, a polymer comprising a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.

The (A) polymethacrylate resin is, for example, (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 It may be at least one polymer selected from the group consisting of (meth)acrylic acid lauryl ester, preferably a methyl methacrylate polymer, and in this case, it has appropriate fluidity and excellent weather resistance and heat resistance.

The (A) polymethacrylate resin is, for example, (A) a polymethacrylate resin, (B) a graft copolymer, (C) a graft copolymer, and (D) additives to be described below, based on 100% by weight of 55 to 86% by weight, 60 to 86% by weight, or 62 to 84% by weight, preferably 63 to 83% by weight, and within this range, not only excellent impact strength and gloss resistance properties, but also a high level of By realizing blackness, there is an advantage in that it can be applied with high quality to automobile parts such as automobile exterior materials.

When the content of the polymethacrylate resin (A) is less than the above range, the blackness is lowered, and when it exceeds the above range, a weak impact problem occurs.

The (A) polymethacrylate resin may have, for example, a glass transition temperature of 105 ° C. or more, preferably 110 to 120 ° C., and excellent heat resistance within this range, particularly requiring high heat resistance, such as automotive exterior materials. There is an advantage that it can be applied with high quality to the field of application.

In the present description, the glass transition temperature (Tg) can be measured using a differential scanning calorimetry (DSC), and as a specific example, it can be measured using a differential scanning calorimeter manufactured by TA Instrument.

The (A) polymethacrylate resin may have, for example, a melt index of 2 to 6 g/10min, 2.1 to 5.5 g/10min, preferably 2.3 to 5 g/10min, and fluidity within this range. This is excellent and can provide an advantage of easy injection molding into various shapes.

In this substrate, the melt index can be measured under the condition of 230 ° C. and 3.8 kgf according to standard measurement ASTM D1238.

The (A) polymethacrylate resin may have a Vicat softening point of 105 to 115 ° C, preferably 108 to 110 ° C, and has excellent heat resistance within this range, especially in areas requiring high heat resistance such as automobile exterior materials. There are advantages that can be applied as

Unless otherwise specified herein, the Vicat softening point is measured using a Vicat measuring device under B/50 conditions.

The (A) polymethacrylate resin may have a Rockwell hardness of 93 to 102, specifically 97 to 100, and has excellent hardness within this range, so that it can be applied with high quality to fields requiring high hardness, such as automobile exterior materials. There is an advantage to being

Unless otherwise specified in this description, the Rockwell hardness is 60 in accordance with ASTM D785 and ISO 2039, using a specimen with a thickness of 1/2", placing the measuring part on a flat surface, and using an R-scale offset of 1.0. Measure the hardness when a force of kfg/cm ² is applied At this time, Zwick's ZHR can be used as the measuring equipment.

The (B) graft copolymer of the present description may be, for example, an acrylate "(rubber)"-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 250 to 600 nm, In this case, there is an advantage in that it has excellent impact strength and gloss resistance characteristics, and provides economic advantages by not increasing processing cost while realizing high blackness.

The (B) acrylate rubber included in the graft copolymer may have an average particle diameter of, for example, 250 to 600 nm, or 300 to 500 nm, and preferably 350 to 450 nm, and the impact strength within this range is It has an excellent effect.

In the present substrate, the average particle diameter of the graft copolymer is a specimen that is extruded with a heterogeneous resin such as polymethacrylate resin by microtoming in a pellet or strand state. (B) Penetrates the graft copolymer It can be measured using an electron microscope (TEM) ER100.

The (B) graft copolymer may include, for example, 43 to 48% by weight of acrylate rubber, 37 to 40% by weight of an aromatic vinyl compound, and 15 to 18% by weight of a vinyl cyan compound, and within this range, painting or By omitting an additional processing process such as a plating process, economic feasibility is increased, and excellent heat resistance, scratch resistance, and high blackness are all satisfied.

The acrylate rubber may be, for example, an alkyl acrylate rubber, and the alkyl acrylate rubber may be, for example, an acrylate rubber having 1 to 10 carbon atoms in an alkyl group.

