ASA-based resin composition, preparation method therefor, and molded product comprising same

Abstract

The present invention relates to an ASA-based resin composition, a preparation method therefor, and a molded product comprising same. According to the present invention, an ASA-based resin composition is provided which replaces a conventional transparent material, has improved releasability during injection molding while maintaining transparency, and can prevent injection cracking even when small medical transparent products or transparent food containers are injection molded.

Description

ASA resin composition, method for producing the same, and molded article comprising the same

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0122497, filed September 14, 2023, and Korean Patent Application No. 10-2024-0108280, filed August 13, 2024, which is hereby incorporated by reference herein, and all disclosures contained in the documents of the Korean patent applications are hereby incorporated by reference herein.

[0003] The present invention relates to an ASA resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to an ASA resin composition suitable as a small transparent material capable of providing an excellent balance of properties between injection molding release properties and transparency, a method for producing the same, and a molded article comprising the same.

[0004] Due to environmental concerns, acrylate-styrene-acrylonitrile graft copolymers (hereinafter referred to as "ASA resins") are attracting attention as transparent materials to replace existing transparent materials such as PVC resin and PC resin used in medical containers, food containers, etc. The ASA resins have excellent weather resistance, aging resistance, chemical resistance, and processability, and are widely used in various fields such as automobiles, home appliances, leisure goods, construction materials, gardening goods, and building materials.

[0005] However, the above ASA resin has poor release properties during the injection molding process for small transparent products, and cracks frequently occur during the injection molding process.

[0006] Accordingly, research was attempted to improve the release properties by adding additives to ABS resin, but in this case, transparency decreased rapidly, making it difficult to replace existing transparent materials.

[0007] Therefore, there is a need to develop an ASA resin composition that can provide excellent physical property balance with transparency while imparting injection molding release properties to the ASA resin.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] Korean Patent Publication No. 2011-0082121

[0011] The purpose of the present invention is to provide an ASA resin composition that has a level of injection molding release suitable for small transparent materials and an excellent balance of properties between the two and transparency, and a method for producing the same.

[0012] In addition, the present invention aims to provide a molded product manufactured from the ASA resin composition.

[0013] The above and other objects of the present invention can all be achieved by the present invention described below.

[0014] In order to achieve the above object, the present invention provides an ASA resin composition comprising: I) a base resin comprising (A) an acrylic graft copolymer, (B) a methacrylate copolymer, (C) a saturated carboxylic acid compound, and (D) an unsaturated carboxamide compound, wherein the (C) saturated carboxylic acid compound and (D) unsaturated carboxamide compound are contained in a total amount of 0.51 to 1.44 parts by weight based on 100 parts by weight of the base resin.

[0015] II) In the above I), the saturated carboxylic acid compound may be a compound having at least one -COOH group at the terminal and an alkyl group of C5 to C30 and having a refractive index (80° C.) of 1.35 to 1.45.

[0016] III) In the above I) or II), the unsaturated carboxamide compound may be a compound having at least one -CON group at the terminal and an alkyl group of C5 to C50 and having a refractive index (80° C.) of 1.5 to 1.6.

[0017] IV) In the above I) to III), the -CON group may be -CONH2, -CONHR1, -CONR1R2, etc., and the R1 and R2 may be, for example, an alkyl group having 1 to 5 carbon atoms.

[0018] V) In the above I) to IV), the saturated carboxylic acid compound and the unsaturated carboxamide compound may be included in a weight ratio of 1:0.5 to 1:1.5 (saturated carboxylic acid compound: unsaturated carboxamide compound).

[0019] VI) In the above I) to V), the total amount of the saturated carboxylic acid compound and the unsaturated carboxamide compound may be included in an amount of 1.5 parts by weight or less based on 100 parts by weight of the base resin, wherein the base resin may include an acrylic graft copolymer and a methacrylate copolymer.

[0020] VII) In the above I) to VI), the base resin may include (A) an acrylic graft copolymer: (B) a methacrylate copolymer in a weight ratio of 1:0.5 to 1:1.5 (A:B).

[0021] VIII) In the above I) to VII), the (A) acrylic graft copolymer may be included in an amount of 40 wt% or more.

[0022] IX) In the above I) to VIII), the (A) acrylic graft copolymer may include (A1) a small-particle-diameter acrylic graft copolymer and (A2) a large-particle-diameter acrylic graft copolymer.

[0023] X) In the above I) to IX), the (A) acrylic graft copolymer may include (A1) small-particle-diameter acrylic graft copolymer: (A2) large-particle-diameter acrylic graft copolymer in a weight ratio of 1:3.5 to 1:10 (A1:A2).

[0024] XI) In the above I) to X), the (A1) small-particle acrylic graft copolymer comprises 35 to 45 wt% of a rubbery polymer having an average particle diameter of 50 to 100 nm, 40 to 50 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyan compound, and / or may have a weight average molecular weight in the range of 50,000 to 150,000 g / mol.

[0025] XII) In the above I) to XI), the (A2) large-particle-diameter acrylic graft copolymer comprises 35 to 45 wt% of a rubbery polymer having an average particle diameter of 150 to 300 nm, 40 to 50 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyan compound, and / or may have a weight average molecular weight in the range of 50,000 to 150,000 g / mol.

[0026] XIII) In the above I) to XII), the saturated carboxylic acid compound may be included in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin.

[0027] XIV) In the above I) to XIII), the unsaturated carboxamide compound may be included in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin.

[0028] XV) In the above I) to XIV), the ASA resin composition may be continuously injected into a removable mold core using an injection molding machine (LS, molding force: 220 tons) at a temperature of 250 to 280° C. and a pressure of 25 to 35 bar for 200 shots, and the mold deposit calculated by the following mathematical formula 1 by measuring the weight of gas deposited in the mold core may be 40 mg or less.

[0029] [Mathematical Formula 1]

[0030] Mold deposit (mg) = Weight of mold core after 200 shots - Weight of initial mold core

[0031] XVI) In the above I) to XV), the ASA resin composition may have a force value of 1600 N or less as measured by installing an ejection force measuring device in the ejection step of a cup mold injection molding machine.

[0032] XVII) In the above I) to XVI), the ASA resin composition may have a haze measured according to ASTM D1003 of less than 3.0%.

