KR20210152736A - 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 article including the same. Particularly, the thermoplastic resin composition includes: (A-1) 25-55 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including acrylate rubber having an average particle diameter of 350-550 nm; (A-2) 3-30 wt% of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer including acrylate rubber having an average particle diameter of 70-200 nm; (B-1) 15-45 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer having a weight average molecular weight of 70,000-120,000 g/mol; and (B-2) 5-30 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer having a weight average molecular weight of 130,000-200,000 g/mol, wherein the combined weight of (A-1) graft copolymer and (A-2) graft copolymer is 45-60 wt%, and the thermoplastic resin composition has a flow index (220℃, 10 kg) of 6.9-10.5 g/10min, as determined according to ASTM D1238. According to the present invention, the thermoplastic resin composition has excellent calendering processability, while showing excellent mechanical properties, such as impact strength, tensile strength and elongation, gloss and surface hardness.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article comprising the same

The present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article including the same, and more particularly, to have excellent calender processability by controlling fluidity, mechanical properties such as impact strength, tensile strength, elongation, gloss and surface hardness. It relates to an excellent thermoplastic resin composition, a method for manufacturing the same, and a molded article comprising the same.

A calender is a rolling machine in which several heating rollers are arranged. In addition, forming a film, sheet, etc. using a calender and coating plastic on the surface of fabric, paper, etc. is called calendering or calendering. A calendering process was applied to manufacture rubber sheets and gradually applied to manufacture vinyl chloride (PVC) films and sheets. This calendering has the disadvantage that it requires a high investment in equipment compared to the extrusion process, but because the quality is superior to that of the extrusion process, it is used a lot, especially for PVC films.

PVC resin is a homopolymer of vinyl chloride and a hybrid polymer containing 50% by weight or more of vinyl chloride, and is one of five general-purpose thermoplastic resins manufactured by suspension polymerization and emulsion polymerization. Among them, polyvinyl chloride resin produced by suspension polymerization is a plasticizer, a stabilizer, a filler, a pigment, a fat sugar (TiO ₂ ) and a variety of processing methods by mixing additives with special functions. It is widely used in films, sheets, wires, pipes, etc. However, PVC resin generates chlorine and hydrogen chloride gas during combustion, which is very harmful in case of fire, and the plasticizer used to give flexibility is a phthalate-based compound, which is an environmental hormone that is harmful to the human body.

In order to solve this problem, research on materials that can replace PVC resin is active. Among them, acrylonitrile-styrene-acrylate resin (hereinafter referred to as 'ASA resin') has only excellent weather resistance and light resistance. In addition, it has excellent colorability, chemical resistance and impact resistance, so it is used in various fields such as automobiles, building materials, and miscellaneous goods. In particular, ASA resin is attracting attention as an eco-friendly material because it has superior processing stability and does not contain heavy metal components compared to PVC resin.

However, ASA resin has a problem in that it is difficult to apply to calendering because it lacks physical properties such as dimensional stability and surface hardness such as press marks compared to PVC resin.

Therefore, there is a need to develop an ASA resin that can be applied to calendering by improving the above problems of the ASA resin.

Korean Patent Publication No. 2006-0118820

In order to solve the problems of the prior art as described above, the present substrate is to provide a thermoplastic resin composition excellent in calendering property by controlling fluidity, mechanical properties such as impact strength, tensile strength, elongation, etc., glossiness and surface hardness do it with

In addition, an object of the present disclosure is to provide a method for preparing the above-mentioned thermoplastic resin composition.

Another object of the present invention is to provide a molded article prepared from the above-mentioned thermoplastic resin composition.

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

In order to achieve the above object, the present substrate includes (A-1) 25 to 55 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 350 to 550 nm; (A-2) 3 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 70 to 200 nm; (B-1) 15 to 45% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 70,000 to 120,000 g/mol; and (B-2) 5 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 130,000 to 200,000 g/mol; including, wherein the (A-1) graft copolymer and the (A-) 2) The sum of the weight of the graft copolymer is 45 to 60% by weight, and the flow index (220°C, 10kg) measured according to ASTM D1238 is 6.9 to 10.5 g/10min. Provides a thermoplastic resin composition do.

