Thermoplastic resin composition, method for preparing same, and molded article comprising same

Abstract

Disclosed are a thermoplastic resin composition, a method of preparing the same, and a molded article including the thermoplastic resin composition. More specifically, provided is a thermoplastic resin composition comprising: 100 parts by weight of a base resin comprising 25% to 75% by weight of one or more copolymers (A) and 25% to 75% by weight of one or more matrix resins (B), the copolymer (A) is selected from the group consisting of: a copolymer (a-1) comprising an alkyl acrylate rubber having an average particle diameter of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound; a copolymer (a-2) comprising an alkyl acrylate rubber having an average particle diameter of more than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound; and a copolymer (a-3) comprising an alkyl acrylate rubber having an average particle diameter of 50 nm to 120 nm, an aromatic vinyl compound and a vinyl cyanide compound, the matrix resin (B) being selected from the group consisting of an aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) and an alkyl (meth) acrylate polymer (b-2); and 0.3 to 2 parts by weight of a pentaerythritol-based lubricant (C), wherein the graft copolymer (a-3) has an alkyl acrylate coverage (X) value of 65% by weight or more as calculated by Equation 1 below; a method for preparing the thermoplastic resin composition; and a molded article including the thermoplastic resin composition. According to the present invention, provided are: a thermoplastic resin composition which has processability equal to or higher than that of a conventional material PVC resin for calendering, has excellent surface quality without flow marks, bubbles, and plate out, and can be calendered using existing calendering equipment; a method for preparing the thermoplastic resin composition; and a molded article including the thermoplastic resin composition.

Description

Technical Field

[0001] [Cross - Reference to Related Applications]

[0002] This application claims priority based on Korean Patent Application No. 10 - 2023 - 0143765, filed with the Korean Intellectual Property Office on October 25, 2023, the disclosure of which is incorporated herein by reference.

[0003] The present invention relates to a thermoplastic resin composition, a method for preparing the thermoplastic resin composition, and a molded article including the thermoplastic resin composition. More specifically, the present invention relates to: a thermoplastic resin composition having a processing performance equal to or higher than that of a conventional material, PVC resin, used for calendering, having excellent surface quality without flow marks, bubbles, and exudation, and capable of being calendered using existing calendering equipment without changing the equipment; a method for preparing the thermoplastic resin composition; and a molded article including the thermoplastic resin composition. Background Art

[0004] A calender is a roll press in which several heating rolls are arranged. In addition, a process of forming a film, sheet, etc. using a calender or a process of coating the surface of a fabric, paper, etc. with plastic using a calender is called a calendering process or calendering. Compared with an extrusion process, calendering has the disadvantage of high equipment cost, but calendering can achieve excellent quality. Therefore, calendering is widely used in the manufacture of polyvinyl chloride resin (hereinafter referred to as 'PVC resin').

[0005] PVC resin is a homopolymer of vinyl chloride or a copolymer containing 50 wt% or more of vinyl chloride, and is one of five general thermoplastic resins prepared by suspension polymerization or emulsion polymerization. Among them, the PVC resin prepared by suspension polymerization is mixed with a plasticizer, a stabilizer, a filler, a pigment, titanium dioxide (TiO2), and an additive having a special function, and is widely used for manufacturing films, sheets, wires, pipes, etc. by various processing methods. PVC resin is widely used as a surface treatment material for furniture due to its low cost, excellent physical properties, and high processing performance. However, PVC resin is difficult to reprocess and generates harmful chlorine and hydrogen chloride gases when burned. In addition, phthalate compounds used as plasticizers to impart flexibility are harmful to the human body, and harmful substances are generated during the preparation and handling of phthalate compounds.

[0006] To solve these problems, research is actively underway on materials that can replace PVC resin. Among the materials studied, acrylonitrile-styrene-acrylate resin (hereinafter referred to as "ASA resin") has excellent weather resistance, light resistance, colorability, chemical resistance, and impact resistance, and is used in various fields such as automobiles, building materials, and groceries. In particular, compared with PVC resin, since ASA resin has excellent processing stability and does not contain heavy metal components, ASA resin has attracted attention as an environmentally friendly material.

[0007] However, in the case of conventional ASA resin for calendering, the calendering processability is low, and flow marks, bubbles, exudation, etc. occur, which deteriorate the surface quality. Therefore, it is difficult to achieve the luxurious appearance required in the market.

[0008] Therefore, there is a need to develop an environmentally friendly material with excellent coloring, gloss, and calendering processability to achieve the luxurious appearance required in the market.

[0009] [Related Technical Literature]

[0010] [Patent Literature]

[0011] KR 2006-0118820A Summary of the Invention

[0012] Technical Problem

[0013] Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to provide: a thermoplastic resin composition having a processability equal to or higher than that of conventional material PVC resin for calendering, having excellent surface quality without flow marks, bubbles, and exudation, capable of generating less harmful substances during molding and incineration, and capable of being calendered using existing calendering equipment without changing the equipment; a method for preparing the thermoplastic resin composition; and a molded article including the thermoplastic resin composition.

[0014] Another object of the present invention is to provide a method for preparing the thermoplastic resin composition.

[0015] Still another object of the present invention is to provide a molded article manufactured using the thermoplastic resin composition.

[0016] The above and other objects can be achieved by the present invention described below.

[0017] Technical Solution

[0018] I) According to one aspect of the present invention, the above and other objects can be achieved by providing a thermoplastic resin composition comprising: 100 parts by weight of a base resin comprising 25% to 75% by weight of one or more copolymers (A) and 25% to 75% by weight of one or more matrix resins (B), the copolymer (A) being selected from copolymers (a-1) comprising an acrylic alkyl ester rubber having an average particle size of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound, copolymers (a-2) comprising an acrylic alkyl ester rubber having an average particle size greater than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound, and copolymers (a-3) comprising an acrylic alkyl ester rubber having an average particle size of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound, the matrix resin (B) being selected from aromatic vinyl compound-vinyl cyanide copolymers (b-1) and (meth)acrylic alkyl ester polymers (b-2); and 0.3 parts by weight to 2 parts by weight of a pentaerythritol lubricant (C), wherein the copolymer (a-3) has an acrylic alkyl ester coverage (X) value of 65% by weight or more calculated by the following Equation 1:

[0019] [Equation 1]

[0020] X = {(G - Y) / Y} * 100

[0021] wherein G represents the gel content (wt%) based on the total weight of the copolymer (A), and Y represents the acrylic alkyl ester content (wt%) in the gel based on the total weight of the copolymer (A).

[0022] II) According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising: 100 parts by weight of a base resin, which comprises 25% to 75% by weight of one or more graft copolymers (A) and 25% to 75% by weight of one or more matrix resins (B), wherein the graft copolymer (A) is selected from an alkyl acrylate - aromatic vinyl compound - vinyl cyanide graft copolymer (a-1) containing an alkyl acrylate rubber having an average particle diameter of 50 nm to 150 nm, an alkyl acrylate - aromatic vinyl compound - vinyl cyanide graft copolymer (a-2) containing an alkyl acrylate rubber having an average particle diameter greater than 150 nm and 600 nm or less, and an alkyl acrylate - aromatic vinyl compound - vinyl cyanide graft copolymer (a-3) containing an alkyl acrylate rubber having an average particle diameter of 50 nm to 120 nm, and the matrix resin (B) is selected from an aromatic vinyl compound - vinyl cyanide copolymer (b-1) and an alkyl (meth)acrylate polymer (b-2); and 0.3 parts by weight to 2 parts by weight of a pentaerythritol lubricant (C), wherein the graft copolymer (a-3) has an acrylic alkyl ester coverage rate (X) value of 65% by weight or more calculated by the following Equation 1. In this case, the processability can be equal to or higher than that of a conventional material PVC resin for calendering processing, the surface quality can be excellent due to no flow marks, bubbles, and exudation, and calendering processing can be performed using existing calendering equipment.

[0023] [Equation 1]

[0024] X = {(G - Y) / Y} * 100

[0025] Wherein G represents the gel content (% by weight) based on the total weight of the graft copolymer, and Y represents the acrylic alkyl ester content (% by weight) in the gel based on the total weight of the graft copolymer.

[0026] III) In I), the copolymer (a-1), copolymer (a-2) and / or copolymer (a-3) may be a graft copolymer.

[0027] IV) In I) to III), the pentaerythritol lubricant (C) may have a melting point of 100 °C or lower.

[0028] V) In I) to IV), based on 100 parts by weight of the base resin, the thermoplastic resin composition may further comprise 0.1 parts by weight to 1.5 parts by weight of a glycerol lubricant (D).

[0029] VI) In I) to V), the glycerol lubricant (D) may have a molecular weight of 400 g / mol or less.

[0030] VII) In I) to VI), based on the total weight of the graft copolymer (a-1), the copolymer (a-1) may contain 35% to 65% by weight of an alkyl acrylate rubber, 20% to 55% by weight of an aromatic vinyl compound, and 3% to 25% by weight of a vinyl cyanide compound.

[0031] VIII) In I) to VII), based on the total weight of the copolymer (a-2), the copolymer (a-2) may contain 35% to 65% by weight of an alkyl acrylate rubber, 20% to 55% by weight of an aromatic vinyl compound, and 3% to 25% by weight of a vinyl cyanide compound.

[0032] IX) In I) to VIII), the copolymer (a-3) may have a grafting degree of more than 60% calculated by the following Equation 2:

[0033] [Equation 2]

[0034] Grafting degree (%) = [Weight of graft monomer (g) / Weight of rubber (g)] * 100

[0035] Wherein the weight of the graft monomer (g) is obtained by subtracting the weight of the rubber (g) from the weight of the insoluble matter (gel) obtained by dissolving the copolymer in acetone and then centrifuging, and the weight of the rubber (g) is the weight of the rubber component theoretically added to the copolymer powder.

[0036] X) In I) to IX), based on the total weight of the copolymer (a-3), the copolymer (a-3) may contain 20% to 60% by weight of an alkyl acrylate rubber; and 40% to 80% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding the alkyl acrylate rubber.

[0037] XI) In I) to X), the aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) may be one or more selected from an aromatic vinyl compound-vinyl cyanide compound copolymer having a weight average molecular weight of 100,000 g / mol to 150,000 g / mol and an aromatic vinyl compound-vinyl cyanide compound copolymer having a weight average molecular weight of more than 150,000 g / mol and 200,000 g / mol or less.

[0038] XII) Among I) to XI), the (meth)acrylic acid alkyl ester polymer (b-2) may include one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate.

[0039] XIII) Among I) to XII), the polymer (b-2) may have a weight average molecular weight of 50,000 g / mol to 150,000 g / mol.