[0033]

[0034] In addition, the present invention provides a method for producing an ASA resin composition, characterized in that XVIII) (A) a base resin including an acrylic graft copolymer, (B) a methacrylate copolymer, (C) a saturated carboxylic acid compound, and (D) an unsaturated carboxamide compound are kneaded and extruded under conditions of 200 to 300° C. and 100 to 500 rpm, wherein the (C) saturated carboxylic acid compound and the (D) unsaturated carboxamide compound are used in a total amount of 0.51 to 1.44 parts by weight based on 100 parts by weight of the base resin.

[0035]

[0036] In addition, the present invention provides a molded article characterized by including the ASA resin composition described above XIX).

[0037] XX) In the above XIX), the molded product may be a small transparent product including a small medical transparent product and a transparent food container.

[0038] XXI) In the above XIX) or XX), the small medical transparent product may be a syringe, a tube connector, etc.

[0039] The ASA resin composition according to the present invention can provide an injection molding release property suitable for small transparent materials and an excellent balance of properties between the injection molding release property and the transparency.

[0040] That is, a molded product manufactured using the ASA resin composition according to the present invention has the effect of improving both injection molding release properties and transparency and reducing mold deposit.

[0041] Therefore, the ASA resin composition according to the present invention can be widely applied to molded products such as small medical transparent products, transparent food containers, etc., including syringes and tube connectors that require it.

[0042] Figure 1 is a cross-sectional view of a cup mold injection machine used for measuring ejection force according to the present invention.

[0043]

[0044] To help understand the present invention, the present invention will be described in more detail below.

[0045] Terms or words used in this specification and claims should not be construed as limited to their usual or dictionary meanings, but should be construed as meanings and concepts that conform to the technical spirit of the present invention, taking into account that the inventor can appropriately define the concept of the term in order to explain the invention in the best way.

[0046] The present inventors have confirmed that injection molding release properties suitable for small transparent materials can be achieved by including a predetermined injection lubricity improving agent, and that a balance of properties between the injection molding release properties and the transparency can be achieved, and thus the present invention has been completed.

[0047]

[0048] The ASA resin composition according to the present invention is characterized by including an injection lubricity improving agent.

[0049] The term "injection lubricity improver" used herein, unless otherwise specified, refers to a compound that can improve release properties by preventing cracking during product injection without adversely affecting the composition of the ASA resin composition.

[0050]

[0051] Hereinafter, the ASA resin composition of the present invention will be described in detail by composition.

[0052]

[0053] Base resin

[0054] The base resin constituting the above ASA resin composition may be composed of (A) an acrylic graft copolymer and (B) a methacrylate copolymer.

[0055] For example, the base resin may include (A) an acrylic graft copolymer: (B) a methacrylate copolymer in a weight ratio of 1:0.5 to 1:1.5 (A:B), 1:0.7 to 1:1.5 (A:B), or 1:0.7 to 1:1.3 (A:B). In this case, there is an advantage of providing an excellent balance of properties between injection molding release properties and transparency while including an injection lubricity improving agent.

[0056]

[0057] Hereinafter, the base resin constituting the ASA resin composition of the present invention will be described in detail by composition.

[0058] (A) Acrylic graft copolymer

[0059] The above (A) acrylic graft copolymer may include (A1) a small-particle-size acrylic graft copolymer and (A2) a large-particle-size acrylic graft copolymer, and may improve impact strength compared to using a small-particle-size copolymer alone, and may improve whitening properties against alcohol compared to using a large-particle-size copolymer alone.

[0060]

[0061] (A1) Small particle size acrylic graft copolymer

[0062] The acrylate rubber of the above (A1) small-particle acrylic graft copolymer preferably has an average particle diameter of 50 to 100 nm, preferably 60 to 95 nm, more preferably 75 to 90 nm, and within this range has excellent mechanical strength such as impact strength.

[0063] In this paper, the average particle size can be measured using dynamic light scattering, and specifically, it is measured as an intensity value in Gaussian mode using a particle measuring device (product name: Nicomp 380, manufacturer: PSS). As a specific measurement example, 0.1 g of latex with a total solid content of 35 to 50 wt% is prepared by diluting 1,000 to 5,000 times with distilled water, and the measurement method is measured using a flow cell through auto-dilution. The measurement mode is dynamic light scattering / Intensity 300 KHz / Intensity-weight Gaussian Analysis, and the setting values ​​are temperature 23 ℃, measurement wavelength 632.8 nm, and channel width 10 μsec.

[0064]

[0065] The above (A1) small-particle acrylic graft copolymer may be, for example, 1 to 10 wt%, 3 to 10 wt%, 3 to 9 wt%, or 4 to 9 wt% of the total 100 wt% of all components constituting the base resin, and within this range, it has the effect of providing transparency equivalent to or higher than that of a conventional ASA resin composition while providing excellent appearance quality.

[0066] The above (A1) small-particle acrylic graft copolymer comprises, for example, 35 to 45 wt% of an acrylate rubber polymer having an average particle diameter of 50 to 100 nm, 40 to 50 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyan compound, based on 100 wt% of the total, and preferably comprises 35 to 45 wt%, or 12 to 18 wt%, of an acrylate rubber polymer having an average particle diameter of 60 to 95 nm, 40 to 50 wt%, or 58 to 63 wt%, of an aromatic vinyl compound, and 5 to 10 wt%, or 5 to 9 wt% of a vinyl cyan compound, and within this range, excellent mechanical strength such as impact strength is achieved.

[0067] In this description, a polymer comprising a compound means a polymer polymerized including the compound, and the units in the polymerized polymer are derived from the compound.

[0068]

[0069] The above acrylate rubber may be formed by including an alkyl acrylate compound.

[0070] In the present invention, the alkyl acrylate compound may be, for example, an alkyl acrylate having an alkyl group having 1 to 15 carbon atoms, preferably at least one selected from the group consisting of 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 including a chain alkyl group having 1 to 4 carbon atoms, and even more preferably butyl acrylate.

[0071]

[0072] In the present invention, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-bromo styrene, ρ-bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably at least one selected from the group consisting of styrene and α-methyl styrene, more preferably styrene, and in this case, there is an effect of having appropriate fluidity, excellent processability, and excellent mechanical properties such as impact resistance.

[0073]

[0074] In the present invention, the vinyl cyanide compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and is preferably acrylonitrile.