The thermoplastic resin composition is preferably a thermoplastic resin composition for calendering.

In addition, the present substrate includes (A-1) 25 to 55 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate having an average particle diameter of 350 to 550 nm; (A-2) 3 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate having an average particle diameter of 70 to 200 nm; (B-1) 15 to 45% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 70,000 to 120,000 g/mol; And (B-2) 5 to 30% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 130,000 to 200,000 g/mol; melt-kneading at 200 to 300° C. and 150 to 250 rpm, The sum of the weights of the (A-1) graft copolymer and the (A-2) graft copolymer is 45 to 60% by weight, and the flow index (220°C, 10kg) measured according to ASTM D1238 is 6.9 It provides a method for producing a thermoplastic resin composition, characterized in that to 10.5 g / 10 min.

In addition, the present substrate provides a molded article comprising the thermoplastic resin composition.

According to the present invention, compared to PVC resin, a thermoplastic resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer that does not contain a phthalate-based compound, which is an environmental hormone substance harmful to the human body, and does not emit toxic gas in case of fire There is an effect of providing a thermoplastic resin composition excellent in calendering properties by controlling the fluidity of the composition, excellent mechanical properties such as impact strength, tensile strength, elongation, gloss and surface hardness, a method for manufacturing the same, and a molded article including the same.

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

The present inventors prescribed two kinds of acrylate-based rubber-aromatic vinyl compound-vinyl cyan compound graft copolymers having rubber particles having different average particle diameters and two kinds of aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights. When the content is used and the fluidity is adjusted within a predetermined range, it is confirmed that the calender processability is improved and the mechanical properties, surface hardness and gloss are excellent, and based on this, further research was completed to complete the present invention.

A detailed look at the thermoplastic resin composition according to the present disclosure is as follows.

The thermoplastic resin composition of the present disclosure includes (A-1) 25 to 55 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 350 to 550 nm; (A-2) 3 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 70 to 200 nm; (B-1) 15 to 45% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 70,000 to 120,000 g/mol; and (B-2) 5 to 30% by weight of an aromatic vinyl compound having a weight average molecular weight of 130,000 g/mol to 200,000 g/mol-vinyl cyan compound copolymer; (A-2) The sum of the weight of the graft copolymer is 45 to 60% by weight, and the flow index (220°C, 10kg) measured according to ASTM D1238 is 6.9 to 10.5 g/10min, In this case, it has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.

(A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer

The acrylate rubber of the (A-1) graft copolymer may have, for example, an average particle diameter of 350 to 550 nm, preferably 400 to 550 nm, and even more preferably 450 to 520 nm, and the tensile strength within this range, There is an excellent effect of mechanical strength such as elongation and impact strength.

In the present description, the average particle diameter can be measured using dynamic light scattering, and in detail, Nicomp 380 equipment (product name, manufacturer: PSS) is used to Gaussian mode intensity (intensity) value can be measured with

The (A-1) graft copolymer may be, for example, 25 to 55 wt%, preferably 27 to 50 wt%, more preferably 30 to 40 wt%, based on the total weight of the thermoplastic resin composition, in this range It has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

The (A-1) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range Mechanical strength such as tensile strength, elongation and impact strength is excellent.

As a preferred example, the (A-1) graft copolymer may include 45 to 55 wt% of an acrylate rubber, 30 to 40 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound, within this range It has excellent mechanical strength such as tensile strength, elongation and impact strength.

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

The (A-1) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, mechanical strength such as tensile strength, elongation and impact strength is excellent.

The emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.

In the present invention, the acrylate may be, for example, at least one selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acrylate or ethylhexyl acrylate.

In the present invention, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and preferably styrene.

In the present invention, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.

(A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer

The (A-2) acrylate rubber of the graft copolymer may have, for example, an average particle diameter of 70 to 200 nm, preferably 100 to 170 nm, more preferably 120 to 150 nm, and the thermoplastic finally manufactured within this range Excellent impact strength and glossiness can be imparted to the resin composition.

The (A-2) graft copolymer may be, for example, 3 to 30 wt%, preferably 5 to 27 wt%, more preferably 15 to 25 wt%, based on the total weight of the thermoplastic resin composition, in this range It has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

The (A-2) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, within this range There is an effect excellent in glossiness and surface hardness.