[0040] In addition, according to another aspect of the present invention, there is provided XIV) A method for preparing a thermoplastic resin composition, the method comprising: kneading and extruding 100 parts by weight of a base resin and 0.3 parts by weight to 2 parts by weight of a pentaerythritol-based lubricant (C) under the conditions of 200 °C to 300 °C and 100 rpm to 500 rpm, the base resin comprising 25% by weight to 75% by weight of one or more copolymers (A) and 25% by weight to 75% by weight of one or more matrix resins (B), the copolymer (A) being selected from copolymers (a-1) comprising an acrylic acid alkyl ester rubber having an average particle size of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound, copolymers (a-2) comprising an acrylic acid alkyl ester rubber having an average particle size greater than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound, and copolymers (a-3) comprising an acrylic acid alkyl ester rubber having an average particle size of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound, the matrix resin (B) being selected from aromatic vinyl compound-vinyl cyanide copolymers (b-1) and (meth)acrylic acid alkyl ester polymers (b-2);

[0041] Wherein the copolymer (a-3) has an acrylic acid alkyl ester coverage (X) value of more than 65% by weight calculated by the following Equation 1:

[0042] [Equation 1]

[0043] X = {(G - Y) / Y} * 100

[0044] (In Equation 1, G represents the gel content (weight%) based on the total weight of the copolymer (A), and Y represents the acrylic acid alkyl ester content (weight%) in the gel based on the total weight of the copolymer (A).)

[0045] XV) In XIV), the copolymer (a-1), copolymer (a-2), and / or copolymer (a-3) may be a graft copolymer.

[0046] XVI) According to another aspect of the present invention, there is provided a method for preparing a thermoplastic resin composition, the method comprising: kneading and extruding a thermoplastic resin composition comprising 100 parts by weight of a base resin and 0.3 to 2 parts by weight of a pentaerythritol lubricant (C) under conditions of 200 °C to 300 °C and 100 rpm to 500 rpm, the base resin comprising 25 wt% to 75 wt% of one or more graft copolymers (A) and 25 wt% to 75 wt% of one or more matrix resins (B), the graft copolymer (A) being selected from an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-1) comprising an acrylate rubber having an average particle size of 50 nm to 150 nm, an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-2) comprising an acrylate rubber having an average particle size greater than 150 nm and 600 nm or less, and an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-3) comprising an acrylate rubber having an average particle size of 50 nm to 120 nm, the matrix resin (B) being selected from an aromatic vinyl compound-vinyl cyanide copolymer (b-1) and a (meth)acrylate polymer (b-2); wherein the graft copolymer (a-3) has an acrylate coverage (X) value of 65 wt% or more calculated by the following equation 1:

[0047] [Equation 1]

[0048] X = {(G - Y) / Y} * 100

[0049] In Equation 1, G represents the gel content (wt%) based on the total weight of the graft copolymer, and Y represents the acrylate content (wt%) in the gel based on the total weight of the graft copolymer.

[0050] XVII) In XIV) to XVI), based on 100 parts by weight of the base resin, the method for preparing a thermoplastic resin composition may comprise 0.1 to 1.5 parts by weight of a glycerol lubricant (D).

[0051] XVIII) According to still another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition according to any one of I) to XIII).

[0052] Advantageous Effects

[0053] The present invention provides a thermoplastic resin composition which does not contain harmful environmental hormones such as phthalate compounds, does not emit toxic gases in the event of a fire, has processing performance equal to or higher than that of conventional materials, PVC resin, for calendering, and has excellent surface quality without flow marks, bubbles, and exudation, and can be calendered using existing calendering equipment.

[0054] In particular, the thermoplastic resin composition of the present invention can be easily calendered using existing calendering equipment without replacing components, and further has excellent calendering processing performance, thereby improving productivity. Detailed Description of the Invention

[0055] Hereinafter, the thermoplastic resin composition of the present invention, a method for preparing the same, and a molded article including the same will be described in detail.

[0056] The inventors have confirmed that when a base resin containing a copolymer (including an acrylic alkyl ester rubber having a predetermined average particle size, an aromatic vinyl compound, and a vinyl cyanide compound) and a predetermined matrix resin contains a predetermined content of a pentaerythritol-based lubricant and the acrylic alkyl ester coverage value of the copolymer is adjusted to a predetermined range, calendering can be performed using existing equipment for the calendering of PVC resin, and compared with the case of existing materials, PVC resin, for calendering, the same or higher processing performance can be provided, the mechanical properties and weather resistance are excellent, and flow marks, bubbles, and exudation do not occur on the calendered molded article, thereby improving the surface quality. Based on these results, the inventors have conducted further research to complete the present invention.

[0057] The thermoplastic resin composition of the present invention will be described in detail below.

[0058] The thermoplastic resin composition of the present disclosure comprises: 100 parts by weight of a base resin, which comprises 25 wt% to 75 wt% of one or more copolymers (A) and 25 wt% to 75 wt% of one or more matrix resins (B), the copolymer (A) being selected from copolymers (a-1) comprising an acrylic alkyl ester rubber having an average particle size of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound, copolymers (a-2) comprising an acrylic alkyl ester rubber having an average particle size greater than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound, and copolymers (a-3) comprising an acrylic alkyl ester rubber having an average particle size of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound, the matrix resin (B) being selected from aromatic vinyl compound-vinyl cyanide copolymers (b-1) and (meth)acrylic alkyl ester polymers (b-2); and 0.3 parts by weight to 2 parts by weight of a pentaerythritol-based lubricant (C), wherein the graft copolymer (a-3) has an acrylic alkyl ester coverage rate (X) value of 65 wt% or more calculated by the following Equation 1. In this case, the processability can be equal to or higher than that of a conventional material PVC resin for calendering processing, the surface quality can be excellent due to no flow marks, bubbles, and exudation, and calendering processing can be performed using existing calendering equipment.

[0059] [Equation 1]

[0060] X = {(G - Y) / Y} * 100

[0061] (In Equation 1, G represents the gel content (wt%) based on the total weight of the copolymer (A), and Y represents the acrylic alkyl ester content (wt%) in the gel based on the total weight of the copolymer (A).)

[0062] In addition, the thermoplastic resin composition of the present disclosure comprises: 100 parts by weight of a base resin, which comprises 25 wt% to 75 wt% of one or more graft copolymers (A) and 25 wt% to 75 wt% of one or more matrix resins (B), the graft copolymer (A) being selected from an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-1) comprising an acrylate rubber having an average particle size of 50 nm to 150 nm, an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-2) comprising an acrylate rubber having an average particle size greater than 150 nm and 600 nm or less, and an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-3) comprising an acrylate rubber having an average particle size of 50 nm to 120 nm, the matrix resin (B) being selected from an aromatic vinyl compound-vinyl cyanide copolymer (b-1) and an (alkyl) acrylate polymer (b-2); and 0.3 parts by weight to 2 parts by weight of a pentaerythritol-based lubricant (C), wherein the graft copolymer (a-3) has an acrylate coverage rate (X) value of 65 wt% or more calculated by the following Equation 1. In this case, the processability can be equal to or higher than that of a conventional material PVC resin for calendering, the surface quality can be excellent due to no flow marks, bubbles, and exudation, and calendering can be carried out using existing calendering equipment.

[0063] [Equation 1]

[0064] X = {(G - Y) / Y} * 100

[0065] In Equation 1, G represents the gel content (wt%) based on the total weight of the graft copolymer, and Y represents the acrylate content (wt%) in the gel based on the total weight of the graft copolymer.

[0066] Hereinafter, each component of the thermoplastic resin composition of the present invention will be described in detail.

[0067] Copolymer (A)

[0068] For example, based on the total weight of the base resin, the copolymer (A) may be contained in an amount of 25 wt% to 75 wt%, preferably 30 wt% to 70 wt%, more preferably 35 wt% to 65 wt%, even more preferably 45 wt% to 65 wt%, and even still more preferably 47 wt% to 57 wt%. Within this range, the processability can be equal to or higher than that of a conventional material PVC resin for calendering, the mechanical properties, weather resistance, gloss, and transparency can be excellent, the surface quality can be excellent due to no flow marks, bubbles, and exudation, and calendering can be carried out using existing calendering equipment.

[0069] In addition, the copolymer (A) may be, for example, one or more copolymers (A) selected from copolymers (a-1) containing an acrylic alkyl ester rubber having an average particle size of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound, copolymers (a-2) containing an acrylic alkyl ester rubber having an average particle size greater than 150 nm and 600 nm or less, and an aromatic vinyl compound, and a vinyl cyanide compound, and copolymers (a-3) containing an acrylic alkyl ester rubber having an average particle size of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound. A mixture of the copolymer (a-1) and the copolymer (a-2), or the copolymer (a-3) is preferred, and the copolymer (a-3) is more preferred. In this case, the processability may be equal to or higher than that of a conventional material, PVC resin, used for calendering, the mechanical properties and weather resistance may be excellent, the surface quality may be excellent due to the absence of flow marks, bubbles, and exudation, and calendering can be performed using existing calendering equipment.

[0070] The copolymer (a-1), the copolymer (a-2), and / or the copolymer (a-3) may preferably be a graft copolymer. In this case, the mechanical properties and weather resistance may be excellent.

[0071] In addition, the graft copolymer (A) may be, for example, one or more (A) selected from an acrylic alkyl ester - aromatic vinyl compound - vinyl cyanide compound graft copolymer (a-1) containing an acrylic alkyl ester rubber having an average particle size of 50 nm to 150 nm, an acrylic alkyl ester - aromatic vinyl compound - vinyl cyanide compound graft copolymer (a-2) containing an acrylic alkyl ester rubber having an average particle size greater than 150 nm and 600 nm or less, and an acrylic alkyl ester - aromatic vinyl compound - vinyl cyanide compound graft copolymer (a-3) containing an acrylic alkyl ester rubber having an average particle size of 50 nm to 120 nm. A mixture of the graft copolymer (a-1) and the graft copolymer (a-2), or the graft copolymer (a-3) is preferred, and the graft copolymer (a-3) is more preferred. In this case, the processability may be equal to or higher than that of a conventional material, PVC resin, used for calendering, the mechanical properties and weather resistance may be excellent, the surface quality may be excellent due to the absence of flow marks, bubbles, and exudation, and calendering can be performed using existing calendering equipment.

[0072] In this specification, "exudation" means the appearance of a lubricant or a plasticizer on the surface of the product.

[0073] A copolymer (a-1) containing an acrylic alkyl ester rubber having an average particle diameter of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound A copolymer (a-2) containing an acrylic alkyl ester rubber having an average particle diameter greater than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound

[0074] The copolymer (a-1) containing an acrylic alkyl ester rubber having an average particle diameter of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound is preferably an acrylic alkyl ester - aromatic vinyl compound - vinyl cyanide graft copolymer (a-1) containing an acrylic alkyl ester rubber having an average particle diameter of 50 nm to 150 nm. In this case, mechanical properties can be maintained, and gloss, transparency, coloring properties, and calendering processability can be excellent.

[0075] The acrylic alkyl ester rubber of the graft copolymer (a-1) can preferably have an average particle diameter of 60 nm to 140 nm, more preferably 80 nm to 140 nm, even more preferably 100 nm to 140 nm, and even still more preferably 110 nm to 140 nm. Within this range, mechanical properties can be maintained, and gloss, transparency, coloring properties, and calendering processability can be excellent.