[0075]

[0076] The above (A1) small-particle acrylic graft copolymer preferably has a weight average molecular weight of 50,000 to 150,000 g / mol, more preferably 50,000 to 130,000 g / mol, and even more preferably 70,000 to 130,000 g / mol, and within this range, excellent effects such as impact strength and hardness are achieved.

[0077] Specifically, the above weight average molecular weight is prepared by putting tetrahydrofuran (THF) and the compound in a 1 ml glass bottle to prepare a sample sample with a concentration of 1 wt% of the compound, filtering the standard sample (polystyrene) and the sample sample through a filter (pore size of 0.45 μm), and then injecting them into a GPC injector, and comparing the elution time of the sample sample with the calibration curve of the standard sample to obtain the weight average molecular weight and molecular weight distribution of the compound. At this time, Infinity II 1260 (Agilient) can be used as the measuring device, and the flow rate can be set to 1.00 mL / min and the column temperature to 40.0 ℃.

[0078]

[0079] The above (A1) small-particle acrylic graft copolymer can be produced, for example, by emulsion polymerization, and in this case, it has excellent mechanical strength such as impact strength.

[0080] The above emulsion polymerization is not particularly limited to an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and a specific example thereof may be an emulsion graft polymerization method.

[0081]

[0082] (A2) Large-diameter acrylic graft copolymer

[0083] The acrylate rubber of the above (A2) large-diameter acrylic graft copolymer preferably has an average particle diameter of 150 to 300 nm, preferably 180 to 300 nm, more preferably 180 to 250 nm, and within this range has excellent mechanical strength such as impact strength.

[0084]

[0085] The above (A2) large-diameter acrylic graft copolymer may be, for example, 30 to 50 wt%, 32 to 48 wt%, or 35 to 45 wt% of the total 100 wt% of all components constituting the base resin, and within this range, it has the effect of providing transparency equivalent to or higher than that of a conventional ASA resin composition while providing excellent appearance quality.

[0086] The above (A2) large-diameter acrylic graft copolymer comprises, for example, 35 to 45 wt% of an acrylate rubber polymer having an average particle diameter of 150 to 300 nm, 40 to 50 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyan compound, based on 100 wt% of the total, and preferably comprises 35 to 45 wt%, or 12 to 18 wt%, of an acrylate rubber polymer having an average particle diameter of 180 to 300 nm, 40 to 50 wt%, or 58 to 63 wt%, of an aromatic vinyl compound, and 5 to 10 wt%, or 5 to 9 wt% of a vinyl cyan compound, and within this range, excellent mechanical strength such as impact strength is achieved.

[0087] In this description, a polymer comprising a compound means a polymer polymerized including the compound, and the units in the polymerized polymer are derived from the compound.

[0088]

[0089] The above acrylate rubber may be formed by including an alkyl acrylate compound.

[0090] In the present invention, the alkyl acrylate compound may be, for example, an alkyl acrylate having an alkyl group having 1 to 15 carbon atoms, preferably at least one selected from the group consisting of 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 including a chain alkyl group having 1 to 4 carbon atoms, and even more preferably butyl acrylate.

[0091]

[0092] The types of the above aromatic vinyl compound and the above vinyl cyan compound are as described in the description of the above (A1) small-particle-diameter acrylic graft copolymer.

[0093]

[0094] The above (A2) large-diameter acrylic graft copolymer preferably has a weight average molecular weight of 50,000 to 150,000 g / mol, more preferably 50,000 to 130,000 g / mol, and even more preferably 70,000 to 130,000 g / mol, and within this range, excellent effects such as impact strength and hardness are achieved.

[0095]

[0096] The above (A2) large-diameter acrylic graft copolymer can be produced, for example, by emulsion polymerization, and in this case, it has excellent mechanical strength such as impact strength.

[0097] The above emulsion polymerization is not particularly limited to an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and a specific example thereof may be an emulsion graft polymerization method.

[0098]

[0099] The total amount of the above (A1) small-particle-diameter acrylic graft copolymer and the above (A2) large-particle-diameter acrylic graft copolymer may be preferably 40 wt% or more, 40 to 65 wt%, and more preferably 45 to 55 wt%, of the total 100 wt% of all components constituting the base resin, and when an injection lubricity improving agent is included in the ASA resin composition within this range, there is an advantage of providing excellent injection molding release properties and transparency, and further, excellent physical property balance between mold deposits.

[0100]

[0101] (B) Methacrylate copolymer

[0102] The above (B) methacrylate copolymer may be, for example, a methacrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer.

[0103] The above methacrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer preferably has a weight average molecular weight of 150,000 to 300,000 g / mol, more preferably 180,000 to 280,000 g / mol, and even more preferably 180,000 to 250,000 g / mol, and within this range, excellent effects such as impact strength and hardness are achieved.

[0104] The above (B) methacrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer may be, for example, 30 to 60 wt%, 35 to 60 wt%, 40 to 60 wt%, or 45 to 57 wt% based on 100 wt% of the total components constituting the base resin, and within this range, impact resistance, heat resistance, and hardness are maintained at equivalent levels, while fluidity and appearance quality are improved.

[0105]

[0106] The above (B) methacrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer can be formed by including, for example, a methacrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyanide compound, and in this case, there is an advantage of excellent impact resistance and suppressing deterioration of heat resistance characteristics.

[0107] As a preferred example, the methacrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer may comprise 55 to 80 wt% of the methacrylic acid alkyl ester compound, 25 to 45 wt% of the aromatic vinyl compound, and 5 to 15 wt% of the vinyl cyan compound based on 100 wt% of the total, more preferably 60 to 75 wt% of the methacrylic acid alkyl ester compound, 20 to 40 wt% of the aromatic vinyl compound, and 5 to 10 wt% of the vinyl cyan compound, and even more preferably 65 to 75 wt% of the methacrylic acid alkyl ester compound, 20 to 35 wt% of the aromatic vinyl compound, and 5 to 10 wt% of the vinyl cyan compound. In this case, there is an advantage of excellent fluidity and superior appearance quality.

[0108]

[0109] The above (B) methacrylic acid alkyl ester compound may be selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate and decyl methacrylate, among which methyl methacrylate is preferred.

[0110] The types of the above aromatic vinyl compound and the above vinyl cyan compound are as described in the description of the above (A1) small-particle-diameter acrylic graft copolymer.

[0111] The above (B) methacrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer can be produced by, for example, emulsion polymerization, solution polymerization or bulk polymerization, and in this case, it has excellent effects such as heat resistance and fluidity.