As a preferred example, the (A-1) graft copolymer may include 45 to 55 wt% of an acrylate rubber, 30 to 40 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound, within this range It has an excellent effect of glossiness and surface hardness.

The (A-2) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, glossiness and surface hardness are excellent.

The emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.

The (A-1) graft copolymer and the (A-2) graft copolymer have, for example, a total weight of 45 to 60% by weight, preferably 50 to 60% by weight, more preferably 53 to 57 It may be in weight %, and within this range, it has excellent calendering properties and has excellent effects in mechanical properties such as impact strength, tensile strength, elongation, glossiness and surface hardness, and if it exceeds the above range, it is torn or torn during sheet production The sheet or resin adheres to the roll and deteriorates the quality.

The (A-1) graft copolymer may be included in an amount greater than that of the (A-2) graft copolymer, and more preferably the (A-1) graft copolymer and the (A-1) graft copolymer. -2) the graft copolymer may have a weight ratio of 1: 0.07 to 1: 0.85, more preferably 1: 0.1 to 1: 0.83, even more preferably 1: 0.3 to 1: 0.83, within this range It has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

In the present description, the weight ratio of A and B means the weight ratio of A:B.

(B-1) Aromatic vinyl compound-vinyl cyan compound copolymer

The copolymer (B-1) may have, for example, a weight average molecular weight of 70,000 to 120,000 g/mol, preferably 80,000 to 110,000 g/mol, more preferably 85,000 to 95,000 g/mol, and within this range, calender It has excellent processability, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

In the present description, unless otherwise defined, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent. ) can be measured as a relative value with respect to a standard PS (standard polystyrene) sample.

The copolymer (B-1) may be, for example, 15 to 45 wt%, preferably 18 to 40 wt%, more preferably 20 to 35 wt%, based on the total weight of the thermoplastic resin composition, within this range It has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

The (B-1) copolymer may include, for example, 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyan compound, preferably 65 to 75% by weight of an aromatic vinyl compound and a vinyl cyan compound It can be made by including 25 to 35% by weight, there is an excellent effect of glossiness and surface hardness while excellent calendering within this range.

The copolymer (B-1) may be, for example, a styrene-acrylonitrile copolymer (SAN resin), α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof, more preferably It may be a styrene-acrylonitrile copolymer (SAN resin), and in this case, it has excellent calender processability and excellent gloss and surface hardness.

The styrene-acrylonitrile copolymer preferably contains 65 to 75% by weight of styrene and 25 to 35% by weight of acrylonitrile, and within this range, it has excellent calender processability and excellent gloss and surface hardness. have.

The styrene-acrylonitrile copolymer may be, for example, 70,000 to 120,000 g/mol, preferably 80,000 to 110,000 g/mol, more preferably 85,000 to 95,000 g/mol, and has excellent calendering properties within this range. It has excellent luster and surface hardness.

The copolymer (B-1) may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, preferably bulk polymerization, in which case mechanical properties and the like are excellent.

The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains, respectively.

(B-2) Aromatic vinyl compound-vinyl cyan compound copolymer

The (B-2) copolymer may have, for example, a weight average molecular weight of 130,000 to 200,000 g/mol, preferably 140,000 to 190,000 g/mol, more preferably 150,000 to 170,000 g/mol, and within this range, the calender It has excellent processability, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

The (B-2) copolymer may be, for example, 5 to 30 wt%, preferably 8 to 25 wt%, more preferably 10 to 25 wt%, based on the total weight of the thermoplastic resin composition, within this range It has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, as well as excellent gloss and surface hardness.

The (B-2) copolymer may include, for example, 60 to 80 wt% of an aromatic vinyl compound and 20 to 40 wt% of a vinyl cyan compound, preferably 65 to 75 wt% of an aromatic vinyl compound and a vinyl cyan compound It may be made by including 25 to 35% by weight, and within this range, calendering property is excellent, and mechanical properties such as impact strength, tensile strength, elongation, etc., gloss and surface hardness are excellent.

The copolymer (B-2) may be, for example, a styrene-acrylonitrile copolymer (SAN resin), α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof, more preferably It may be a styrene-acrylonitrile copolymer (SAN resin), and in this case, it has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, and excellent gloss and surface hardness.