[0076] In the present disclosure, the average particle diameter can be measured by dynamic light scattering, and specifically, it can be measured as an intensity value using a Nicomp 380 particle size analyzer (manufacturer: PSS) in Gaussian mode. As a specific measurement example, a sample can be prepared by diluting 0.1 g of latex (TSC: 35 wt% to 50 wt%) 1,000 to 5,000 times with distilled water, and the average particle diameter can be measured using a flow cell in an automatic dilution mode and a dynamic light scattering / intensity 300 kHz / intensity - weight Gaussian analysis mode. At this time, the temperature can be set to 23 °C, the measurement wavelength can be set to 632.8 nm, and the channel width can be set to 10 microseconds.

[0077] The graft copolymer (a-1) can preferably contain an acrylic alkyl ester rubber (core) and an aromatic vinyl compound - vinyl cyanide copolymer (shell) surrounding the acrylic alkyl ester rubber. In this case, mechanical properties can be maintained, and gloss, transparency, coloring properties, and processability can be excellent.

[0078] Based on the total weight of the graft copolymer (a-1), the graft copolymer (a-1) can contain 35 wt% to 65 wt% of an acrylic alkyl ester rubber, 20 wt% to 55 wt% of an aromatic vinyl compound, and 3 wt% to 25 wt% of a vinyl cyanide compound. Within this range, mechanical properties can be maintained, and gloss, transparency, coloring properties, and processability can be excellent.

[0079] Preferably, the graft copolymer (a-1) may contain 40% to 60% by weight of an alkyl acrylate rubber, 25% to 50% by weight of an aromatic vinyl compound, and 5% to 20% by weight of a vinyl cyanide compound. Within this range, mechanical properties can be maintained, and gloss, transparency, coloring properties, and processability can be excellent.

[0080] More preferably, the graft copolymer (a-1) may contain 45% to 55% by weight of an alkyl acrylate rubber, 33% to 43% by weight of an aromatic vinyl compound, and 10% to 15% by weight of a vinyl cyanide compound. Within this range, mechanical properties can be maintained, and gloss, transparency, coloring properties, and processability can be excellent.

[0081] The graft copolymer (a-1) can be prepared, for example, by emulsion polymerization. In this case, gloss, transparency, and coloring properties can be excellent while maintaining mechanical properties.

[0082] In the present invention, an emulsion polymerization method commonly used in the art to which the present invention pertains can be used without particular limitation. For example, an emulsion graft polymerization method can be used.

[0083] For example, the graft copolymer (a-1) can have a graft degree of 15% to 60%, preferably 20% to 50%, more preferably 25% to 45% calculated by Equation 2. Within this range, due to excellent process dispersion with the matrix resin (B) described below, calendering processability can be improved.

[0084] [Equation 2]

[0085] Graft degree (%) = [Weight of graft monomer (g) / Weight of rubber (g)] * 100

[0086] (In Equation 2, the weight of the graft monomer (g) is obtained by subtracting the weight of the rubber (g) from the weight of the insoluble matter (gel) obtained by dissolving the copolymer in acetone and centrifuging. The weight of the rubber (g) is the weight of the rubber component theoretically added to the copolymer powder.)

[0087] When measuring the weight of the insoluble matter (gel), 0.5 g of the powdered copolymer is added to 50 ml of acetone, and then stirred at room temperature for 12 hours. Then, centrifugation is performed to separate the insoluble matter that has not dissolved in acetone, followed by drying for 12 hours. Then, the weight of the insoluble matter (gel) is measured. The weight of the rubber (g) is the weight of the rubber component theoretically added to 0.5 g of the powdered copolymer (A).

[0088] As a specific measurement example, when measuring the weight (g) of the insoluble substance (gel), 0.5 g of the powdery copolymer was added to 50 ml of acetone, and then stirred using an orbital shaker (equipment name: Lab companion SKC-6075) at 210 rpm and room temperature for 12 hours. Then, centrifugation was performed using a centrifuge (Supra R30, Hanil Science Co.) at 0 °C and 18,000 rpm for 3 hours to separate the insoluble substance that did not dissolve in acetone, and subsequently dried by forced circulation in a forced convection oven (equipment name: Lab companion OF-12GW) set at 85 °C for 12 hours. Then, the weight of the insoluble substance (gel) was measured.

[0089] For example, based on the total weight of the base resin, the graft copolymer (a-1) can be included in an amount of 0 wt% to 75 wt%, preferably 1 wt% to 55 wt%, more preferably 3 wt% to 35 wt%, and even more preferably 5 wt% to 15 wt%. Within this range, the glossiness and transparency can be excellent, and the occurrence of whitening during bending processing can be reduced.

[0090] In the present disclosure, the alkyl acrylate can be, for example, an alkyl acrylate having 1 to 15 carbon atoms in its alkyl group, preferably one or more selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, more preferably an alkyl acrylate having an alkyl group of 1 to 4 or 8 carbon atoms, even more preferably butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof, and even still more preferably butyl acrylate.

[0091] In the present disclosure, for example, the aromatic vinyl compound can include one or more selected from styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, tert-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably one or more selected from styrene and α-methylstyrene, and more preferably styrene. In this case, due to appropriate fluidity, the processing performance and mechanical properties such as impact resistance can be excellent.

[0092] In the present disclosure, for example, the vinyl cyanide compound can include one or more selected from acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and preferably acrylonitrile.

[0093] In the present disclosure, a polymer containing a certain compound (monomer) refers to a polymer prepared by polymerizing the compound (monomer), and the units in the polymer are derived from the compound.

[0094] A copolymer (a-3) containing an acrylic alkyl ester rubber having an average particle diameter of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound A copolymer (a-2) containing an acrylic alkyl ester rubber having an average particle diameter greater than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound

[0095] The copolymer (a-2) containing an acrylic alkyl ester rubber having an average particle diameter greater than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound can preferably be an acrylic alkyl ester - aromatic vinyl compound - vinyl cyanide compound graft copolymer (a-2) containing an acrylic alkyl ester rubber having an average particle diameter greater than 150 nm and 600 nm or less. In this case, mechanical properties such as impact strength and processability can be excellent.

[0096] The acrylic alkyl ester rubber of the graft copolymer (a-2) can preferably have an average particle diameter of 200 nm to 600 nm, more preferably 250 nm to 500 nm, even more preferably 300 nm to 470 nm, and even still more preferably 330 nm to 430 nm. Within this range, mechanical properties such as impact strength and processability can be excellent.

[0097] The graft copolymer (a-2) can preferably contain an acrylic alkyl ester rubber (core) and an aromatic vinyl compound - vinyl cyanide compound copolymer (shell) surrounding the acrylic alkyl ester rubber. In this case, mechanical properties and processability can be excellent.

[0098] Based on the total weight of the graft copolymer (a-2), the graft copolymer (a-2) can contain, for example, 35% by weight to 65% by weight of an acrylic alkyl ester rubber, 20% by weight to 55% by weight of an aromatic vinyl compound, and 3% by weight to 25% by weight of a vinyl cyanide compound. Within this range, mechanical properties such as impact strength, processability, and transparency can be excellent.

[0099] Preferably, the graft copolymer (a-2) can contain 40% by weight to 60% by weight of an acrylic alkyl ester rubber, 25% by weight to 50% by weight of an aromatic vinyl compound, and 5% by weight to 20% by weight of a vinyl cyanide compound. Within this range, mechanical properties such as impact strength, processability, and transparency can be excellent.

[0100] More preferably, the graft copolymer (a-2) can contain 45% by weight to 55% by weight of an acrylic alkyl ester rubber, 33% by weight to 43% by weight of an aromatic vinyl compound, and 10% by weight to 15% by weight of a vinyl cyanide compound. Within this range, mechanical properties such as impact strength, processability, and transparency can be excellent.

[0101] The types of the alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyanide compound contained in the graft copolymer (a-2) can be within the same range as the types of the alkyl acrylate rubber, aromatic vinyl compound, and vinyl cyanide compound contained in the copolymer (a-1) of the present disclosure.

[0102] The graft copolymer (a-2) can be prepared by emulsion polymerization. In this case, mechanical properties such as impact strength and transparency can be excellent.

[0103] In the present invention, the emulsion polymerization method commonly used in the art to which the present invention pertains can be used without particular limitation. For example, an emulsion graft polymerization method can be used.

[0104] The graft copolymer (a-2) can have a graft degree, for example, of 40% to 120%, preferably 45% to 100%, more preferably 45% to 80% calculated by the above equation 2. Within this range, mechanical properties such as impact strength and processability can be excellent.

[0105] Based on the total weight of the base resin, the graft copolymer (a-2) can be contained in an amount of, for example, 0 wt% to 75 wt%, preferably 5 wt% to 55 wt%, more preferably 15 wt% to 35 wt%, even more preferably 20 wt% to 35 wt%. Within this range, mechanical properties, processability, and transparency can be excellent.

[0106] A copolymer (a-3) containing an acrylic alkyl ester rubber having an average particle diameter of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound A copolymer (a-3) containing an acrylic alkyl ester rubber having an average particle diameter of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound

[0107] The copolymer (a-3) containing an alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyanide compound having an average particle diameter of 50 nm to 120 nm can preferably be an alkyl acrylate - aromatic vinyl compound - vinyl cyanide compound graft copolymer (a-3) containing an alkyl acrylate rubber having an average particle diameter of 50 nm to 120 nm. In this case, the processability can be equal to or higher than that of a conventional material PVC resin for calendering processing, the surface quality can be excellent due to no flow marks, bubbles, and exudation, and calendering processing can be performed using existing calendering equipment.

[0108] The alkyl acrylate rubber of the graft copolymer (a-3) can have an average particle diameter of preferably 50 nm to 110 nm, more preferably 50 nm to 100 nm, even more preferably 60 nm to 90 nm. Within this range, the processability can be equal to or higher than that of a conventional material PVC resin for calendering processing, the surface quality can be excellent due to no flow marks, bubbles, and exudation, and calendering processing can be performed using existing calendering equipment.

[0109] For example, the graft copolymer (a-3) may have an acrylate coverage (X) value of 65% by weight or more, preferably 75% by weight or more, more preferably 85% by weight or more, still more preferably 85% to 140% by weight, and still more preferably 95% to 120% by weight, calculated by Equation 1 below. Within this range, mechanical properties, transparency, gloss, and calendering processability can be excellent. In particular, the occurrence of whitening during bending processing can be reduced, thereby providing a beautiful appearance;

[0110] [Equation 1]

[0111] X = {(G - Y) / Y} × 100

[0112] In Equation 1, G represents the gel content (% by weight) based on the total weight of the copolymer (A), and Y represents the acrylate content (% by weight) in the gel based on the total weight of the copolymer (A).

[0113] In Equation 1, the acrylate content in the gel of the copolymer refers to the acrylate content in the insoluble matter collected during the calculation of the above gel content (based on a total of 100% by weight of the added copolymer). Here, the gel content refers to the content of insoluble matter based on a total of 100% by weight of the copolymer.

[0114] The content of acrylate is quantitatively measured by nuclear magnetic resonance (NMR) analysis or Fourier transform infrared spectroscopy (FT-IR) analysis.

[0115] In the present disclosure, unless otherwise specified, NMR analysis refers to 1 1H NMR analysis.

[0116] In the present disclosure, NMR analysis can be performed using methods commonly practiced in the art. Specific measurement examples are as follows.