[0112] The above emulsion polymerization, solution polymerization and bulk polymerization are not particularly limited when performed using emulsion polymerization, solution polymerization and bulk polymerization methods commonly performed in the technical field to which the present invention belongs.

[0113]

[0114] (C) Saturated carboxylic acid compound

[0115] In one embodiment of the present invention, the saturated carboxylic acid compound may be a compound containing at least one -COOH group at a terminal and having an alkyl group of C5 to C30.

[0116] The above saturated carboxylic acid compound is preferably used with an unsaturated carboxamide compound described below, which has a refractive index (80° C.) within the range of 1.35 to 1.45, or 1.4 to 1.45, to provide an excellent balance of properties between injection molding release properties and transparency.

[0117] Here, the refractive index can be measured by a measurement method known in the art, and a specific example may be a sample formed into a film through film extrusion of less than 0.2T, and then the refractive index of the sample for air is measured under room temperature conditions.

[0118] The above saturated carboxylic acid compound may be included in an amount of 0.1 to 1.0 parts by weight, 0.3 to 1.0 parts by weight, 0.2 to 0.9 parts by weight, or 0.3 to 0.9 parts by weight based on 100 parts by weight of the base resin. When the above range is satisfied, an excellent balance of properties between injection molding release properties and transparency can be provided.

[0119] The above saturated carboxylic acid compound is not particularly limited as long as it follows the definition of the present invention, and a product manufactured directly or commercially available can be used.

[0120]

[0121] (D) Unsaturated carboxamide compound

[0122] In one embodiment of the present invention, the unsaturated carboxamide compound may be a compound containing at least one -CON group at a terminal and having an alkyl group of C5 to C50.

[0123] The above -CON group may be -CONH2, -CONHR1, -CONR1R2, etc., wherein R1 and R2 may be independently alkyl groups having 1 to 5 carbon atoms.

[0124] The above unsaturated carboxamide compound is preferably used together with the above-mentioned saturated carboxylic acid compound having a refractive index (80° C.) within the range of 1.5 to 1.6, or 1.53 to 1.58, to provide an excellent balance of properties between injection molding release properties and transparency.

[0125] The above unsaturated carboxamide compound may be included in an amount of 0.1 to 1.0 parts by weight, 0.3 to 1.0 parts by weight, 0.2 to 0.9 parts by weight, or 0.3 to 0.9 parts by weight based on 100 parts by weight of the base resin. When the above range is satisfied, an excellent balance of properties between injection molding release properties and transparency can be provided.

[0126] The above unsaturated carboxamide compound is not particularly limited as long as it follows the definition of the present invention, and a product manufactured directly or commercially available can be used.

[0127]

[0128] ASA resin composition

[0129] The above ASA resin composition may, for example, contain the contents of (A1) and (A2) in a weight ratio of 1:3.5 to 1:10 (A1:A2), 1:3.5 to 1:9 (A1:A2), or 1:4 to 1:8 (A1:A2). In this case, there is an advantage of providing an excellent balance of properties between injection molding release properties and transparency while including an injection lubricity improving agent.

[0130]

[0131] The total amount of the (C) saturated carboxylic acid compound and the (D) unsaturated carboxamide compound may be preferably included within a range of 0.51 to 1.44 parts by weight, more preferably 0.6 to 1.4 parts by weight, and even more preferably 0.6 to 1.3 parts by weight, based on 100 parts by weight of the base resin. When the above range is satisfied, injection molding release properties and transparency, and further, an excellent balance of physical properties between these and the mold deposit can be provided.

[0132] The above mold deposit is described in detail below, so a detailed description thereof is omitted here.

[0133]

[0134] The above ASA resin composition may further include, for example, an active agent or an additive including the same.

[0135] The above additive may be at least one selected from the group consisting of an activator, a heat stabilizer, a UV stabilizer, a fluorescent whitening agent, a chain extender, a pigment, an antibacterial agent, an antifriction agent, and an antiwear agent.

[0136] The above additives may be further included, for example, in an amount of 0.01 to 5 wt%, preferably 0.05 to 3 wt%, more preferably 0.1 to 3 wt%, and even more preferably 0.1 to 1 wt%, based on 100 wt% of the total components (A1+A2+B+C+D additives) constituting the ASA resin composition. In this case, there is an effect of well implementing the required properties without deteriorating the original properties of the ASA resin composition of the present disclosure.

[0137] The above-mentioned active agent may be, for example, at least one selected from the group consisting of an alkyl acrylate polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 to 70,000 g / mol, a copolymer comprising ethylene, an olefin wax, and an aliphatic amide compound, and preferably at least one selected from the group consisting of an alkyl acrylate polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 to 70,000 g / mol, and an olefin wax, and more preferably an alkyl acrylate polymer, and in this case, the active agent has an excellent balance of physical properties while exhibiting excellent scratch resistance and colorability, thereby providing an excellent appearance quality.

[0138] The above-mentioned alkyl acrylate polymer as an active agent may preferably be at least one selected from the group consisting of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate), and in this case, the formation of mold deposits is suppressed, so that the molded product has an attractive appearance and high gloss.

[0139] The above-mentioned active agent, alkyl acrylate polymer, may be present in an amount of 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the total resin components (A1+A2+B) constituting the ASA resin composition, and within this range, there is an effect of improving both transparency and mold release properties.

[0140] The above-mentioned alkyl acrylate polymer, which is an active agent, is not particularly limited as long as it is an alkyl acrylate polymer commonly used in the technical field to which the present invention belongs, and a product manufactured directly or commercially available can be used.

[0141]

[0142] The above-mentioned styrene-acrylonitrile copolymer as the active agent preferably has a weight average molecular weight of 40,000 to 67,000 g / mol, more preferably 50,000 to 65,000 g / mol, and even more preferably 55,000 to 65,000 g / mol, and within this range, it has the effect of improving fluidity, thereby providing excellent processability and improving appearance quality.

[0143] The above-mentioned styrene-acrylonitrile copolymer, which is an active agent, may have a flow index (190°C, 5kg) measured according to ISO 1133 of, for example, 20 to 60 g / 10min, preferably 25 to 55 g / 10min, and within this range, it has excellent impact strength and flowability and excellent appearance quality.