The styrene-acrylonitrile copolymer preferably contains 65 to 75% by weight of styrene and 25 to 35% by weight of acrylonitrile. It has excellent mechanical properties, glossiness and surface hardness.

The styrene-acrylonitrile copolymer may be, for example, 130,000 to 200,000 g/mol, preferably 140,000 to 190,000 g/mol, more preferably 150,000 to 170,000 g/mol, and has excellent calendering properties within this range. It has excellent mechanical properties such as impact strength, tensile strength, and elongation.

The copolymer (B-2) may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization, preferably bulk polymerization, in which case mechanical properties and the like are excellent.

The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains, respectively.

The (B-1) copolymer and the (B-2) copolymer have, for example, a difference in weight average molecular weight of 60,000 to 80,000 g/mol, preferably 65,000 to 75,000 g/mol, more preferably 68,000 to 73,000 It may be g/mol, and within this range, calendering property is excellent, and mechanical properties such as impact strength, tensile strength, elongation, etc., glossiness and surface hardness are excellent.

The copolymer (B-1) may preferably be included in an amount greater than that of the copolymer (B-2), and more preferably, the weight ratio of the copolymer (B-1) to the copolymer (B-2). is 1: 0.2 to 1: 0.4, more preferably 1: 0.25 to 1: 0.35, within this range, there is an effect of more excellent gloss and elongation.

Thermoplastic resin composition

The thermoplastic resin composition of the present invention preferably has a calendering thermoplastic resin composition, for example, a flow index (220° C., 10 kg) measured according to ASTM D1238 of 6.9 to 10.5 g/10min, preferably 7.2 to 10.3 g/10min. , more preferably 7.7 to 10.1 g/10min, and within this range, calendering property is excellent and mechanical properties as well as glossiness and surface hardness are excellent.

The thermoplastic resin composition has, for example, a Rockwell hardness of 85 or more, preferably 85 to 110, more preferably 88 to 107, even more preferably as measured by R-scale according to ASTM D785. It may be 95 to 106, and there is no press mark within this range and an excellent balance of physical properties has an effect.

The thermoplastic resin composition may have, for example, an elongation of 120% or more, preferably 120 to 145%, more preferably 125 to 135%, measured according to ASTM D638, and has excellent calender processability and physical properties within this range. There is an excellent effect of balance.

The thermoplastic resin composition may have, for example, a gloss of 70 or more, preferably 70 to 100, more preferably 80 to 100, even more preferably 90 to 97, measured at 45° according to ASTM D2457, Within this range, the calendering property is excellent and the physical property balance is excellent.

The thermoplastic resin composition has an Izod impact strength (specimen thickness 1/4", 23° C.) measured according to ASTM D256 as an example of 30 kgf cm/cm or more, preferably 30 to 45 kgf cm/cm, more Preferably, it may be 32 to 42 kgf·cm/cm, and more preferably 32 to 38 kgf·cm/cm, and within this range, calendering property is excellent and the physical property balance is excellent.

The thermoplastic resin composition has, for example, a tensile strength of 340 kgf/cm ² or more, preferably 340 to 400 kgf/cm ² , more preferably 345 to 380 kgf/cm ² , measured according to ASTM D638. Within this range, the calendering property is excellent and the physical property balance is excellent.

For the thermoplastic resin composition, the thickness deviation calculated as the difference between the maximum thickness and the minimum thickness by measuring the thickness of at least 10 places except for 2-3 cm from both ends of the sheet produced after calendering with a roll mill machine for example It may be 0.08 mm or less, preferably 0.07 mm or less, more preferably 0.05 mm or less, even more preferably 0.001 to 0.05 mm, and within this range, the sheet quality and the balance of physical properties are excellent.