The aromatic vinyl compound included in the (B) graft copolymer may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, 2,4-dimethyl styrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Yes, preferably styrene.

The vinyl cyanide compound included in the (B) graft copolymer may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The (B) graft copolymer is, for example, (A) polymethacrylate resin, (B) graft copolymer, (C) graft copolymer, and (D) additives to be described later, based on 100% by weight of 0.1 to 0.1% by weight It may be 12% by weight, or 1 to 12% by weight, preferably 7.5 to 15% by weight, and within this range, impact strength and gloss resistance are excellent, as well as a high level of blackness is realized, especially for automobiles. There is an advantage that it can be applied in high quality to automobile parts such as exterior materials.

When the content of the (B) graft copolymer is less than the above range, the impact strength decreases, and when it exceeds the above range, blackness decreases.

The (C) graft copolymer of the present description may be, for example, an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an acrylate rubber having an average particle diameter of 130 to 200 nm, in which case the impact strength and It has excellent gloss resistance properties and provides economic benefits by not increasing processing costs while realizing high blackness.

The (C) acrylate rubber included in the graft copolymer may have, for example, an average particle diameter of 130 to 200 nm, or 130 to 180 nm, preferably 130 to 170 nm, and within this range, high blackness and has excellent heat resistance, gloss resistance and processability.

The (C) graft copolymer may include, for example, 45 to 50% by weight of acrylate rubber, 40 to 45% by weight of an aromatic vinyl compound, and 10 to 15% by weight of a vinyl cyan compound. It has the advantages of realizing the degree and excellent heat resistance, gloss resistance and processability.

The (C) graft copolymer is, for example, (A) a polymethacrylate resin, (B) a graft copolymer, (C) a graft copolymer, and (D) additives described later. Based on 100% by weight of the total It may be 6 to 27% by weight, or 6 to 23% by weight, preferably 7 to 11% by weight, and within this range, not only excellent gloss resistance wax characteristics but also a high level of blackness are realized, especially for automotive exterior materials There is an advantage that it can be applied in high quality to automobile parts such as

When the content of the (C) graft copolymer is less than the above range, impact strength is lowered, and when it is above the above range, blackness is lowered.

The types of the acrylate rubber, aromatic vinyl compound, and vinyl cyan compound included in the (C) graft copolymer are the acrylate rubber, aromatic vinyl compound, and vinyl cyan compound included in the graft copolymer (B) of the present description. It may be within the same category as the type.

The weight ratio of the graft copolymer (B) and the graft copolymer (C) may be, for example, 1:0.7 to 1:3, specific examples 1:0.5 to 1:2.3, and preferably 1:0.7 to 2.3. Within this range, additional processing processes such as painting or plating process are omitted to increase economic feasibility, while having excellent impact strength and gloss resistance wax characteristics and realizing a high level of blackness, making it particularly suitable for automotive parts such as automobile exterior materials. It has the advantage of being applied in high quality.

The thermoplastic resin composition of the present substrate includes, for example, at least one additive selected from the group consisting of a lubricant, an antioxidant, a UV stabilizer, a flame retardant, a mold release agent, a heat stabilizer, a plasticizer, an anti-wear agent, an antistatic agent, an inorganic filler, and a conductive filler. In this case, there is an advantage in that impact strength and gloss resistance are excellent at the same time without deterioration in mechanical properties.

The additive is, for example, 0.1 to 10% by weight, or 0.5% by weight, based on 100% by weight of the total of (A) polymethacrylate resin, (B) graft copolymer, (C) graft copolymer and (D) additives. to 8% by weight, preferably 1 to 7% by weight.

The lubricant may be, for example, at least one selected from the group consisting of ethylene bis stearate, oxidized polyethylene wax, and magnesium stearate, and preferably may be ethylene bis stearate, in which case the wettability of the composition of the present invention is improved. At the same time, there are excellent effects such as heat resistance and gloss resistance wax characteristics.