[0144] The above-mentioned styrene-acrylonitrile copolymer, which is an active agent, may have a heat distortion temperature of, for example, 82 to 90°C, preferably 84 to 88°C, as measured according to ASTM D648, and within this range, has excellent impact strength and fluidity and excellent appearance quality.

[0145] The above-mentioned active ingredient, styrene-acrylonitrile copolymer, may be, for example, 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the total resin components (A1+A2+B) constituting the ASA resin composition, and within this range, there is an effect of improving both transparency and mold release properties.

[0146]

[0147] The copolymer comprising the above ethylene may be, for example, at least one selected from the group consisting of an ethylene / 1-butene copolymer and an ethylene / n-butyl acrylate / carbon monoxide terpolymer, and in this case, it has the effect of excellent heat resistance and fluidity and superior appearance quality.

[0148] The copolymer comprising the above ethylene preferably has a weight average molecular weight of 40,000 to 67,000 g / mol, more preferably 50,000 to 65,000 g / mol, and even more preferably 55,000 to 65,000 g / mol, and within this range, has the effect of improving fluidity, thereby providing excellent processability and improving appearance quality.

[0149] The copolymer including the above ethylene may be present in an amount of 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the total resin components (A1+A2+B) constituting the ASA resin composition, and within this range, there is an effect of improving both transparency and mold release properties.

[0150]

[0151] The above olefin wax may be, for example, at least one selected from the group consisting of polyethylene wax and polypropylene wax, and preferably polyethylene wax. In this case, it has the effect of excellent heat resistance and fluidity and superior appearance quality.

[0152] The above olefin wax may be, for example, 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the total resin components (A1+A2+B) constituting the ASA resin composition, and within this range, there is an effect of improving both transparency and mold release properties.

[0153]

[0154] The above aliphatic amide compound may be at least one selected from the group consisting of stearamide, behanamide, ethylene bis(stearamide), ethylene bis 12-hydroxy stearamide, erucamide, oleamide, and ethylene bis oleamide, and preferably ethylene bis stearamide. In this case, the aliphatic amide compound has excellent impact strength and fluidity and excellent appearance quality.

[0155] In particular, the thermoplastic resin composition of the present invention preferably does not contain an excessive amount of a stearate-based lubricant, and in this case, as seen in Example 2 compared to Comparative Examples 7 to 8 described below, the molded product has an attractive appearance and high gloss.

[0156] The above stearate-based active agent may be, for example, at least one selected from the group consisting of barium stearate, calcium stearate, magnesium stearate, zinc stearate, and stearic acid.

[0157] The aliphatic amide compound may be, for example, 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the total resin components (A1+A2+B) constituting the ASA resin composition, and within this range, there is an effect of improving both transparency and mold release properties.

[0158] The above-mentioned active agent may be, for example, 0.1 to 3 wt%, preferably 0.5 to 2.5 wt%, and more preferably 0.7 to 2.2 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+active agent) constituting the ASA resin composition, and within this range, both impact resistance and fluidity are excellent.

[0159]

[0160] Other additives other than the above-mentioned active agent may further include, for example, one or more additives selected from the group consisting of a heat stabilizer, a UV stabilizer, a fluorescent whitening agent, a chain extender, a pigment, an antibacterial agent, an antifriction agent, and an antiwear agent, for example, at an amount of 0.1 to 5 wt%, preferably 1 to 3 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+other additives) constituting the ASA-based resin composition. In this case, there is an effect of well implementing the required properties without lowering the original properties of the ASA-based resin composition of the present disclosure.

[0161] The above heat stabilizer may be, for example, 0.1 to 2 wt%, more preferably 0.2 to 1.5 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+heat stabilizer) constituting the ASA resin composition, and within this range, there is an effect of improving heat resistance.

[0162] The above heat stabilizer may be, for example, at least one selected from the group consisting of a phenol-based heat stabilizer, a phosphite-based heat stabilizer, and a thioether-based heat stabilizer, and is preferably a phenol-based heat stabilizer and a phosphite-based heat stabilizer.

[0163] The above phenolic heat stabilizer may be, for example, at least one selected from the group consisting of tetrakis methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methane, 1,3,5-tris-(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.

[0164] The above phosphite-based heat stabilizer may be, for example, trisnonylphenyl phosphite, tris-(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, or a mixture thereof.

[0165] The above thioether-based heat stabilizer may be, for example, at least one selected from the group consisting of dilauryl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate, 2-mercaptobenzimidazole, phenothiazine, octadecyl thioglycolate, butyl thioglycolate, octyl thioglycolate, and thiocresol.

[0166] The above UV stabilizer may be preferably 0.1 to 3 wt%, more preferably 0.5 to 1.5 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+heat stabilizer) constituting the ASA resin composition, and in this case, there is an effect of improving weather resistance.

[0167] The UV stabilizer may be, for example, a hindered amine light stabilizer (HALS), and preferably, 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-N-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid. Condensation products, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, At least one selected from the group consisting of a linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, and poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], and more preferably Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate2-(2H-benzotriazol-2-yl)-4-(-(1,1,3,3-tetramethylbutyl)phenol), poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino] or a mixture thereof, and more preferably Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacade, poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino], or a mixture thereof, in which case there is an advantage of significantly improving weather resistance without compromising impact resistance and fluidity.

[0168] The above pigment may be, for example, a carbon black pigment.

[0169] The pigment may be, for example, preferably 0.5 to 5 wt%, more preferably 1 to 4.5 wt%, and even more preferably 2 to 4.5 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+pigment) constituting the ASA resin composition, and has the advantage of excellent physical property balance and excellent coloring properties within this range.

[0170] As the above antibacterial agent, an inorganic antibacterial agent including, for example, a zinc-based antibacterial agent and a copper-based antibacterial agent, or an organic antibacterial agent known in the art can be used.

[0171] The above antibacterial agent may be preferably 0.5 to 5 wt%, more preferably 1 to 4.5 wt%, and even more preferably 2 to 4.5 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+antibacterial agent) constituting the ASA resin composition, and within this range, there is an advantage of excellent antibacterial properties while maintaining excellent physical property balance.

[0172] The above-mentioned anti-friction agent may be preferably 0.5 to 5 wt%, more preferably 1 to 4.5 wt%, and even more preferably 2 to 4.5 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+anti-friction agent) constituting the ASA resin composition, and within this range, there is an advantage of excellent physical property balance and excellent friction resistance.