[0117] - Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy probe

[0118] - Measurement conditions: 1H NMR (zg30): ns = 32, d1 = 5s, TCE-d2, at room temperature

[0119] In the present disclosure, FT-IR analysis can be performed using methods commonly practiced in the art. Specific measurement examples are as follows.

[0120] - Equipment name: Agilent Cary 660

[0121] - Measurement condition: ATR mode

[0122] When measuring the gel content, 1 g of the copolymer is added to 30 ml of acetone and then stirred at room temperature for 12 hours. Then, centrifugation is performed to separate the insoluble matter that is not dissolved in acetone, and then dried for 12 hours. Then, the weight of the insoluble matter is measured, and the gel content is calculated by Equation 3 below. As a specific measurement example, when measuring the gel content, 1 g of the copolymer is added to 30 ml of acetone, and then stirred at 210 rpm and room temperature for 12 hours using an orbital shaker (equipment name: Lab companion SKC-6075). Then, centrifugation is performed at 0 °C and 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Science Co.) to separate the insoluble matter that is not dissolved in acetone, and then dried for 12 hours in a forced convection oven (equipment name: Lab companion OF-12GW) set at 85 °C by forced circulation. Then, the weight of the insoluble matter is measured.

[0123] [Equation 3]

[0124] Gel content (wt%) = [weight of insoluble matter (gel) (g) / weight of sample (g)] × 100

[0125] In the present disclosure, the acrylic alkyl ester coverage value is a parameter indicating the dispersion degree of the aromatic vinyl compound-vinyl cyanide compound polymer grafted onto the acrylic alkyl ester rubber in the copolymer containing acrylic alkyl ester rubber, aromatic vinyl compound, and vinyl cyanide compound. A high acrylic alkyl ester coverage value indicates that the aromatic vinyl compound-vinyl cyanide compound polymer grafted onto the acrylic alkyl ester rubber is uniformly distributed. That is, the polymer uniformly surrounds the rubber. In this case, the glossiness and transparency can be increased, and the mechanical properties, colorability, and non-whitening properties can be excellent. In addition, as the acrylic alkyl ester coverage value increases, the acrylic alkyl ester homogeneity between the inside and outside of the graft copolymer gel increases. Therefore, when the acrylic alkyl ester coverage value is high, the defect area caused by external stress can be reduced, and the voids caused by cracks occurring inside the graft copolymer can be reduced, thereby suppressing whitening during bending.

[0126] Check the difference between the acrylic alkyl ester coverage value and the grafting degree, calculate the acrylic alkyl ester coverage value using an NMR analyzer or FT-IR based on the content of the acrylic alkyl ester actually present in the graft copolymer, and calculate the grafting degree based on the content of the rubber component added during polymerization.

[0127] The graft copolymer (a-3) may preferably contain an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyanide copolymer (shell) surrounding the alkyl acrylate rubber.

[0128] For example, based on the total weight of the graft copolymer (a-3), the graft copolymer (a-3) may contain 20% to 60% by weight of an alkyl acrylate rubber and 40% to 80% by weight of an aromatic vinyl compound-vinyl cyanide copolymer surrounding the alkyl acrylate rubber, preferably 30% to 50% by weight of an alkyl acrylate rubber and 50% to 70% by weight of an aromatic vinyl compound-vinyl cyanide copolymer surrounding the alkyl acrylate rubber, more preferably 40% to 50% by weight of an alkyl acrylate rubber and 50% to 60% by weight of an aromatic vinyl compound-vinyl cyanide copolymer surrounding the alkyl acrylate rubber. Within this range, mechanical properties, gloss, transparency, weather resistance, and calendering processability can be excellent, and the occurrence of whitening during bending processing can be reduced, thereby providing a luxurious appearance.

[0129] For example, the alkyl acrylate rubber can be prepared by emulsion polymerizing an alkyl acrylate. Preferably, the alkyl acrylate rubber can be prepared by mixing an alkyl acrylate, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent, and emulsion polymerizing the mixture. In this case, due to excellent grafting efficiency, the mechanical properties can be excellent.

[0130] For example, the alkyl acrylate rubber may further contain an aromatic vinyl compound. In this case, chemical resistance and impact resistance can be excellent.

[0131] For example, based on a total of 100% by weight of the alkyl acrylate rubber, the alkyl acrylate rubber may contain 0.1% to 25% by weight, preferably 2% to 23% by weight, more preferably 5% to 20% by weight of an aromatic vinyl compound. Within this range, impact resistance, gloss, transparency, and weather resistance can be excellent without deteriorating the physical properties.

[0132] For example, the aromatic vinyl compound-vinyl cyanide copolymer (shell) may have a weight-average molecular weight of 40,000 g / mol to 120,000 g / mol, preferably 50,000 g / mol to 110,000 g / mol, more preferably 60,000 g / mol to 110,000 g / mol. Within this range, processability can be excellent without reducing the impact strength, and the occurrence of whitening during bending processing can be reduced.

[0133] In the present disclosure, unless otherwise defined, the weight-average molecular weight can be measured by gel permeation chromatography (GPC, Waters Breeze). As a specific example, the weight-average molecular weight can be measured by gel permeation chromatography (GPC, Waters Breeze) using tetrahydrofuran (THF) as an eluent. In this case, the weight-average molecular weight is obtained as a relative value with respect to a polystyrene (PS) standard sample. As a specific measurement example, the weight-average molecular weight can be measured under the conditions of solvent: THF, column temperature: 40 °C, flow rate: 0.3 ml / min, sample concentration: 20 mg / ml, injection volume: 5 μl, column model: 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B (250×4.6 mm) + 1×PLgel 10 μm MiniMix-B Guard (50×4.6 mm), equipment name: Agilent 1200 series system, refractive index detector: Agilent G1362RID, RI temperature: 35 °C, data processing: Agilent ChemStation S / W, and test method (Mn, Mw and PDI): OECD TG 118.

[0134] For example, based on the total weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (shell), the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) can contain 55% to 85% by weight of the aromatic vinyl compound and 15% to 45% by weight of the vinyl cyanide compound, preferably 60% to 80% by weight of the aromatic vinyl compound and 20% to 40% by weight of the vinyl cyanide compound, more preferably 65% to 75% by weight of the aromatic vinyl compound and 25% to 35% by weight of the vinyl cyanide compound. Within this range, the impact resistance and weather resistance can be excellent.

[0135] Preferably, the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) can further contain an alkyl acrylate. In this case, the impact resistance, weather resistance, processability, and calendering processability can be excellent, and the occurrence of whitening during bending processing can be reduced.

[0136] For example, based on the total weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (shell), the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may contain 55% to 85% by weight of an aromatic vinyl compound, 10% to 35% by weight of a vinyl cyanide compound, and 1% to 25% by weight of an alkyl acrylate, preferably 60% to 80% by weight of an aromatic vinyl compound, 15% to 30% by weight of a vinyl cyanide compound, and 3% to 20% by weight of an alkyl acrylate, more preferably 65% to 72% by weight of an aromatic vinyl compound, 20% to 25% by weight of a vinyl cyanide compound, and 5% to 15% by weight of an alkyl acrylate. Within this range, the impact resistance and weather resistance can be excellent.

[0137] For example, the graft copolymer (a-3) can be prepared by emulsion polymerization. In this case, the glossiness and surface hardness can be excellent.

[0138] In the present invention, the emulsion polymerization method commonly used in the field to which the present invention pertains can be used without particular limitation. For example, an emulsion graft polymerization method can be used.

[0139] The graft copolymer (a-3) can have a graft degree, for example, of more than 60%, preferably 60% to 150%, preferably 65% to 140%, more preferably 65% to 130%, still more preferably 65% to 100%, and even still more preferably 65% to 80% calculated by the following Equation 2. Within this range, the impact resistance and processability can be excellent, and the occurrence of whitening during bending processing can be reduced.

[0140] [Equation 2]

[0141] Graft degree (%) = [weight of graft monomer (g) / weight of rubber (g)] * 100

[0142] (In Equation 2, the weight of the graft monomer (g) is obtained by subtracting the weight of the rubber (g) from the weight of the insoluble matter (gel) obtained by dissolving the copolymer in acetone and then centrifuging. The weight of the rubber (g) is the weight of the rubber component theoretically added to the copolymer powder.)

[0143] When measuring the weight of the insoluble matter (gel), 0.5 g of the powdered copolymer (A) is added to 50 ml of acetone, and then stirred at room temperature for 12 hours. Then, centrifugation is performed to separate the insoluble matter that is not dissolved in acetone, followed by drying for 12 hours. Then, the weight of the insoluble matter (gel) is measured. The weight of the rubber (g) is the theoretical weight of the rubber component added to 0.5 g of the powdered copolymer (A).

[0144] As a specific measurement example, when measuring the weight (g) of the insoluble substance (gel), 0.5 g of the powdery copolymer was added to 50 ml of acetone, and then stirred using an orbital shaker (equipment name: Lab companion SKC-6075) at 210 rpm and room temperature for 12 hours. Then, centrifugation was performed using a centrifuge (Supra R30, Hanil Science Co.) at 0 °C and 18,000 rpm for 3 hours to separate the insoluble substance that did not dissolve in acetone, and then dried by forced circulation in a forced convection oven (equipment name: Lab companion OF-12GW) set at 85 °C for 12 hours. Then, the weight of the insoluble substance (gel) was measured.

[0145] For example, based on the total weight of the base resin, the graft copolymer (a-3) can be included in an amount of 0 wt% to 75 wt%, preferably 30 wt% to 75 wt%, more preferably 40 wt% to 70 wt%, even more preferably 45 wt% to 65 wt%, and even still more preferably 47 wt% to 57 wt%. Within this range, mechanical properties, gloss, transparency, and processability can be excellent, and the occurrence of whitening during bending processing can be reduced.

[0146] Matrix resin (B)

[0147] Based on the total weight of the base resin, the matrix resin (B) can be included in an amount of, for example, 25 wt% to 75 wt%, preferably 30 wt% to 70 wt%, more preferably 35 wt% to 65 wt%, even more preferably 35 wt% to 55 wt%, and even still more preferably 43 wt% to 53 wt%. Within this range, tensile strength, elongation at break, surface hardness, and processability can be excellent.

[0148] In the present disclosure, the matrix resin refers to a thermoplastic linear copolymer, particularly an uncrosslinked polymer, and serves as a matrix within the resin composition.

[0149] The matrix resin (B) can be, for example, one or more selected from an aromatic vinyl compound-vinyl cyanide copolymer (b-1) and an (alkyl) (meth)acrylate polymer (b-2), preferably an aromatic vinyl compound-vinyl cyanide copolymer (b-1). In this case, flow marks, bubbles, and exudation can be significantly reduced, and thus a beautiful appearance can be provided. In addition, calendering can be performed using existing calendering equipment.

[0150] An aromatic vinyl compound-vinyl cyanide copolymer (b-1)

[0151] Based on the total weight of the base resin, the aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) can be contained in an amount of, for example, 0% by weight to 75% by weight, preferably 25% by weight to 75% by weight, more preferably 35% by weight to 70% by weight, and even more preferably 40% by weight to 65% by weight. Within this range, the tensile strength, elongation at break, surface hardness, and processability can be excellent.