For example, the lubricant may be 0.1 to 3% by weight based on 100% by weight of the total of (A) polymethacrylate resin, (B) graft copolymer, (C) graft copolymer and (D) additives, preferably It may be 0.5 to 1.2% by weight, and within this range, there is an effect of improving the wettability of the composition of the present substrate and at the same time having excellent mechanical properties.

As the antioxidant, for example, a known antioxidant formulated in a thermoplastic resin composition may be used. Examples of such antioxidants include phosphorus antioxidants and phenolic antioxidants. Among them, hindered phenolic antioxidants are preferably used, for example, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , thiodiethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like, in which case the polymerization reaction is facilitated to improve mechanical properties, weather resistance and heat resistance. And there is an effect of maintaining excellent scratch resistance.

For example, the UV stabilizer may be at least one selected from the group consisting of hindered amine, hydroxyphenyl benzotriazole, and hydroxyphenyl triazine.

The UV stabilizer is, for example, 0.1 to 3% by weight, or 0.3 to 0.3% by weight, based on 100% by weight of (A) polymethacrylate resin, (B) graft copolymer, (C) graft copolymer and (D) additives It may be 2% by weight, preferably 0.5 to 1% by weight, and within this range, there is an effect of maintaining excellent heat resistance and gloss resistance without deteriorating mechanical properties.

The heat stabilizer is, for example, tris (nonylphenyl) phosphite (tris (nonylphenyl) phosphite), tris (2,4-di-t-butylphenyl) phosphite (tris (2,4-dit-butyl phenyl) phosphite; TBPP), 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite (2,4,6-tri-tert-butylphenyl-2-butyl-2 -ethyl-1,3-propanediol phosphite), diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t -butylphenyl) pentaerythritol diphosphite (bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; PEP24), bis (2,4-di-cumylphenyl) pentaerythritol diphosphite (bis (2 ,4-dicumylphenyl)pentaerythritol diphosphite), and tetrakis(2,4-di-t-butylphenyl)[1,1-biphenyl]-4,4'-diyl bisphosphonite (tetrakis(2,4- di-tertbutylphenyl) [1,1-biphenyl] -4,4'-diyl bisphosphonate) may be one or more selected from the group consisting of.

For example, the heat stabilizer may be 0.1 to 1% by weight based on 100% by weight of the total of (A) polymethacrylate resin, (B) graft copolymer, (C) graft copolymer and (D) additives, It is preferably 0.3 to 0.7% by weight, and within this range, there is an effect of excellent heat resistance.

In the present disclosure, flame retardants used in related fields may be used as long as they do not affect impact strength, gloss resistance, and high blackness.

Examples of the flame retardant include phosphate-based, phthalate-based, and halogen-based flame retardants, and any one or two or more of these may be used.

In the present description, the release agent used in the related art may be used as long as it does not affect impact strength, gloss resistance, and high blackness.

In the present description, the plasticizer used in the related art may be used as long as it does not affect impact strength, gloss resistance, and high blackness.

In this description, the antistatic agent used in the related art may be used as long as it does not affect impact strength, gloss resistance, and high blackness.

In the present disclosure, inorganic fillers used in the related art may be used as long as they do not affect impact strength, gloss resistance, and high blackness. However, care should be taken when using glass fibers in molded products for which the appearance characteristics are important, as the appearance characteristics may be deteriorated.

In the present description, the type of conductive filler used in the related art may be used as long as it does not affect impact strength, gloss resistance, and high blackness.

The colorant may be, for example, a black dye, and as a specific example, may be selected from anthraquinone dyes and nonanthraquinone dyes. In this case, there is an advantage in providing a product having a luxurious appearance due to a high level of blackness.

The colorant is 0.1 to 4 parts by weight, or 0.5 to 3.5 parts by weight based on 100 parts by weight of the total content of (A) polymethacrylate resin, (B) graft copolymer, (C) graft copolymer and (D) additives It may be negative, and within this range, there is an effect of achieving excellent heat resistance and high blackness.