[0173] The above-mentioned wear-resistant agent may be preferably 0.5 to 5 wt%, more preferably 1 to 4.5 wt%, and even more preferably 2 to 4.5 wt%, based on 100 wt% of the total components (A1+A2+B+C+D+wear-resistant agent) constituting the ASA resin composition, and within this range, there is an advantage of excellent physical property balance and excellent wear resistance.

[0174]

[0175] In addition, the present invention provides a base resin comprising 100 parts by weight of (A1) 1 to 10 wt% of a small-particle acrylic graft copolymer; (A2) 35 to 50 wt% of a large-particle acrylic graft copolymer; and (B) 40 to 60 wt% of a methacrylate copolymer.

[0176] (C) Containing 0.1 to 1 part by weight of a saturated carboxylic acid compound having at least one -COOH group at the terminal and an alkyl group of C5 to C30 and having a refractive index (80° C.) of 1.35 to 1.45;

[0177] (D) Contains 0.1 to 1 part by weight of an unsaturated carboxamide compound having at least one -CON group at the terminal, an alkyl group of C5 to C50, and a refractive index (80° C.) of 1.5 to 1.6;

[0178] (C) Provided is an ASA resin composition characterized by comprising a total of 0.51 to 1.44 parts by weight of a saturated carboxylic acid compound and (D) an unsaturated carboxamide compound.

[0179]

[0180] The above ASA resin composition is, for example, injected continuously with an injection molding machine (LS, molding force: 220 tons) into a removable mold core at injection molding conditions of 250 to 280° C. and a pressure of 25 to 35 bar for 200 shots, and then the weight of gas deposited in the mold core is measured and the mold deposit is calculated using the following mathematical formula 1, and is 40 mg or less, 36 mg or less, and 35.5 mg or less, and within this range, the physical property balance is excellent while maintaining transparency, so that the appearance quality is excellent.

[0181] [Mathematical Formula 1]

[0182] Mold deposit (mg) = Weight of mold core after 200 shots - Weight of initial mold core

[0183]

[0184] The above ASA resin composition has an ejection force of 1600 N or less or 1590 N or less as measured by installing an ejection force measuring device in the ejection stage of a cup mold injection molding machine, for example, and within this range, the ejection force is excellent, so that cracks hardly occur after injection, resulting in excellent appearance quality.

[0185] The above ASA resin composition may have a haze of less than 3.0%, preferably less than 2.9%, as measured according to ASTM 1003dp, and within this range, it has an excellent balance of physical properties while maintaining transparency, thereby providing an excellent appearance quality.

[0186] The above ASA resin composition may have a heat distortion temperature (HDT) of 74°C or higher, preferably 74 to 76°C, as measured by an Auto HDT Tester 6A-2 (trade name, manufacturer: TOYOSEIKI) according to ISO 75-1,2, for example, and has excellent heat resistance characteristics without affecting mechanical strength within this range.

[0187]

[0188] Method for manufacturing ASA resin composition

[0189] The method for producing an ASA resin composition of the present invention is characterized by including, for example, a step of mixing and extruding (A) an acrylic graft copolymer and (B) a methacrylate copolymer, (C) a saturated carboxylic acid compound, and (D) an unsaturated carboxamide compound under conditions of 200 to 300°C and 100 to 500 rpm. In this case, there is provided a method for producing an ASA resin composition, which includes an injection lubricity improving agent and provides an excellent balance of properties between transparency, injection molding release properties, and mold deposits.

[0190]

[0191] For example, it is characterized by including a step of mixing and extruding under conditions of 200 to 300°C and 100 to 500 rpm, comprising 100 parts by weight of a base resin including (A) an acrylic graft copolymer and (B) a methacrylate copolymer; and a total of 0.51 to 1.44 parts by weight of (C) a saturated carboxylic acid compound and (D) an unsaturated carboxamide compound. In this case, there is an advantage of providing excellent physical property balance between injection molding release properties, transparency, and mold deposits.

[0192]

[0193] As a preferred example, (A1) 1 to 10 wt% of a small-particle-diameter acrylic graft copolymer; (A2) 35 to 50 wt% of a large-particle-diameter acrylic graft copolymer; And (B) 40 to 60 wt% of a methacrylate copolymer; 100 parts by weight of a base resin comprising (C) 0.1 to 1 part by weight of a saturated carboxylic acid compound having at least one -COOH group at the terminal, a C5 to C30 alkyl group, and a refractive index (80° C.) of 1.35 to 1.45, (D) 0.1 to 1 part by weight of an unsaturated carboxamide compound having at least one -CON group at the terminal, a C5 to C50 alkyl group, and a refractive index (80° C.) of 1.5 to 1.6, wherein the total input amount of the saturated carboxylic acid compound and the unsaturated carboxamide compound is 0.51 to 1.44 parts by weight based on 100 parts by weight of the base resin, and the step of mixing and extruding under conditions of 200 to 300° C. and 100 to 500 rpm is characterized by comprising the steps of: In these cases, there is an advantage in providing excellent property balance between injection molding release properties, transparency and mold deposit by including an injection lubricity improver.

[0194] The method for manufacturing the above ASA resin composition shares all the technical characteristics of the aforementioned ASA resin composition. Therefore, a description of the overlapping portions will be omitted.

[0195]

[0196] The step of manufacturing pellets using the above extrusion mixer may preferably be performed at a temperature of 200 to 300°C with a size of 25 to 75 pi, more preferably at a temperature of 220 to 260°C with a size of 20 to 70 pi, and within this range, stable extrusion is possible and the mixing effect is excellent. At this time, the temperature is the temperature set in the cylinder, and pi means the outer diameter (unit: mm).

[0197] The above extrusion mixer is not particularly limited as long as it is an extrusion mixer commonly used in the technical field to which the present invention belongs, and may preferably be a twin-screw extrusion mixer.

[0198]

[0199] molded products

[0200] The molded article of the present invention is characterized by including, for example, the ASA resin composition of the present invention, and in this case, compared to a conventional ASA resin composition, it has the advantage of providing excellent balance of properties between injection molding release properties, transparency, and mold deposits while including an injection lubricity improving agent.

[0201]

[0202] The method for manufacturing a molded product of the present invention is characterized by including a step of injecting pellets manufactured by the method for manufacturing the ASA resin composition under the conditions of an injection temperature of 200 to 300°C, an injection pressure of 60 to 100 bar, and a holding pressure of 30 to 65 bar, and in this case, there is an advantage in that an injection molded product having high impact strength can be easily manufactured.