[0152] The aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) can be one or more selected from, for example, an aromatic vinyl compound-vinyl cyanide compound copolymer (b-1-1) having a weight average molecular weight of 100,000 g / mol to 150,000 g / mol and an aromatic vinyl compound-vinyl cyanide compound copolymer (b-1-2) having a weight average molecular weight of more than 150,000 g / mol and 200,000 g / mol or less. Preferably, both the copolymer (b-1-1) and the copolymer (b-1-2) can be contained. In this case, mechanical properties such as tensile strength and elongation at break, surface gloss, and surface hardness can be excellent.

[0153] When both the copolymer (b-1-1) and the copolymer (b-1-2) are contained, the copolymer (b-1-1) can be contained in an amount greater than that of the copolymer (b-1-2). The copolymer (b-1-1) and the copolymer (b-1-2) can be contained in a weight ratio (b-1-1:b-1-2) of preferably 5.5:4.5 to 8.5:1.5, more preferably 6:4 to 8:2, and even more preferably 6.5:3.5 to 7.8:2.2. Within this range, mechanical properties such as tensile strength and elongation at break, surface gloss, and surface hardness can be excellent, and the appearance quality can be excellent due to the absence of flow marks, bubbles, and precipitation, and the calendering processability can be excellent.

[0154] The copolymer (b-1) can preferably be a styrene-acrylonitrile copolymer (SAN resin), an α-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof, more preferably a styrene-acrylonitrile copolymer (SAN resin). In this case, mechanical properties such as tensile strength and elongation at break, surface gloss, and surface hardness can be excellent.

[0155] The types of the aromatic vinyl compound and the vinyl cyanide compound contained in the aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) can be within the same range as the types of the aromatic vinyl compound and the vinyl cyanide compound contained in the copolymer (A) of the present disclosure.

[0156] The copolymer (b-1) can be prepared by solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, preferably bulk polymerization.

[0157] In the present invention, solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization methods commonly used in the field to which the present invention pertains can be used without particular limitation.

[0158] The copolymer (b-1-1) may preferably have a weight-average molecular weight of 110,000 g / mol to 140,000 g / mol, more preferably 110,000 g / mol to 130,000 g / mol. Within this range, mechanical properties such as tensile strength and elongation, surface gloss, and surface hardness can be excellent.

[0159] Based on the total weight of the copolymer (b-1-1), the copolymer (b-1-1) may contain, for example, 60% by weight to 85% by weight of an aromatic vinyl compound and 15% by weight to 40% by weight of a vinyl cyanide compound, preferably 65% by weight to 80% by weight of an aromatic vinyl compound and 20% by weight to 35% by weight of a vinyl cyanide compound, more preferably 72% by weight to 80% by weight of an aromatic vinyl compound and 20% by weight to 28% by weight of a vinyl cyanide compound. Within this range, mechanical properties such as tensile strength and elongation, surface gloss, and surface hardness can be excellent.

[0160] The copolymer (b-1-2) may preferably have a weight-average molecular weight of 160,000 g / mol to 190,000 g / mol, more preferably 160,000 g / mol to 180,000 g / mol. Within this range, mechanical properties such as tensile strength and elongation, surface gloss, and surface hardness can be excellent.

[0161] Based on the total weight of the copolymer (b-1-2), the copolymer (b-1-2) may contain, for example, 55% by weight to 80% by weight of an aromatic vinyl compound and 20% by weight to 45% by weight of a vinyl cyanide compound, preferably 60% by weight to 75% by weight of an aromatic vinyl compound and 25% by weight to 40% by weight of a vinyl cyanide compound, more preferably 63% by weight to 71% by weight of an aromatic vinyl compound and 29% by weight to 37% by weight of a vinyl cyanide compound. Within this range, mechanical properties such as tensile strength and elongation, surface gloss, and surface hardness can be excellent.

[0162] (Meth)acrylic acid alkyl ester polymer (b-2)

[0163] Based on the total weight of the base resin, the (meth)acrylic acid alkyl ester polymer (b-2) can be included in an amount of, for example, 0 wt% to 75 wt%, preferably 15 wt% to 75 wt%, more preferably 20 wt% to 55 wt%, even more preferably 25 wt% to 45 wt%, and even still more preferably 30 wt% to 40 wt%. Within this range, mechanical properties can be maintained, transparency and gloss can be excellent, and the occurrence of whitening during bending processing can be reduced.

[0164] (The (meth)acrylic acid alkyl ester polymer (b-2) can include one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate. Preferably, it is an alkyl methacrylate, an alkyl acrylate, or a mixture thereof, and more preferably a polymethyl methacrylate resin. In this case, mechanical properties, fluidity, and transparency can be excellent.

[0165] In the present disclosure, the (meth)acrylic acid alkyl ester polymer can be a polymer containing 85 wt% or more, 90 wt% or more, or 95 wt% or more of (meth)acrylic acid alkyl ester.

[0166] In the present disclosure, unless otherwise specified, both "acrylic acid alkyl ester" and "methyl acrylic acid alkyl ester" can refer to "(meth)acrylic acid alkyl ester".

[0167] The polymethyl methacrylate resin can include, for example, methyl methacrylate and methyl acrylate. Preferably, based on the total weight of the polymethyl methacrylate resin, it can include 85 wt% to 99 wt% of methyl methacrylate and 1 wt% to 15 wt% of methyl acrylate, preferably 90 wt% to 98 wt% of methyl methacrylate and 2 wt% to 10 wt% of methyl acrylate. Within this range, gloss, fluidity, and mechanical properties can be improved.

[0168] For example, the polymer (b-2) can have a weight-average molecular weight of 50,000 g / mol to 150,000 g / mol, preferably 60,000 g / mol to 130,000 g / mol, more preferably 70,000 g / mol to 110,000 g / mol, and still more preferably 70,000 g / mol to 100,000 g / mol. Within this range, transparency, gloss, and fluidity can be excellent while maintaining impact resistance.

[0169] The polymer (b-2) can have a glass transition temperature of 80 °C to 130 °C, preferably 90 °C to 120 °C. Within this range, heat resistance can be excellent.

[0170] In the present disclosure, the glass transition temperature can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM D3418. As a specific example, the glass transition temperature can be measured using a differential scanning calorimeter (Q100 DSC, TA Instruments Co.) at a heating rate of 10 °C / min.

[0171] For example, the polymer (b-2) can have a melt flow index, for example, of 15 g / 10 min to 120 g / 10 min, preferably 30 g / 10 min to 80 g / 10 min, more preferably 40 g / 10 min to 50 g / 10 min, measured at 220 °C under a load of 10 kg in accordance with ASTM D1238. Within this range, the processability can be excellent.

[0172] For example, the polymer (b-2) can have a refractive index of, for example, 1.480 to 1.500, preferably 1.485 to 1.495, more preferably 1.488 to 1.492. Within this range, the transparency can be excellent.

[0173] In the present disclosure, the refractive index can be measured by a measurement method commonly used in the technical field to which the present invention pertains. Specifically, the refractive index can be measured at room temperature (20 ± 5 °C) using an Abbe refractometer in accordance with ASTM D542.

[0174] For example, the (meth)acrylic acid alkyl ester polymer (b-2) can be prepared by suspension polymerization. In the present invention, a suspension polymerization method commonly used in the field to which the present invention pertains can be used without particular limitation.

[0175] Pentaerythritol lubricant (C)

[0176] Based on 100 parts by weight of the base resin, the pentaerythritol-based lubricant (C) can be included in an amount of, for example, 0.3 parts by weight to 2 parts by weight, preferably 0.3 parts by weight to 1.7 parts by weight, more preferably 0.5 parts by weight to 1.5 parts by weight. Within this range, the processability can be equal to or higher than that of a conventional material, PVC resin, used for calendering. Due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent, and calendering can be performed using existing calendering equipment.

[0177] The pentaerythritol-based lubricant (C) can preferably be a compound represented by the following formula 1. In this case, the processability can be equal to or higher than that of a conventional material, PVC resin, used for calendering. Due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent, and calendering can be performed using existing calendering equipment.

[0178] [Formula 1]

[0179]

[0180] In Formula 1, R1, R2, R3, and R4 are each independently an alkyl group having 1 to 18 carbon atoms or an alkyl group having 1 to 18 carbon atoms substituted with 1, 2, or more carboxylic acid groups.

[0181] The pentaerythritol-based lubricant (C) can be more preferably a compound and / or complex containing pentaerythritol and a carboxylic acid. In this case, the processability can be equal to or higher than that of conventional materials for calendering, such as PVC resin. Due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent, and calendering can be performed using existing calendering equipment.

[0182] The carboxylic acid can be preferably a monocarboxylic acid, a dicarboxylic acid, or a mixture thereof.

[0183] The carboxylic acid can be, for example, one or more selected from myristic acid, stearic acid, palmitic acid, oleic acid, and linolenic acid, and more preferably stearic acid.

[0184] The dicarboxylic acid can be, for example, one or more selected from oxalic acid, maleic acid, malic acid, succinic acid, and adipic acid, and more preferably adipic acid.

[0185] The pentaerythritol-based lubricant (C) can have a melting point of, for example, 100 °C or lower, preferably 80 °C or lower, more preferably 70 °C or lower, even more preferably 65 °C or lower, and even still more preferably 30 °C to 65 °C. Within this range, the processability can be equal to or higher than that of conventional materials for calendering, such as PVC resin. Due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent, and calendering can be performed using existing calendering equipment.

[0186] In the present disclosure, a differential scanning calorimeter 2920 (DSC 2920, TA Co.) can be used to measure the melting point. As a specific example of measuring the melting point, after equilibrating the DSC at a temperature of 0 °C, the temperature is raised to 180 °C at a rate of 20 °C / min, the temperature is lowered to -60 °C at a rate of 20 °C / min, and then the temperature is raised to 180 °C at a rate of 10 °C / min. At this time, in the second temperature-raising section, the melting point is obtained from the top region of the endothermic curve.

[0187] The pentaerythritol-based lubricant (C) may have an acid value, as measured according to ASTM E203, of, for example, 20 mg KOH / g or less, preferably 17 mg KOH / g or less, more preferably 15 mg KOH / g or less, and even more preferably from 1 mg KOH / g to 15 mg KOH / g. Within this range, the processability may be equal to or higher than that of conventional materials such as PVC resin used for calendering. Due to the absence of flow marks, bubbles, and exudation, the surface quality may be excellent, and calendering can be performed using existing calendering equipment.

[0188] The pentaerythritol-based lubricant (C) may have a moisture content, as measured according to ASTM E203, of, for example, 1.5 wt% or less, preferably 1 wt% or less, and more preferably from 0.01 wt% to 1 wt%. Within this range, the processability may be equal to or higher than that of conventional materials such as PVC resin used for calendering. Due to the absence of flow marks, bubbles, and exudation, the surface quality may be excellent, and calendering can be performed using existing calendering equipment.