The thermoplastic resin composition of the present substrate may have, for example, a tensile strength of 48 MPa or more, 48 to 55 Mpa, or 48 to 51 Mpa, measured according to ISO 527, and excellent mechanical properties are effective within this range.

The thermoplastic resin composition of the present substrate has, for example, a Charpy notch impact strength (1/4″, 23 ° C.) of 3 kJ/m ² or more, 3.5 to 10 kJ/m ² , or 3.7 to 8.5 kJ, measured according to ISO 179. / m ² , and within this range, there is an effect of excellent impact resistance.

The thermoplastic resin composition of the present substrate may have a flexural strength of, for example, 65 MPa or more, 65 to 70 Mpa, or 65 to 68 Mpa, respectively, measured according to ISO 178, and excellent mechanical properties are obtained within this range.

The thermoplastic resin composition of the present substrate may have, for example, a flexural modulus of 1900 MPa or more, 1900 to 2200 Mpa, or 1970 to 2010 Mpa, respectively, measured according to ISO 178, and excellent mechanical properties are effective within this range.

The thermoplastic resin composition of the present substrate may have, for example, a heat deflection temperature of 75 ° C. or more, 75 to 80 ° C., preferably 75 to 77 ° C., and the effect of improving heat resistance while maintaining excellent physical property balance within this range there is

The thermoplastic resin composition of the present substrate may have, for example, a blackness (L) of 10 or less, preferably 1.0 to 7.5, and has the advantage of providing a product with a luxurious feeling by implementing a high blackness within this range. there is.

For example, the thermoplastic resin composition of the present substrate is prepared by dropping 0.2 ml of gloss wax on the surface of a specimen, leaving it at room temperature for 24 hours, and then sequentially placing it at 80 ± 2 ° C for 3 hours, at 23 ± 2 ° C for 1 hour, and then at 40 ± 2 ° C. 3 hours at 23 ± 2 ℃, 1 hour at 23 ± 2 ℃, 7 hours at 90 % RH or higher, 1 hour at 23 ± 2 ℃, then the gloss resistance characteristics measured by the SCI measurement method using a colormeter device are Delta L values It may be 17 or less, 12 to 16.5, and in this case, there is an effect of excellent gloss resistance wax properties.

Hereinafter, a method for preparing the thermoplastic resin composition of the present invention will be described.

In describing the manufacturing method of the thermoplastic resin composition of the present description, all contents of the thermoplastic resin composition described above are included.

A method for producing the thermoplastic resin composition of the present disclosure is, for example, (A) 55 to 86% by weight of a polymethacrylate resin; (B) 0.1 to 12% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 250 to 600 nm; (C) 6 to 27% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 130 to 200 nm; It is characterized in that it includes the step of kneading and extruding (D) the additive and (F) the colorant, and in this case, the impact strength and gloss resistance properties are excellent, and the processing cost is not increased, providing economic advantages while providing high blackness. There are advantages to implementing

The method for preparing the thermoplastic resin composition may include, for example, (A) preparing a polymethacrylate resin, and the (A) polymethacrylate resin prepared in this step is then (B) a graft copolymer And (C) it can be extruded by kneading with a graft copolymer.

In the method for preparing the thermoplastic resin composition, kneading and extrusion may be performed through a single screw extruder, a twin screw extruder, or a Banbury mixer, and preferably performed through a twin screw extruder, in which case the composition is uniformly dispersed for compatibility. This has an excellent effect.

The step of producing pellets using the extrusion kneader may be performed, for example, within a range of a barrel temperature of 200 to 240° C., preferably 210 to 230° C., in which case, adequate and sufficient melt kneading is performed per unit time. It may be possible, and there is an effect of not causing problems such as thermal decomposition of the resin component.

The step of producing pellets using the extrusion kneader may be performed, for example, under the condition that the number of rotations of the screw is 200 to 300 rpm, preferably 250 to 300 rpm, and in this case, the throughput per unit time is appropriate and the process efficiency is excellent It has the effect of suppressing excessive cutting.