The thermoplastic resin composition is optionally used as a heat stabilizer, light stabilizer, dye, pigment, colorant, mold release agent, antistatic agent, antibacterial agent, processing aid, metal deactivator, flame retardant, flame retardant, dripping inhibitor, anti-friction agent and abrasion-resistant agent, if necessary. At least one selected from the group consisting of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight may further include, within this range, the original properties of the thermoplastic resin composition of the present invention There is an effect that the necessary physical properties are well realized without lowering the

Method for producing a thermoplastic resin composition

The method for producing the thermoplastic resin composition of the present invention is preferably a method for producing a thermoplastic resin composition for calendering, for example, (A-1) an acrylate-aromatic vinyl compound containing an acrylate rubber having an average particle diameter of 350 to 550 nm. - 25 to 55 wt% of a vinyl cyan compound graft copolymer; (A-2) 3 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 70 to 200 nm; (B-1) 15 to 45% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 70,000 to 120,000 g/mol; And (B-2) 5 to 30% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 130,000 to 200,000 g/mol; 1) The sum of the weight of the graft copolymer and the (A-2) graft copolymer is 45 to 60% by weight, and the flow index (220°C, 10kg) measured according to ASTM D1238 is 6.9 to 10.5 g/ It is characterized in that it is 10 min, and in this case, it has excellent calendering properties, mechanical properties such as impact strength, tensile strength, and elongation, and excellent gloss and surface hardness.

The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.

The step of preparing the pellets using the extrusion kneader may be preferably carried out under 210 to 280 ℃, more preferably under 220 to 250 ℃, wherein the temperature means the temperature set in the cylinder.

The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.

molded product

The molded article of the present base material may preferably be a calendered (molded) article, and as an example, it is characterized by including the thermoplastic resin composition of the present base material. In this case, mechanical properties such as impact strength, tensile strength and elongation as well as glossiness and excellent surface hardness.

The molded article is preferably a housing for home appliances such as air conditioners, vacuum cleaners, washing machines, refrigerators and TV back covers; housings of OA equipment such as computers, notebook computers, monitors, facsimiles, telephones, copiers and scanners; It may be parts for automobiles such as interior and exterior materials for automobiles, and specifically, may be interior and exterior construction materials, toy members, leisure products, or decorative sheets used for indoor furniture and interior decorations.

In describing the thermoplastic resin composition of the present disclosure, its manufacturing method and molded article, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation do.

Hereinafter, preferred examples are presented to help the understanding of the present disclosure, but the following examples are merely illustrative of the present disclosure, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present disclosure, It goes without saying that such 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-1) Graft copolymer: butyl acrylate-styrene-acrylonitrile copolymer having an average particle diameter of acrylate rubber of 500 nm (butyl acrylate 50% by weight, styrene 35% by weight, and acrylonitrile 15% by weight )

* (A-2) Graft copolymer: butyl acrylate-styrene-acrylonitrile copolymer having an average particle diameter of acrylate rubber of 130 nm (butyl acrylate 50% by weight, styrene 35% by weight, and acrylonitrile 15% by weight )

* (B-1) copolymer: a styrene-acrylonitrile copolymer having a weight average molecular weight of 91,000 g/mol prepared by bulk polymerization (66.6% by weight of styrene and 33.4% by weight of acrylonitrile)

* (B-2) copolymer: a styrene-acrylonitrile copolymer having a weight average molecular weight of 160,000 g/mol prepared by bulk polymerization (70.6 wt% of styrene and 29.4 wt% of acrylonitrile)

* (B-3) copolymer: a styrene-acrylonitrile copolymer having a weight average molecular weight of 270,000 g/mol prepared by bulk polymerization (73% by weight of styrene and 27% by weight of acrylonitrile)

Examples 1 to 4 and Comparative Examples 1 to 13

Each of the components and contents described in Tables 1 to 13 below were put into a twin-screw extruder, and then kneaded and extruded at 230° C. to prepare pellets. The flow index was measured with the prepared pellets.

Thereafter, a specimen for measuring physical properties was prepared by injection at 220° C. with an injection machine.

[Test Example]

The properties of the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 13 were measured by the following method, and the results are shown in Tables 1 to 3 below.

How to measure

* Flow index (g/10min): Measured for 10 minutes at 220 ℃, 10kg load according to ASTM D1238.

* Surface hardness: Rockwell hardness was measured with R-Scale according to ASTM D785.

* Tensile strength (kgf/cm ² ): It was measured according to ASTM D638.

* Elongation (%): Measured according to ASTM D638.