[0189] The pentaerythritol-based lubricant (C) may have a saponification value, as measured according to ASTM D97, of, for example, from 220 mg KOH / g to 320 mg KOH / g, preferably from 240 mg KOH / g to 300 mg KOH / g, more preferably from 260 mg KOH / g to 290 mg KOH / g, and even more preferably from 270 mg KOH / g to 280 mg KOH / g. Within this range, the processability may be equal to or higher than that of conventional materials such as PVC resin used for calendering. Due to the absence of flow marks, bubbles, and exudation, the surface quality may be excellent, and calendering can be performed using existing calendering equipment.

[0190] The pentaerythritol-based lubricant (C) may have an iodine value, as measured according to the American Oil Chemists' Society ("AOCS") method Cd 1-92, of, for example, 2.3 or less, preferably 2.1 or less, and more preferably from 1 to 2.1. Within this range, the processability may be equal to or higher than that of conventional materials such as PVC resin used for calendering. Due to the absence of flow marks, bubbles, and exudation, the surface quality may be excellent, and calendering can be performed using existing calendering equipment.

[0191] Glycerol lubricant (D)

[0192] Based on 100 parts by weight of the base resin, the glycerol-based lubricant (D) can be included in an amount of, for example, 0.1 to 1.5 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.1 to 0.7 parts by weight, and even more preferably 0.3 to 0.7 parts by weight. Within this range, the synergistic effect with the pentaerythritol-based lubricant (C) can be expressed, such that the processing performance can be equal to or higher than that of the conventional material PVC resin used for calendering, and due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent. Therefore, a beautiful appearance can be achieved, and calendering can be performed using existing calendering equipment.

[0193] The glycerol-based lubricant (D) can have a molecular weight of, for example, 400 g / mol or less, preferably 100 to 400 g / mol, more preferably 200 to 400 g / mol, and even more preferably 300 to 400 g / mol. Within this range, the synergistic effect with the pentaerythritol-based lubricant (C) can be expressed, such that the processing performance can be equal to or higher than that of the conventional material PVC resin used for calendering, and due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent. Therefore, a beautiful appearance can be achieved, and calendering can be performed using existing calendering equipment.

[0194] In the present disclosure, the molecular weight can be measured by GC / MS structural analysis. Specifically, the column is HP-5 (0.32 mm (ID) * 30 m, 0.25 μm d.f. capillary), the gas flow rate (column (He)) is 1 ml / min, the oven temperature is initially 40 °C, then after 5 minutes it is increased to 330 °C at 10 °C / min and held for 15 minutes, and the injector temperature is 250 °C, the split ratio is 1 / 120, and the injection volume can be adjusted to 0.2 μl for measurement.

[0195] The glycerol-based lubricant (D) can have a melting point of, for example, 100 °C or less, preferably 80 °C or less, more preferably 70 °C or less, even more preferably 65 °C or less, and even still more preferably 30 to 65 °C. Within this range, the synergistic effect with the pentaerythritol-based lubricant (C) can be expressed, such that the processing performance can be equal to or higher than that of the conventional material PVC resin used for calendering, and due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent. Therefore, a beautiful appearance can be achieved, and calendering can be performed using existing calendering equipment.

[0196] The glycerol-based lubricant (D) can be, for example, a glycerol fatty acid ester compound, preferably selected from one or more of glycerol monostearate, glycerol monolaurate, glycerol monooleate, glycerol monopalmitate, glycerol monomyristate, glycerol distearate, glycerol dilaurate, glycerol dioleate, glycerol dipalmitate, and glycerol dimyristate, more preferably a mixture of glycerol monostearate and glycerol monopalmitate. In this case, a synergistic effect with the pentaerythritol-based lubricant (C) can be expressed, such that the processing performance can be equal to or higher than that of the conventional material PVC resin for calendering processing, and the surface quality can be excellent due to the absence of flow marks, bubbles, and exudation. Therefore, a beautiful appearance can be achieved, and calendering processing can be carried out using existing calendering equipment.

[0197] In the mixture of glycerol monostearate and glycerol monopalmitate, the weight ratio of glycerol monostearate to glycerol monopalmitate can preferably be from 3:7 to 7:3, more preferably from 4:6 to 6:4. Within this range, a synergistic effect with the pentaerythritol-based lubricant (C) can be expressed, such that the processing performance can be equal to or higher than that of the conventional material PVC resin for calendering processing, and the surface quality can be excellent due to the absence of flow marks, bubbles, and exudation. Therefore, a beautiful appearance can be achieved, and calendering processing can be carried out using existing calendering equipment.

[0198] Thermoplastic resin composition

[0199] For example, at a roll temperature of 170 °C, a calendering roll speed of 15 rpm, and a calendering roll gap of 0.28 mm, the thermoplastic resin composition can be roll-rolled and extruded to produce a sheet having a thickness of 0.3 mm. During the roll-rolling and extrusion, the processes of plasticizing, coating, and degassing on the surface of the roll can be carried out within 3 minutes. The formed sheet can be attached to and separated from the roll without deformation or damage, thus exhibiting excellent calendering processing performance.

[0200] Unless otherwise specified, in the present disclosure, the sheet can be any one of a sheet, a film, or a foil.

[0201] For example, at a roll temperature of 170 °C, a calendering roll speed of 15 rpm, and a calendering roll gap of 0.28 mm, the thermoplastic resin composition can be roll-rolled and extruded to produce a sheet having a thickness of 0.3 mm. When the thermoplastic resin composition is melted for 1 minute, mixed for 3 minutes, and then held for 1 minute, under the roll-rolling and extrusion conditions, based on visual observation, exudation may not occur, thereby improving the appearance quality.

[0202] For example, when the thermoplastic resin composition is made into a sheet by calendering processing, based on visual observation, bubbles may not be generated in the sheet, thereby improving the appearance quality.

[0203] The thermoplastic resin composition may have a Rockwell hardness measured by the R-scale according to ASTM D785 of, for example, 78 or more, preferably 81 or more, more preferably 81 to 115. Within this range, the balance of properties and scratch resistance can be excellent.

[0204] As needed, based on 100 parts by weight of the base resin, the thermoplastic resin composition may contain 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 part by weight of one or more selected from heat stabilizers, dyes, pigments, colorants, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, smoke suppressants, antifogging agents, antifriction agents, and antiwear agents. Within this range, the desired physical properties of the thermoplastic resin composition of the present invention can be achieved without degrading its inherent physical properties.

[0205] The heat stabilizer may preferably include a first heat stabilizer, a second heat stabilizer, or a mixture thereof.

[0206] For example, the first heat stabilizer may be a phenolic heat stabilizer. Preferably, the first heat stabilizer may include one or more selected from 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate, 1,6-hexanediol bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, tris(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 2,2-bis[4-(2-3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane, and octadecyl B-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, more preferably octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IR1076).

[0207] For example, the second heat stabilizer may be a phosphorus heat stabilizer. Preferably, the second heat stabilizer may include one or more selected from bis(dialkylphenyl)pentaerythritol diphosphite, phosphite, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, tris(mono- and di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tris[4,4'-isopropylidene bis(2-tert-butylphenol)] phosphite, bis(isodecyl)phenyl phosphite, 4,4'-isopropylidene bis(2-tert-butylphenol) bis(nonylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]-dioxaphosphin-6-yl)oxy]-N,N-bis[2-[(2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1.3.2]-dioxaphosphin-6-yl)oxy]ethyl]-ethylamine, and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]-dioxaphosphin, and more preferably tris(2,4-di-tert-butylphenyl) phosphite (IF168).

[0208] Method for preparing a thermoplastic resin composition

[0209] The method for preparing a thermoplastic resin composition according to the present disclosure comprises kneading and extruding 100 parts by weight of a base resin and 0.3 to 2 parts by weight of a pentaerythritol-based lubricant (C) under the conditions of 200°C to 300°C and 100 rpm to 500 rpm; the base resin comprises 25% to 75% by weight of one or more copolymers (A) and 25% to 75% by weight of one or more matrix resins (B), the copolymer (A) is selected from copolymers (a-1) comprising an acrylic alkyl ester rubber having an average particle size of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound, copolymers (a-2) comprising an acrylic alkyl ester rubber having an average particle size greater than 150 nm and up to 600 nm, an aromatic vinyl compound, and a vinyl cyanide compound, and copolymers (a-3) comprising an acrylic alkyl ester rubber having an average particle size of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound, the matrix resin (B) is selected from aromatic vinyl compound-vinyl cyanide copolymers (b-1) and (meth)acrylic alkyl ester polymers (b-2); wherein the copolymer (a-3) has an acrylic alkyl ester coverage rate (X) value of 65% by weight or more calculated by the following Equation 1.

[0210] [Equation 1]

[0211] X = {(G - Y) / Y} * 100

[0212] (In Equation 1, G represents the gel content (% by weight) based on the total weight of the copolymer (A), and Y represents the acrylic alkyl ester content (% by weight) in the gel based on the total weight of the copolymer (A).)

[0213] In addition, the method for preparing a thermoplastic resin composition according to the present disclosure includes kneading and extruding 100 parts by weight of a base resin and 0.3 to 2 parts by weight of a pentaerythritol-based lubricant (C) under the conditions of 200°C to 300°C and 100 rpm to 500 rpm; the base resin contains 25% to 75% by weight of one or more graft copolymers (A) and 25% to 75% by weight of one or more matrix resins (B), the graft copolymer (A) is selected from an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer (a-1) containing an alkyl acrylate rubber with an average particle size of 50 nm to 150 nm, an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer (a-2) containing an alkyl acrylate rubber with an average particle size greater than 150 nm and 600 nm or less, and an alkyl acrylate-aromatic vinyl compound-vinyl cyanide graft copolymer (a-3) containing an alkyl acrylate rubber with an average particle size of 50 nm to 120 nm, the matrix resin (B) is selected from an aromatic vinyl compound-vinyl cyanide copolymer (b-1) and an (alkyl) acrylate polymer (b-2); wherein the graft copolymer (a-3) has an acrylic alkyl ester coverage rate (X) value of more than 65% calculated by the following Equation 1. In this case, compared with a conventional ASA resin composition, the mechanical properties and weather resistance are maintained at the same level, while flow marks and bubbles do not occur, and the die deposits are significantly reduced, resulting in excellent appearance quality. It can be processed using existing calendering equipment and has excellent calendering processability.

[0214] [Equation 1]

[0215] X = {(G - Y) / Y} * 100

[0216] In Equation 1, G represents the gel content (wt%) based on the total weight of the graft copolymer, and Y represents the acrylic alkyl ester content (wt%) in the gel based on the total weight of the graft copolymer.

[0217] Based on 100 parts by weight of the base resin, the method for preparing a thermoplastic resin composition may further include, for example, a glycerol-based lubricant (D) in an amount of 0.3 to 1.5 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.1 to 0.7 part by weight, and even more preferably 0.3 to 0.7 part by weight. Within this range, a synergistic effect with the pentaerythritol-based lubricant (C) can be expressed, such that the mechanical properties and weather resistance can be equal to or higher than those of a conventional material PVC resin for calendering processing, and due to the significant reduction of flow marks, bubbles, and exudation, the appearance quality can be excellent. Therefore, calendering processing can be performed using existing calendering equipment, and the calendering processability can be excellent.