The thermoplastic resin composition pellets may be manufactured into an injection-molded article using an injection molding machine, for example, under an injection barrel temperature of 210 to 240 °C, preferably 220 to 230 °C.

Hereinafter, a molded article comprising the thermoplastic resin composition of the present invention will be described. In describing the molded article of the present invention, all contents of the above-described thermoplastic resin composition are included.

The molded product of the present substrate may be, for example, a molded product containing the thermoplastic resin composition of the present substrate, and the molded product has excellent impact strength and gloss resistance characteristics, resulting in little change by the external environment and a high level of blackness. It has the effect of providing a luxurious feeling.

The molded article may be, for example, an automobile exterior material, and in this case, the thermoplastic resin composition of the present substrate satisfies all of the heat resistance, gloss resistance wax characteristics, high blackness, and economic feasibility required by the market, thereby providing a high-quality molded article. .

The automotive exterior material may be, for example, a side mirror housing, a radiator grill, a filler garnish, a fog light garnish, and the like, which provides economical advantages by increasing cost competitiveness compared to the prior art, while satisfying all of heat resistance, gloss resistance characteristics, and high blackness, It has the advantage of satisfying consumer needs.

In describing the thermoplastic resin composition of the present description, its manufacturing method and molded article, it is stated that other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art and are not particularly limited. do.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, It goes without saying that these variations and modifications fall within the scope of the appended claims.

[Example]

Materials used in the following Examples and Comparative Examples are as follows.

(A) PMMA resin: polymethyl methacrylate (230 ° C., 3.8 kg load, melt index 2.3 to 5.0 g / 10 min, Vicat softening point 109 ° C., Rockwell hardness 96-99 measured by R-scale under ASTM D785 conditions)

(B) Graft copolymer: Graft copolymer having an average particle diameter of 340 nm of acrylate rubber (45% by weight of acrylate rubber, 39% by weight of styrene, 16% by weight of acrylonitrile)

(C) Graft copolymer: Graft copolymer having an average particle diameter of acrylate rubber of 170 nm (46% by weight of acrylate rubber, 41% by weight of styrene, 13% by weight of acrylonitrile)

(D) additives

* Lubricant: Ethylene Bis Stearamide (EBA)

* Thermal stabilizer: BASF's IR1076

* UV stabilizer: BASF's Tin-770

(E) Acrylic rubber: Dow Chemical's PARALOID KM-357

(G) Graft Copolymer: A graft copolymer having an average particle diameter of 120 nm of acrylate rubber (43 wt% of acrylate rubber, 39 wt% of styrene, 18 wt% of acrylonitrile)

Examples 1 to 4

According to the components and contents shown in Table 1 below, the (A) PMMA resin, (B) graft copolymer, (C) graft copolymer, (D) additive and (F) colorant were mixed and then L / D = A resin composition in a pellet state was prepared by melting and kneading at a temperature range of 220 to 230 ° C. using a twin-screw extruder having a diameter of 42 and Φ = 40 mm. At this time, 0.6 parts by weight of the colorant (F) was added based on 100 parts by weight of the total amount of (A), (B), (C) and (D). Also, as additives (D), 1.0 parts by weight of a scratch resistant agent, 1.0 parts by weight of a lubricant, 0.2 parts by weight of a heat stabilizer, and 0.4 parts by weight of a UV stabilizer were added.

The prepared resin composition in a pellet state was dried at 80 ° C. for 4 hours or more, then injected at an injection temperature of 220 to 230 ° C. and a mold temperature of 60 ° C., and stored in a constant temperature and humidity room at 23 ° C. for 24 hours or more.