* Glossiness: measured at 45° according to ASTM D2457.

* Izod impact strength (kgf·cm/cm): It was measured under 23 ℃ according to ASTM D256 using a notched specimen (thickness 1/4").

* Calendering processability: Calendering is performed while maintaining the rolls at 190°C in a roll mill where two rolls with a diameter of 30cm are installed with an interval of 0.3mm. It was evaluated as follows by comprehensively evaluating the degree of adhesion and tearing.

◎: superior to PVC, ○: equal to PVC, X: inferior to PVC

* Thickness deviation (mm): A sheet was manufactured by calendering while maintaining the roll at 190°C in a roll mill device in which two rolls with a diameter of 30 cm were installed with an interval of 0.3 mm. The thickness of the portion excluding 2 to 3 cm from both ends of the prepared sheet was measured at 10 or more places, and the thickness deviation was calculated as the difference between the maximum thickness and the minimum thickness.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 (A-1) 30 40 40 50 55 0 (A-2) 25 15 15 5 0 55 (B-1) 35 35 20 35 35 35 (B-2) 10 10 25 10 10 10 flow index 10.1 8.6 7.2 8.2 5.5 16.2 impact strength 32.4 36.2 37.0 40.2 42.2 12.1 glossiness 95.2 90.3 90.4 70.5 62.8 101.2 The tensile strength 365 348 371 346 350 343 elongation 129 131 125 133 142 62 rockwell hardness 99 102 106 89 64 97 calendar machinability ◎ ◎ ◎ ◎ X X thickness deviation 0.05 0.05 0.04 0.05 0.16 0.07

division Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 (A-1) 40 60 20 30 30 40 (A-2) 15 5 30 35 5 25 (B-1) 0 27 40 25 55 10 (B-2) 45 8 10 10 10 25 flow index 3.8 2.1 11.1 4.8 20.2 4.2 impact strength 37.8 45.8 25.4 35.6 12.8 38.7 glossiness 91.0 61.1 93.5 96.0 89.2 86.2 The tensile strength 384 287 373 332 435 352 elongation 122 141 92 135 56 126 rockwell hardness 109 58 101 94 102 101 calendar machinability X X X X X X thickness deviation 0.21 0.22 0.06 0.17 0.1 0.17

division Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 (A-1) 40 40 45 30 30 (A-2) 10 15 20 10 25 (B-1) 15 45 25 35 35 (B-2) 35 0 10 25 (B-3) - - - - 10 flow index 5.8 19.1 4.6 14.8 6.6 impact strength 36.9 34.4 39.5 14.2 34.1 glossiness 91.2 80.4 70.8 87.6 94.9 The tensile strength 386 329 318 452 373 elongation 120 124 131 65 124 rockwell hardness 107 100 68 99 101 calendar machinability ○ X X ○ X thickness deviation 0.16 0.09 0.21 0.08 0.12

As shown in Tables 1 to 3, Examples 1 to 4 prepared according to the present invention have excellent calendering properties, excellent gloss and surface hardness, and impact strength, compared to Comparative Examples 1 to 13, which is out of the scope of the present invention. In addition to excellent mechanical properties such as , tensile strength and elongation, the sheet quality was excellent because the thickness variation was small.

Specifically, the present invention does not contain any one of (A-1) graft copolymer, (A-2) graft copolymer, (B-1) copolymer or (B-2) copolymer, and the flow index of the present invention Comparative Examples 1 to 3 and 10 out of the range had poor calendering property, a large thickness variation, and low impact strength, gloss, or surface hardness.

In addition, (A-1) Comparative Example 4 containing an excess of the graft copolymer and having a flow index less than the range of the present invention had significantly lower gloss and surface hardness, and a large thickness variation due to a decrease in roll adhesion during calendering and calendering. The workability was poor.

In addition, (A-1) Comparative Example 5 containing a small amount of the graft copolymer and having a flow index exceeding the range of the present invention had poor calender workability and lower elongation and impact strength.

In addition, (A-2) Comparative Example 6 containing an excess of the graft copolymer and having a flow index less than the range of the present invention had poor calender workability, a large thickness deviation, and lower tensile strength and surface hardness.