[0218] The method for preparing the thermoplastic resin composition shares all the technical features of the above-mentioned thermoplastic resin composition. Therefore, its repeated description will be omitted.

[0219] Kneading and extrusion can be carried out using an extruder at a temperature preferably of 200°C to 300°C, more preferably 210°C to 260°C, still more preferably 220°C to 250°C. Within this range, extrusion can be carried out stably and kneading can be carried out effectively. At this time, the temperature is the temperature set in the cylinder.

[0220] For example, kneading and extrusion can be carried out at a screw rotation speed of 100 rpm to 500 rpm, preferably 150 rpm to 450 rpm, more preferably 200 rpm to 400 rpm. In this case, due to an appropriate production amount per unit time, the process efficiency can be excellent.

[0221] For example, the thermoplastic resin composition obtained by extrusion can be made into pellets using a pelletizer.

[0222] An extruder commonly used in the field to which the present invention pertains can be used without particular limitation, and a twin-screw extruder is preferably used.

[0223] Molded article

[0224] The molded article of the present disclosure includes the thermoplastic resin composition. In this case, the processability can be equal to or higher than that of the conventional material PVC resin used for calendering processing. Due to the absence of flow marks, bubbles, and exudation, the surface quality can be excellent, and calendering processing can be carried out using existing calendering equipment.

[0225] The calendered molded article can preferably be a film, sheet, or foil, particularly a decorative sheet for furniture decoration, a decorative material for outdoor building materials, a decorative material for roofing, an inner film, wallpaper, an edge band, vinyl-coated metal (VCM), a floor material, plastic-steel-plastic (PSP) for molding, or a packaging film.

[0226] The method for manufacturing a film product preferably includes kneading and extruding 100 parts by weight of a base resin and 0.3 to 2 parts by weight of a pentaerythritol-based lubricant (C) under the conditions of 200°C to 300°C and 100 rpm to 500 rpm to prepare an extrudate; and forming the extrudate to manufacture a film product; the base resin contains 25% to 75% by weight of one or more copolymers (A) and 25% to 75% by weight of one or more matrix resins (B), the copolymer (A) is selected from copolymers (a-1) containing an acrylic alkyl ester rubber having an average particle size of 50 nm to 150 nm, an aromatic vinyl compound, and a vinyl cyanide compound, copolymers (a-2) containing an acrylic alkyl ester rubber having an average particle size greater than 150 nm and 600 nm or less, an aromatic vinyl compound, and a vinyl cyanide compound, and copolymers (a-3) containing an acrylic alkyl ester rubber having an average particle size of 50 nm to 120 nm, an aromatic vinyl compound, and a vinyl cyanide compound, the matrix resin (B) is selected from aromatic vinyl compound-vinyl cyanide copolymers (b-1) and (meth)acrylic alkyl ester polymers (b-2); wherein the copolymer (a-3) has an acrylic alkyl ester coverage rate (X) value of 65% by weight or more calculated by the following Equation 1. In this case, the processability can be equal to or higher than that of the conventional material PVC resin for calendering processing, the surface quality may be excellent due to no flow marks, bubbles, and exudation, and calendering processing can be performed using existing calendering equipment.

[0227] [Equation 1]

[0228] X = {(G - Y) / Y} * 100

[0229] (In Equation 1, G represents the gel content (wt%) based on the total weight of the copolymer (A), and Y represents the acrylic alkyl ester content (wt%) in the gel based on the total weight of the copolymer (A).)

[0230] In addition, the method for manufacturing a film product preferably includes kneading and extruding 100 parts by weight of a base resin and 0.3 to 2 parts by weight of a pentaerythritol-based lubricant (C) under the conditions of 200°C to 300°C and 100 rpm to 500 rpm to prepare an extrudate; and shaping the extrudate to manufacture a film product; the base resin contains 25% to 75% by weight of one or more graft copolymers (A) and 25% to 75% by weight of one or more matrix resins (B), the graft copolymer (A) is selected from an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-1) containing an acrylate rubber with an average particle size of 50 nm to 150 nm, an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-2) containing an acrylate rubber with an average particle size greater than 150 nm and 600 nm or less, and an acrylate- aromatic vinyl compound-vinyl cyanide graft copolymer (a-3) containing an acrylate rubber with an average particle size of 50 nm to 120 nm, the matrix resin (B) is selected from an aromatic vinyl compound-vinyl cyanide copolymer (b-1) and a (meth)acrylate polymer (b-2); wherein the graft copolymer (a-3) has an acrylate coverage rate (X) value of 65% by weight or more calculated by the following Equation 1. In this case, the processability can be equal to or higher than that of a conventional material PVC resin for calendering processing, the surface quality can be excellent due to no flow marks, bubbles, and exudation, and calendering processing can be performed using existing calendering equipment.

[0231] [Equation 1]

[0232] X = {(G - Y) / Y} * 100

[0233] In Equation 1, G represents the gel content (% by weight) based on the total weight of the graft copolymer, and Y represents the acrylate content (% by weight) in the gel based on the total weight of the graft copolymer.

[0234] For example, the extrudate can have a pellet shape or a plate shape.

[0235] In the present disclosure, there is no particular limitation on the plate shape as long as the plate shape is generally defined as the plate shape in the field to which the present invention belongs. For example, the plate shape can include a flat shape, a sheet shape, a film shape, and a foil shape.

[0236] In describing the thermoplastic resin composition of the present invention, the method for preparing the thermoplastic resin composition, and the molded article including the thermoplastic resin composition, it should be noted that other conditions or equipment not specifically described herein can be appropriately selected within the range that can be generally implemented in the art without particular limitation.

[0237] Hereinafter, the present invention will be described in more detail with reference to the following preferred embodiments. However, these embodiments are provided for illustrative purposes only and should not be construed as limiting the scope and concept of the present invention. In addition, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the concept and scope of the present invention, and such changes and modifications are also within the scope of the appended claims.

[0238] [Examples]

[0239] The materials used in the following examples and comparative examples are as follows.

[0240] * ASA graft copolymer (a-1) containing acrylic alkyl ester rubber with an average particle size of 50 nm to 150 nm: An ASA graft copolymer prepared by emulsion polymerization (rubber (core): 50% by weight of butyl acrylate, shell: 37.5% by weight of styrene and 12.5% by weight of acrylonitrile, grafting degree: 35%) and containing acrylic alkyl ester rubber with an average particle size of 130 nm.

[0241] * ASA graft copolymer (a-2) containing acrylic alkyl ester rubber with an average particle size greater than 150 nm and 600 nm or less: An ASA graft copolymer prepared by emulsion polymerization (rubber (core): 50% by weight of butyl acrylate, shell: 37.5% by weight of styrene and 12.5% by weight of acrylonitrile, grafting degree: 50%) and containing acrylic alkyl ester rubber with an average particle size of 350 nm.

[0242] * ASA graft copolymer (a-3) containing acrylic alkyl ester rubber with an average particle size of 50 nm to 120 nm: An ASA graft copolymer prepared by emulsion polymerization (rubber (core): 36% by weight of butyl acrylate, 7% by weight of styrene, shell: 4% by weight of butyl acrylate, 39.5% by weight of styrene and 13.5% by weight of acrylonitrile, acrylic alkyl ester coverage value: 99% by weight, grafting degree: 77%) and containing acrylic alkyl ester rubber with an average particle size of 70 nm.

[0243] * SAN resin (b-1-1) having a Mw of 120,000 mol: Styrene-acrylonitrile copolymer (acrylonitrile 27% by weight)

[0244] * SAN resin (b-1-2) having a Mw of 170,000 mol: Styrene-acrylonitrile copolymer (acrylonitrile 30% by weight)

[0245] *PMMA resin (b-2) prepared by suspension polymerization: polymethyl methacrylate resin (weight average molecular weight: 80,000 g / mol, melt flow index (220 °C, 10 kg): 45 g / 10 min, refractive index: 1.490)

[0246] *Pentaerythritol lubricant (C-1): pentaerythritol adipate stearate (melting point: 57 °C, acid value: 15 mg KOH / g or less, saponification degree: 278 mg KOH / g)

[0247] *EBA: ethylenebisstearamide (C-2)

[0248] *St-acid: stearic acid (C-3)

[0249] *Ethylene glycol dipalmitate (C-4)

[0250] *Glycerol lubricant (D): mixture of glycerol monostearate (molecular weight: 358 g / mol) and glycerol monopalmitate (molecular weight: 345 g / mol) (weight ratio: 1:1)

[0251] Examples 1 to 8 and Comparative Examples 1 to 7

[0252] According to the content shown in Table 1 and Table 2, the components shown in Table 1 and Table 2 were fed into a twin-screw extruder. Then, melt kneading and extrusion were carried out at 230 °C and 150 rpm to prepare pellets. The prepared pellets were injection molded at 220 °C to manufacture injection molded specimens.

[0253] In addition, using a roll mill (MR-LM0820, Mirae RPM Co.) with two calendering rolls having a diameter of 30 cm installed at an interval of 0.3 mm, the pellets were calendered while maintaining the temperature of the rolls at 180 °C to obtain a sheet with a thickness of 0.3 mm.

[0254] [Test Example]

[0255] According to the following method, the properties of the pellets, injection molded specimens or sheets prepared in Examples 1 to 8 and Comparative Examples 1 to 7 were measured, and the results are shown in Table 1 and Table 2 below.

[0256] Measurement method

[0257] *Acrylic alkyl ester coverage value (X value, wt%) of the graft copolymer (a-3): The acrylic alkyl ester coverage value of the graft copolymer (a-3) was calculated by the following Equation 1.

[0258] [Equation 1]

[0259] X = {(G - Y) / Y} * 100

[0260] In Equation 1, G represents the gel content (wt%) based on the total weight of the graft copolymer, and Y represents the alkyl acrylate content (wt%) in the gel based on the total weight of the graft copolymer.

[0261] Here, 1 an NMR analyzer or FT-IR is used to quantitatively calculate the alkyl acrylate content in the gel. The specific measurement conditions are as follows.

[0262] 1 H NMR

[0263] - Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy probe

[0264] - Measurement conditions: 1H NMR (zg30): ns = 32, d1 = 5s, TCE-d2, at room temperature.

[0265] FT-IR

[0266] - Equipment name: Agilent Cary 66

[0267] - Measurement conditions: ATR mode

[0268] * Gel content (%): Add 1 g of the graft copolymer to 30 ml of acetone, and then stir for 12 hours at 210 rpm and room temperature using an orbital shaker (equipment name: Lab companion SKC-6075). Then, centrifuge at 0 °C and 18,000 rpm for 3 hours using a centrifuge (Supra R30, Hanil Science Co.) to separate the insoluble matter that is not dissolved in acetone. Subsequently, dry in a forced convection oven (equipment name: Lab companion OF-12GW) set at 85 °C for 12 hours by forced circulation. Then, measure the weight of the insoluble matter, and calculate the gel content using Equation 3 below.