[0203] The above injection temperature is preferably 220 to 280°C, more preferably 230 to 270°C, and within this range, there is an advantage in that an injection molded product requiring a complex design can be easily manufactured.

[0204] The above injection pressure is preferably 70 to 90 bar, more preferably 75 to 85 bar, and within this range, there is an advantage in that an injection molded product requiring a complex design can be easily manufactured.

[0205] The above pressure may preferably be 35 to 60 bar, more preferably 40 to 55 bar, and within this range, there is an advantage in that injection molded products requiring complex designs can be easily manufactured.

[0206]

[0207] The above molded product can be used in the field of transparent small medical products including syringes and tube connectors and in the field of transparent food containers.

[0208]

[0209] In describing the ASA resin composition, its manufacturing method, and molded product of this invention, it is stated that other conditions or equipment, etc. that are not explicitly described can be appropriately selected within the range commonly practiced in the art and are not particularly limited.

[0210] Hereinafter, preferred examples are presented to help understand the present disclosure; however, the following examples are merely illustrative of the present disclosure, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present disclosure, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0211] [Example]

[0212] The materials used in the following examples and comparative examples are as follows.

[0213] * (A1) Small particle size acrylic graft copolymer: ASA graft copolymer having an average particle size of 80 nm of acrylate rubber (35 to 45 wt% of butyl acrylate, 40 to 50 wt% of styrene and 5 to 10 wt% of acrylonitrile, weight average molecular weight 50,000 to 150,000 g / mol)

[0214] * (A2) Large particle size acrylic graft copolymer: ASA graft copolymer having an average particle size of 220 nm of acrylate rubber (35 to 45 wt% of butyl acrylate, 40 to 50 wt% of styrene, and 5 to 10 wt% of acrylonitrile, weight average molecular weight of 50,000 to 150,000 g / mol)

[0215] * (B) Methacrylate copolymer: Methacrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer (methyl methacrylate 71 wt%, styrene 22 wt% and acrylonitrile 7 wt%, weight average molecular weight 120,000 to 150,000 g / mol)

[0216] * (C) Saturated carboxylic acid compound: A stearic acid compound containing a -COOH group at one terminal, a C18 alkyl group, and a refractive index (80°C) of 1.4299 (LG Household & Health Care, Elofad TH100 product)

[0217] * (D) Unsaturated carboxamide compound: An erucamide compound having an alkyl group with a total of 22 carbon atoms, including a -CON-containing group at one end and one double bond at the center of the skeleton, and a refractive index (80°C) of 1.5614 (Akzo Nobel, ArmoslipE product)

[0218]

[0219] Examples 1 to 4 and Comparative Examples 1 to 8

[0220] The ingredients and contents described in Tables 1 and 2 below were fed into a twin-screw extruder. (C) and (D) were fed in corresponding weight parts relative to a total of 100 weight parts of the aforementioned ingredients (A1), (A2), and (B).

[0221] Then, pellets were manufactured by kneading and extruding at a cylinder temperature of 240 ℃, and the flow index was measured using the manufactured pellets.

[0222] Afterwards, a specimen for measuring physical properties was produced by injection molding at an injection temperature of 240 ℃ using an injection molding machine (Engel's 120MT).

[0223]

[0224] [Example Exam]

[0225] The characteristics of the specimens manufactured in Examples 1 to 4 and Comparative Examples 1 to 8 were measured by the following methods, and the results are shown in Tables 1 and 2 below.

[0226] measurement method

[0227] * Injection molding release force (unit: N): This was measured using an injection temperature of 210℃, a mold temperature of 40℃, and a holding pressure of 80 MPa. Specifically, the injection molding release force measuring equipment shown in Fig. 1 was separately installed in a molding machine for a cup-shaped injection molded product (ejection molded product of a cup mold injection machine) after injection using only holding pressure, and the injection molding release force was measured by measuring the ejection pressure during the ejection process.

[0228] Specifically, the release force was monitored through a sensor attached to the injection molding release force measuring device, and the data was processed to obtain the result value.

[0229] * Haze (unit %): Measured at 25 ℃ according to ASTM D1003dp.

[0230] * Mold deposit (unit: mg): The weight of gas deposited on the mold core was measured after 200 shots were continuously injected using an injection molding machine (LS, molding force: 220 tons) on a removable mold core under injection molding conditions of 250 to 280°C and 25 to 35 bar, and the weight was calculated using the following mathematical formula 1.

[0231] [Mathematical Formula 1]

[0232] Mold deposit (mg) = Weight of mold core after 200 shots - Weight of initial mold core

[0233] * Heat deflection temperature (HDT, ℃): Measured using TOYOSEIKI Auto HDT Tester 6A-2 according to ISO 75-1,2.

[0234] Classification Example 1 Example 2 Example 3 Example 4 (A1) Graft copolymer 105810 (A2) Graft copolymer 35404540 (B) Methacrylate copolymer 55554750 (C) + (D) Total amount (parts by weight) 1.311.30.6 (C) Content (parts by weight) 0.80.50.50.3 (D) Content (parts by weight) 0.50.50.80.3 Injection molding release property (N) 1350148013801580 Haze (%) 2.822.482.742.01 Mold deposit (mg) 36253814 HDT (℃) 75.175,576.377.1

[0235] Classification Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 (A1) Graft copolymer 55555555 (A2) Graft copolymer 404040404040404040 (B) Methacrylate copolymer 5555555555555555 (C) + (D) Total amount (parts by weight) 0 1 1 0.4 1.6 2 1.6 1.6 (C) Content (parts by weight) 0 1 0.2 0.8 1 1.2 0.4 (D) Content (parts by weight) 0 1 0.2 0.8 1 0.4 1.2 Injection molding Heterogeneity (N) 20501410149017101210107011801290 Haze (%) 1.563.343.271.733.854.514.033.94 Mold Deposit (mg) 628261051685851 HDT (℃) 75.375.675.475.175.875.975.175.3

[0236] (In the above Tables 1 and 2, the total amount (parts by weight) of (C)+(D) is the sum of the input amount (parts by weight) of (C) and the input amount (parts by weight) of (D), where the input amount (parts by weight) of (C) and the input amount (parts by weight) of (D) are based on 100 parts by weight of the base resin (A1+A2+B))

[0237] As shown in Tables 1 and 2 above, Examples 1 to 4 according to the present invention showed injection molding release properties equivalent to or higher than those of Comparative Examples 1 to 8, while transparency was improved and mold deposits were reduced, thereby preventing deterioration of surface properties that may occur during molding processing and confirming the effect of excellent appearance quality even when producing small products.