Comparative Examples 1 to 8

According to the components and contents shown in Table 2 below, the (A) PMMA resin, (B) graft copolymer, (C) graft copolymer, (D) additive, (E) acrylic rubber, (F) colorant, and (G) After mixing the graft copolymer, a resin composition in a pellet state was prepared by melting and kneading at a temperature range of 220 to 230 ° C using a twin screw extruder having L / D = 42 and Φ = 40 mm. At this time, 0.6 parts by weight of the colorant (F) was added based on 100 parts by weight of the total amount of (A), (B), (C), (D), (E), (F) and (G). Also, as additives (D), 1.0 parts by weight of a scratch resistant agent, 1.0 parts by weight of a lubricant, 0.2 parts by weight of a heat stabilizer, and 0.4 parts by weight of a UV stabilizer were added.

The prepared resin composition in a pellet state was dried at 80 ° C. for 4 hours or more, then injected at an injection temperature of 220 to 230 ° C. and a mold temperature of 60 ° C., and stored in a constant temperature and humidity room at 23 ° C. for 24 hours or more.

Reference Examples 1 to 3

According to the components and contents shown in Table 3, the (A) PMMA resin, (B) graft copolymer, (C) graft copolymer, (D) additive, and (F) colorant were mixed and then L / D = 42, Φ = 40 mm using a twin-screw extruder was melted and kneaded at a temperature range of 220 to 230 ℃ to prepare a resin composition in a pellet state. At this time, 0.6 parts by weight of the colorant (F) was added based on 100 parts by weight of the total amount of (A), (B), (C), (D) and (F). Also, as additives (D), 1.0 parts by weight of a scratch resistant agent, 1.0 parts by weight of a lubricant, 0.2 parts by weight of a heat stabilizer, and 0.4 parts by weight of a UV stabilizer were added.

The prepared resin composition in a pellet state was dried at 80 ° C. for 4 hours or more, then injected at an injection temperature of 220 to 230 ° C. and a mold temperature of 60 ° C., and stored in a constant temperature and humidity room at 23 ° C. for 24 hours or more.

[Test Example]

The characteristics of the specimens prepared in Examples 1 to 4, Comparative Examples 1 to 8, and Reference Examples 1 to 3 were measured by the following method, and the results are shown in Tables 1 to 3 below, respectively.

* Tensile strength: The tensile strength of the specimen was measured at a rate of 50 mm/min according to ISO 527.

* Flexural strength and elastic modulus: The flexural properties of the specimen were measured at a rate of 2 mm/min according to ISO 178.

* Charpy impact strength: The impact strength of a notched Charpy injection specimen was measured according to ISO 179 using a specimen thickness of 4 mm.

* Heat deflection temperature (HDT): measured under 1.8 MPa in the flat direction using a specimen having a thickness of 4 mm in accordance with ISO 75.

* Blackness: SCI standard blackness (L value) was measured using a color meter (model name: Color Eye 7000A) after injection of a rectangular specimen with a thickness of 3mm X 10cm in width X 10cm in length. The lower the L value, the better the black feeling.

* Characteristics of gloss-resistant wax: Each of three types of glossy wax, CHEMICAL GUYS' SPEED WIPE, Bullsone's Crystal COAT PLUS, and PIAA's ACCUR, were used as glossy wax on a rectangular specimen with a thickness of 3mm X 10cm in width X 10cm in length, and 0.2 After dropping ml, it was left at room temperature for 24 hours.

Then, sequentially, 3 hours at 80 ± 2 °C, 1 hour at 23 ± 2 °C, 3 hours at 40 ± 2 °C, 1 hour at 23 ± 2 °C, 7 hours at 90 % RH or higher, 23 After placing at ± 2 ° C. for 1 hour, the SCI standard blackness (L value) was measured using a Colormeter (model name Color Eye 7000A). The temperature condition of 23° C. indicates that it was left in a constant temperature and humidity room, and a temperature higher than that indicates that it was treated by putting it into a gear oven.