[0269] [Equation 3]

[0270] Gel content (wt%) = [weight of insoluble matter (gel) (g) / weight of sample (g)] × 100

[0271] *Degree of grafting (%): Add 0.5 g of dry graft copolymer powder to 50 ml of acetone, stir at room temperature for 12 hours, centrifuge to separate only the insoluble matter that has not dissolved in acetone, and dry the separated insoluble matter for 12 hours. Then, measure the weight of the dried insoluble matter and calculate the degree of grafting using Equation 2 below.

[0272] [Equation 2]

[0273] Degree of grafting (%) = [Weight of graft monomer (g) / Weight of rubber (g)] * 100

[0274] In Equation 2, the weight of the graft monomer (g) is obtained by subtracting the weight of the rubber (g) from the weight of the insoluble matter (gel) obtained by dissolving the graft copolymer in acetone and centrifuging. The weight of the rubber (g) is the weight of the rubber component theoretically added to the graft copolymer powder.

[0275] As a specific measurement example, when measuring the weight of the insoluble matter (gel), add 0.5 g of dry graft copolymer powder to 50 ml of acetone, then stir using an orbital shaker (equipment name: Lab companion SKC-6075) at 210 rpm and room temperature for 12 hours. Then, centrifuge using a centrifuge (Supra R30, Hanil Science Co.) at 0 °C and 18,000 rpm for 3 hours to separate the insoluble matter that has not dissolved in acetone, and then dry it by forced circulation in a forced convection oven (equipment name: Lab companion OF-12GW) set at 85 °C for 12 hours. Then, measure the weight of the insoluble matter (gel).

[0276] *Exudation: At a roll temperature of 170 °C, a calender roll speed of 15 rpm, and a calender roll gap of 0.28 mm, roll and extrude the thermoplastic resin composition pellets to produce a sheet with a thickness of 0.3 mm. Under the roll and extrusion conditions, melt it for 1 minute, mix for 3 minutes, and then hold for 1 minute. Then, visually observe whether exudation occurs on the sheet and evaluate as follows.

[0277] Satisfactory: No exudation

[0278] Occurrence: Exudation occurs

[0279] *Flow marks: Visually observe the degree of appearance of flow marks on the manufactured sheet and evaluate as follows:

[0280] ★★★: No flow marks

[0281] ★★☆: Some flow marks appear

[0282] ★☆☆: A large number of flow marks appear.

[0283] * Roller adhesion: At a roller temperature of 170 °C, a calender roll speed of 15 rpm, and a calender roll gap of 0.28 mm, thermoplastic resin composition pellets are roll-milled and extruded to produce a sheet with a thickness of 0.3 mm. During roll-milling and extrusion, if the stabilization process of plasticization, coating, and degassing of the thermoplastic resin composition on the roller surface is carried out within 3 minutes, and the formed sheet can be attached to and separated from the roller without deformation or damage, the processability is evaluated as excellent.

[0284] ★★★: Excellent processability

[0285] ★★☆: Ordinary processability

[0286] ★☆☆: Poor processability

[0287] * Hardness: Rockwell hardness is measured on the R-scale according to ASTM D785.

[0288] * Occurrence of migration after long-term storage: After a calendered sheet with a width of 10 cm is stored in a roll at 25 °C and a humidity of 50 RH% for 5 months, it is visually observed whether lubricant migrates to the sheet surface. If no migration occurs, it is marked as "X", and if migration occurs, it is marked as "○".

[0289] [Table 1]

[0290]

[0291] [Table 2]

[0292]

[0293] (In Tables 1 and 2, the content of each of (a-1), (a-2), (b-1-1), (b-1-2), and (b-2) is given in weight % based on the total weight of (a-1), (a-2), (b-1-1), (b-1-2), and (b-2), and the content of each of (C-1), (C-2), (C-3), (C-4), and (D) is given in parts by weight based on a total of 100 parts by weight of (C-1), (C-2), (C-3), (C-4), and (D).)

[0294] As shown in Tables 1 to 2, compared with Comparative Examples 1 to 7, the thermoplastic resin compositions of Examples 1 to 8 according to the present invention did not exhibit exudation, flow marks, and bubbles, indicating excellent appearance quality and excellent processability. Here, Examples 1 to 4, 7, and 8 containing glycerol-based lubricant (D) showed a reduction in the appearance of flow marks and excellent roll adhesion and hardness.

[0295] On the other hand, Comparative Example 1 containing ethylene glycol dipalmitate (C-4) showed exudation and flow marks, resulting in deterioration of the appearance quality.

[0296] In addition, Comparative Example 2 containing stearic acid (C-3) had poor appearance quality due to the appearance of flow marks and bubbles and had poor roll adhesion.

[0297] In addition, Comparative Example 3 containing EBA (C-2) had poor appearance quality due to the appearance of exudation, flow marks, and bubbles and had poor roll adhesion.

[0298] In addition, Comparative Example 4 containing a small amount of pentaerythritol-based lubricant (C-1) showed exudation, bubbles, and flow marks, while Comparative Example 5 containing an excessive amount of pentaerythritol-based lubricant (C-1) showed migration of the lubricant to the sheet surface after long-term storage.

[0299] In addition, Comparative Example 6 containing a small amount of graft copolymer (A) and an excessive amount of matrix resin (B) could not perform the calendering process, while Comparative Example 7 containing an excessive amount of graft copolymer (A) and a small amount of matrix resin (B) showed a significant reduction in hardness.

[0300] In summary, according to the present invention, when a predetermined content of pentaerythritol-based lubricant is added to a base resin (including one or more copolymers of three types of copolymers of acrylic alkyl esters, aromatic vinyl compounds, and vinyl cyanide compounds containing acrylic alkyl ester rubbers with different average particle sizes); and one or more matrix resins of aromatic vinyl compound-vinyl cyanide copolymer and (meth)acrylic alkyl ester polymer, and further the acrylic alkyl ester coverage value of the copolymer containing acrylic alkyl ester rubber, aromatic vinyl compound, and vinyl cyanide compound is adjusted to a predetermined range, the processability is equal to or higher than that of the conventional material PVC resin for calendering processing, the surface quality is excellent due to the absence of flow marks, bubbles, and exudation, and it can be calendered using existing calendering equipment.

Claims

1. A thermoplastic resin composition, comprising: 100 parts by weight of a base resin, comprising 25 to 75% by weight of one or more copolymers (A) and 25 to 75% by weight of one or more matrix resins (B), wherein the copolymer (A) is selected from a copolymer (a-1) comprising an alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound having an average particle size of 50 to 150 nm, a copolymer (a-2) comprising an alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound having an average particle size of greater than 150 nm and less than 600 nm, and a copolymer (a-3) comprising an alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound having an average particle size of 50 to 120 nm, wherein the matrix resin (B) is selected from an aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) and an alkyl (meth)acrylate polymer (b-2); and 0.3 to 2 parts by weight of a pentaerythritol-based lubricant (C), in, The copolymer (a-3) has an alkyl acrylate coverage (X) value of 65 wt % or more calculated by the following equation 1: [Equation 1] X={(GY) / Y}*100 wherein G represents the gel content (wt%) based on the total weight of the copolymer (A), and Y represents the alkyl acrylate content (wt%) in the gel based on the total weight of the copolymer (A).

2. The thermoplastic resin composition according to claim 1, wherein The copolymer (a-1), the copolymer (a-2) and / or the copolymer (a-3) is a graft copolymer.

3. The thermoplastic resin composition according to claim 1, wherein The pentaerythritol lubricant (C) has a melting point of 100° C. or less.

4. The thermoplastic resin composition according to claim 1, wherein The thermoplastic resin composition further includes 0.3 parts by weight to 1.5 parts by weight of a glycerin-based lubricant (D) based on 100 parts by weight of the base resin.

5. The thermoplastic resin composition according to claim 4, wherein The glycerin-based lubricant (D) has a molecular weight of 400 g / mol or less.

6. The thermoplastic resin composition according to claim 1, wherein The copolymer (a-1) includes 35 to 65 wt % of an alkyl acrylate rubber, 20 to 55 wt % of an aromatic vinyl compound, and 3 to 25 wt % of a vinyl cyanide compound, based on the total weight of the copolymer (a-1).

7. The thermoplastic resin composition according to claim 1, wherein The copolymer (a-2) includes 35 to 65 wt % of an alkyl acrylate rubber, 20 to 55 wt % of an aromatic vinyl compound, and 3 to 25 wt % of a vinyl cyanide compound, based on the total weight of the copolymer (a-2).

8. The thermoplastic resin composition according to claim 1, wherein The copolymer (a-3) has a grafting degree of 60% or more calculated by the following equation 2: [Equation 2] Grafting degree (%) = [weight of grafted monomer (g) / weight of rubber (g)] * 100 wherein the weight (g) of the graft monomer is obtained by subtracting the weight (g) of the rubber, which is the weight (g) of the rubber component theoretically added to the copolymer powder, from the weight (g) of the insoluble matter (gel) obtained by dissolving the copolymer in acetone and subjecting it to centrifugation.

9. The thermoplastic resin composition according to claim 1, wherein The copolymer (a-3) comprises 20 wt % to 60 wt % of an alkyl acrylate rubber based on the total weight of the copolymer (a-3); and 40 to 80 wt % of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding the alkyl acrylate rubber.

10. The thermoplastic resin composition according to claim 1, wherein The aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) is one or more selected from an aromatic vinyl compound-vinyl cyanide compound copolymer having a weight average molecular weight of 100,000 g / mol to 150,000 g / mol and an aromatic vinyl compound-vinyl cyanide compound copolymer having a weight average molecular weight of greater than 150,000 g / mol and less than 200,000 g / mol.

11. The thermoplastic resin composition according to claim 1, wherein The alkyl (meth)acrylate polymer (b-2) includes one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate and lauryl (meth)acrylate.

12. The thermoplastic resin composition according to claim 1, wherein The polymer (b-2) has a weight average molecular weight of 50,000 g / mol to 150,000 g / mol.

13. A method for preparing a thermoplastic resin composition, the method comprising: kneading and extruding 100 parts by weight of a base resin and 0.3 to 2 parts by weight of a pentaerythritol-based lubricant (C) at 200 to 300° C. and 100 to 500 rpm, wherein the base resin comprises 25 to 75% by weight of one or more copolymers (A) and 25 to 75% by weight of one or more matrix resins (B), wherein the copolymer (A) is selected from a copolymer (a-1) comprising an alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound having an average particle diameter of 50 to 150 nm, a copolymer (a-2) comprising an alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound having an average particle diameter of greater than 150 nm and less than 600 nm, and a copolymer (a-3) comprising an alkyl acrylate rubber, an aromatic vinyl compound and a vinyl cyanide compound having an average particle diameter of 50 to 120 nm, and the matrix resin (B) is selected from an aromatic vinyl compound-vinyl cyanide compound copolymer (b-1) and an alkyl (meth)acrylate polymer (b-2); Wherein, the copolymer (a-3) has an alkyl acrylate coverage (X) value of 65 wt % or more calculated by the following equation 1: [Equation 1] X={(GY) / Y}*100 wherein G represents the gel content (wt%) based on the total weight of the copolymer (A), and Y represents the alkyl acrylate content (wt%) in the gel based on the total weight of the copolymer (A).

14. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 12.

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