[0238] In particular, Example 4, in which a small amount of an injection lubricity improver was used within an appropriate range in a base resin using a combination of a methacrylate copolymer of (B) and a graft copolymer of (A-1) and (A-2), it was confirmed that injection molding release property and transparency were improved and mold deposits were reduced compared to Example 1, in which a large amount of an injection lubricity improver was used within an appropriate range in a base resin using a combination of a methacrylate copolymer of (B) and a graft copolymer of (A-1) and (A-2).

[0239] Meanwhile, Comparative Example 1, which did not use either compound (C) or compound (D), had poor injection molding properties.

[0240] In addition, Comparative Example 2 or Comparative Example 3, which used the compound of (C) or the compound of (D) alone, had poor transparency. For reference, if the measured haze is less than 3.0, it is judged as Pass.

[0241] In addition, Comparative Example 4, which used a smaller amount of the compound (C) and the compound (D) in combination than the total amount within the range of the present invention, exhibited poor injection molding release properties. For reference, if the measured pressure is 1600 N or higher, cracks occur in the injection-molded product during injection.

[0242] In addition, Comparative Examples 5 and 6, which used the compound of (C) and the compound of (D) in combination but in excess of the total amount within the range according to the present invention, had poor transparency and mold deposits. For reference, if the measured weight is less than 50 mg, it is considered as Pass.

[0243] In addition, Comparative Example 7 using an excessive amount of the compound of (C) or Comparative Example 8 using an excessive amount of the compound of (D) all had poor release force, transparency, and mold deposit.

[0244]

[0245] In summary of these results, it was confirmed that even when using an injection lubricity improver, by controlling the content of graft copolymers and styrene copolymers containing acrylate rubbers with different average particle sizes, the injection molding release property and transparency are improved and mold deposits are reduced due to the synergistic effect of these combinations, thereby providing transparency equivalent to or higher than that of conventional transparent materials, and the release property is also improved during injection, thereby preventing injection cracking even when injecting small transparent materials, thereby providing a resin composition with excellent product reliability.

Claims

1. (A) a base resin comprising an acrylic graft copolymer, (B) a methacrylate copolymer, (C) a saturated carboxylic acid compound, and (D) an unsaturated carboxamide compound, An ASA resin composition characterized in that the (C) saturated carboxylic acid compound and (D) unsaturated carboxamide compound are contained in a total amount of 0.51 to 1.44 parts by weight based on 100 parts by weight of the base resin.

2. In paragraph 1, An ASA resin composition characterized in that the above saturated carboxylic acid compound is a compound having at least one -COOH group at the terminal, an alkyl group of C5 to C30, and a refractive index (80° C.) of 1.35 to 1.

45.

3. In paragraph 1, An ASA resin composition characterized in that the above unsaturated carboxamide compound is a compound having at least one -CON group at the terminal, an alkyl group of C5 to C50, and a refractive index (80° C.) of 1.5 to 1.

6.

4. In paragraph 1, An ASA resin composition characterized in that it comprises the (C) saturated carboxylic acid compound and the (D) unsaturated carboxamide compound in a weight ratio of 1:0.5 to 1:1.5 (C:D).

5. In paragraph 1, The above base resin is an ASA resin composition characterized in that it contains (A) an acrylic graft copolymer: (B) a methacrylate copolymer in a weight ratio of 1:0.5 to 1:1.5 (A:B).

6. In paragraph 5, The above (A) acrylic graft copolymer is an ASA resin composition characterized in that it comprises (A1) small-particle-diameter acrylic graft copolymer: (A2) large-particle-diameter acrylic graft copolymer in a weight ratio of 1:3.5 to 1:10 (A1:A2).

7. In paragraph 6, The above (A1) small-particle-diameter acrylic graft copolymer comprises 35 to 45 wt% of a rubbery polymer having an average particle diameter of 50 to 100 nm, 40 to 50 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyanide compound, and is characterized in that the ASA resin composition has a weight average molecular weight within a range of 50,000 to 150,000 g / mol.

8. In paragraph 6, The above (A2) large-particle-diameter acrylic graft copolymer comprises 35 to 45 wt% of a rubbery polymer having an average particle diameter of 150 to 300 nm, 40 to 50 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyan compound, and is characterized in that the ASA resin composition has a weight average molecular weight within a range of 50,000 to 150,000 g / mol.

9. In paragraph 1, An ASA resin composition characterized in that the saturated carboxylic acid compound is contained in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin.

10. In paragraph 1, An ASA resin composition characterized in that the unsaturated carboxamide compound is contained in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin.

11. In paragraph 1, The above ASA resin composition is a thermoplastic resin composition characterized in that the mold deposit calculated by the following mathematical formula 1 is 6.2 mg or less by measuring the weight of gas deposited in the mold core after continuous injection of 200 shots using an injection molding machine (LS, molding force: 220 tons) into a removable mold core under injection molding conditions of 250 to 280° C. and a pressure of 25 to 35 bar. [Mathematical Formula 1] Mold deposit (mg) = Weight of mold core after 200 shots - Weight of initial mold core 12. In paragraph 1, The above ASA resin composition is a thermoplastic resin composition characterized in that the ejection force measured by installing an ejection force measuring device in the ejection stage of a cup mold injection molding machine is 1600 N or less.

13. In paragraph 1, The above ASA resin composition is characterized in that the ASA resin composition has a haze of less than 3.0% as measured according to ASTM D1003.

14. (A) A step of mixing and extruding a base resin including an acrylic graft copolymer, (B) a methacrylate copolymer, (C) a saturated carboxylic acid compound, and (D) an unsaturated carboxamide compound under conditions of 200 to 300°C and 100 to 500 rpm, A method for producing an ASA resin composition, characterized in that the (C) saturated carboxylic acid compound and (D) unsaturated carboxamide compound are used in a total amount of 0.51 to 1.44 parts by weight based on 100 parts by weight of the base resin.

15. A molded product characterized by comprising an ASA resin composition according to any one of claims 1 to 13.

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