In Tables 1 to 3, the measurement results of CHEMICAL GUYS' SPEED WIPE product are shown as Polish wax 1, Bullsone's Crystal COAT PLUS product measurement result as Polish wax 2, and PIAA's ACCUR product measurement result as Polish wax 3.

division Example 1 Example 2 Example 3 Example 4 Furtherance (A)PMMA 64.4 82.4 82.4 82.4 (B) Graft 10 7.5 8.0 8.5 (C) Graft 23 7.5 7.0 6.5 (D) additives 2.6 2.6 2.6 2.6 Properties Tensile strength [MPa] 48 51 50 51 Charpy impact strength [kJ/m ² ] 8.5 3.7 4.3 4.6 Flexural strength [MPa] 68 65 65 65 Flexural modulus [MPa] 2090 2000 1985 1980 Heat deflection temperature [°C] 75 77 77 77 Blackness (L) 7.54 1.02 1.13 1.23 polish wax 1
[Delta L] 1.47 2.23 2.11 2.05 polish wax 2
[Delta L] 2.2 3.21 2.86 2.62 polish wax 3
[Delta L] 16.09 12.34 12.60 13.02

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Furtherance (A) PMMA 64.4 64.4 64.4 64.4 64.4 64.4 67.4 82.9 (B) Graft 33 - - 23 - - 7 7.5 (C) Graft - - 33 - - 23 23 - (D) additives 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 (E) Acrylic rubber - - - 10 10 10 - 7.5 (G) Graft - 33 - - 23 - - - Properties Tensile strength [MPa] 45 51 50 43 47 47 47 45 Charpy impact strength [kJ/m ² ] 7.7 5.6 4.8 8.1 7.0 6.4 5.9 4.4 Flexural strength [MPa] 63 70 70 60 62 63 67 64 Flexural modulus [MPa] 1990 2160 2120 1880 1950 1930 2020 2010 heat deflection temperature
[℃] 75 75 76 74 75 75 75 76 Blackness (L) 13.74 4.55 1.87 14.99 7.63 6.72 4.32 1.22 polish wax 1
[Delta L] 0.22 2.68 4.38 1.05 4.90 4.08 1.88 5.06 polish wax 2
[Delta L] 2.28 4.16 2.56 4.26 5.85 5.86 2.14 8.66 polish wax 3
[Delta L] 17.27 14.01 11.80 20.04 22.92 23.31 16.31 24.19

division Reference example 1 Reference example 2 Reference example 3 Furtherance (A)PMMA 50 90 64.4 (B) Graft 10 7.4 18.0 (C) Graft 37.4 - 15.0 (D) additives 2.6 2.6 2.6 Properties Tensile strength [MPa] 45 64 48 Charpy impact strength [kJ/m ² ] 8.7 2.2 9.0 Flexural strength [MPa] 66 101 68 Flexural modulus [MPa] 1960 2740 2000 Heat deflection temperature [°C] 73 82 75 Blackness (L) 7.88 1.03 9.33 polish wax 1
[Delta L] 1.26 5.01 1.11 polish wax 2
[Delta L] 2.13 7.98 2.1 polish wax 3
[Delta L] 15.51 22.38 16.90

As shown in Table 1, it was confirmed that, when prepared according to Examples 1 to 4 of the present invention, it had mechanical properties equal to or better than, excellent impact strength and gloss resistance, and high blackness.

On the other hand, as shown in Table 2, (C) in the case of Comparative Example 1 without introducing the graft copolymer, it was confirmed that the impact strength was poor and high blackness could not be realized.

In addition, in the case of Comparative Example 2 in which (E) graft copolymer was added instead of (B) graft copolymer and (C) graft copolymer, it was confirmed that the wax resistance property was not provided.

In addition, (B) In the case of Comparative Example 3 in which the graft copolymer was not introduced, it was confirmed that the wax resistant property was not provided.

In addition, in the case of Comparative Examples 4 and 8 in which (C) graft copolymer was not introduced and (E) acrylic rubber was added, flexural modulus, heat distortion temperature, blackness, and gloss resistance were not realized. Able to know.