In addition, (B-1) Comparative Example 7, which contained an excess of the copolymer and had a flow index exceeding the range of the present invention, produced bubbles during calendering, resulting in poor calendering properties and significantly lowered impact strength and elongation, ( B-1) Comparative Example 8 containing a small amount of the copolymer and having a flow index less than the range of the present invention had poor calender processability and increased thickness variation due to reduced roll adhesion during calendering.

In addition, (B-2) Comparative Example 9 containing an excessive amount of the copolymer and the flow index is less than the range of the present invention, the calender processability is similar to that of PVC, but the elongation is lowered and the thickness deviation is large.

In addition, in Comparative Example 11, in which the sum of the weights of (A-1) graft copolymer and (A-2) graft copolymer was 65% by weight, and the flow index was less than the range of the present invention, calender processability was lowered and the surface The hardness became poor and the thickness deviation increased, and the sum of the weights of (A-1) graft copolymer and (A-2) graft copolymer was 40% by weight, which was a small amount and the flow index exceeded the range of the present invention. In Comparative Example 12, the calendering property was similar to that of PVC resin, but the impact strength and elongation were lowered, and the thickness deviation was increased.

In addition, Comparative Example 13 using the (B-3) copolymer having a higher weight average molecular weight than the (B-2) copolymer and having a flow index less than the range of the present invention had poor calender processability and increased thickness variation.

Claims (13)

(A-1) 25 to 55 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having an average particle diameter of 350 to 550 nm;
(A-2) 3 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 70 to 200 nm;
(B-1) 15 to 45% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 70,000 to 120,000 g/mol; and
(B-2) 5 to 30% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer having a weight average molecular weight of 130,000 to 200,000 g/mol; including;
The sum of the weight of the (A-1) graft copolymer and the (A-2) graft copolymer is 45 to 60% by weight,
Characterized in that the flow index (220 ℃, 10kg) measured according to ASTM D1238 is 6.9 to 10.5 g/10min
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is a thermoplastic resin composition for calendering
Thermoplastic resin composition.
The method of claim 1,
The weight ratio of the (A-1) graft copolymer and the (A-2) graft copolymer is 1: 0.07 to 1: 0.85, characterized in that
Thermoplastic resin composition.
The method of claim 1,
The (A-1) graft copolymer is characterized in that it comprises 40 to 60% by weight of an acrylate-based rubber, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound.
Thermoplastic resin composition.
The method of claim 1,
The (A-2) graft copolymer is characterized in that it comprises 40 to 60% by weight of an acrylate-based rubber, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound.
Thermoplastic resin composition.
The method of claim 1,
The (B-1) copolymer is characterized in that it comprises 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyanide compound.
Thermoplastic resin composition.
The method of claim 1,
The (B-2) copolymer is characterized in that it comprises 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyanide compound.
Thermoplastic resin composition.
The method of claim 1,
The weight average molecular weight difference between the (B-1) copolymer and the (B-2) copolymer is 60,000 to 80,000 g/mol
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that the Rockwell (Rockwell) hardness measured by R-Scale according to ASTM D785 is 85 or more
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that the elongation measured according to ASTM D638 is 120% or more
Thermoplastic resin composition.
(A-1) 25 to 55 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 350 to 550 nm, (A-2) having an average particle diameter of 70 to 200 3 to 30 wt% of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an acrylate rubber having a thickness of nm, (B-1) Aromatic vinyl compound having a weight average molecular weight of 70,000 to 120,000 g/mol-vinyl cyan compound 15 to 45 wt% of the copolymer, and (B-2) melt-kneading 5 to 30 wt% of an aromatic vinyl compound having a weight average molecular weight of 130,000 to 200,000 g/mol-vinyl cyan compound copolymer under 200 to 300 °C conditions; including,
The sum of the weight of the (A-1) graft copolymer and the (A-2) graft copolymer is 45 to 60% by weight,
Characterized in that the flow index (220 ℃, 10kg) measured according to ASTM D1238 is 6.9 to 10.5 g/10min
A method for producing a thermoplastic resin composition.
Claims 1 to 10, characterized in that it comprises the thermoplastic resin composition of any one of
molded article.
13. The method of claim 12,
The molded article is characterized in that the calendered article
molded article.