In addition, in the case of Comparative Example 5 in which (E) acrylic rubber was added while (G) graft copolymer was added instead of (B) graft copolymer and (C) graft copolymer, flexural modulus, blackness, and gloss resistance wax It can be seen that the characteristic is not implemented.

In addition, in the case of Comparative Example 6 in which (E) acrylic rubber was added while (B) the graft copolymer was not introduced, it can be seen that the flexural modulus, blackness, and gloss resistance characteristics of the wax were not implemented.

In addition, in the case of Comparative Example 7 in which the weight ratio of (B) graft copolymer and (C) graft copolymer was out of 1:0.7 to 1:3, it can be seen that the impact strength was poor.

Furthermore, in the case of Reference Examples 1 and 2 in which the content of (A) is small or excessive, it can be seen that blackness, flexural modulus or impact strength are poor.

In addition, (B) it can be seen that in the case of Reference Example 3 in which the graft copolymer is out of the appropriate amount, the impact strength is poor.

In conclusion, when graft copolymers having different average particle diameters and specific content ratios are blended with polymethacrylate resins having a relatively low refractive index, not only are the impact strength and gloss resistance characteristics excellent, but also high blackness is realized. It was confirmed that a thermoplastic resin composition suitable for a molded article that can satisfy the needs of consumers is provided.

Claims (11)

(A) 55 to 86% by weight of a polymethacrylate resin;
(B) 0.1 to 12% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 250 to 600 nm; and
(C) 6 to 27% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 130 to 200 nm;
The thermoplastic resin composition, characterized in that the weight ratio of the (B) graft copolymer and (C) graft copolymer is 1:0.7 to 1:3. According to claim 1,
The (A) polymethacrylate resin has a melt index (230 ℃, 3.8 kg) of 2 to 6 g / 10 min, and a Rockwell hardness of 93 to 102, characterized in that the thermoplastic resin composition. According to claim 1,
The (B) graft copolymer is a thermoplastic resin composition, characterized in that it comprises 43 to 48% by weight of acrylate rubber, 37 to 40% by weight of an aromatic vinyl compound, and 15 to 18% by weight of a vinyl cyan compound. According to claim 1,
The (C) graft copolymer is a thermoplastic resin composition, characterized in that it comprises 45 to 50% by weight of acrylate rubber, 40 to 45% by weight of an aromatic vinyl compound, and 10 to 15% by weight of a vinyl cyan compound. According to claim 1,
The thermoplastic resin composition comprises at least one selected from the group consisting of a lubricant, an antioxidant, a UV stabilizer, a flame retardant, a mold release agent, a heat stabilizer, a plasticizer, abrasion resistant friction agent, an antistatic agent, an inorganic filler, and a conductive filler. A thermoplastic resin composition to be. According to claim 1,
The thermoplastic resin composition, characterized in that the heat distortion temperature (HDT) of 75 ℃ or more. According to claim 1,
The thermoplastic resin composition is prepared by dropping 0.2 ml of glossy wax on the surface of the specimen, leaving it at room temperature for 24 hours, and then sequentially placing it at 80 ± 2 ° C for 3 hours, 23 ± 2 ° C for 1 hour, 40 ± 2 ° C for 3 hours, After 1 hour at 23 ± 2 ℃, 7 hours at 90 % RH or higher, and 1 hour at 23 ± 2 ℃, the gloss resistance characteristics measured by the SCI measurement method using a colormeter device showed that the Delta L value was 17 or less. Characterized by thermoplastic resin composition. According to claim 1,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the blackness (L) measured on the SCI standard using a color meter is 26 or less. (A) 55 to 86% by weight of a polymethacrylate resin; (B) 0.1 to 12% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 250 to 600 nm; (C) 6 to 27% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 130 to 200 nm; (D) kneading and extruding the additive and (F) the colorant;
The method for producing a thermoplastic resin composition, characterized in that the weight ratio of the (B) graft copolymer and (C) graft copolymer is 1:0.7 to 1:3. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 8. According to claim 10,
The molded article is characterized in that the molded article is an automobile exterior material.