ASA-based resin composition, method for preparing same, and molded article comprising same

Abstract

The present invention relates to an ASA-based resin composition, a method for preparing the same, and a molded article comprising the same. According to the present invention, the present invention has the effect of providing an ASA-based resin composition which can replace a conventional transparent material, maintain transparency, and improve mold release properties during injection, and thus can prevent injection cracking even when a small medical transparent product or a transparent food container is injected.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority to Korean Patent Application No. 10 - 2023 - 0122497, filed on September 14, 2023, and Korean Patent Application No. 10 - 2024 - 0108280, refiled on August 13, 2024, with the Korean Intellectual Property Office, and based on the priority of the above patents, the disclosure of which is incorporated herein by reference. Technical field

[0003] This application relates to an ASA - type resin composition, a method for preparing the same, and a molded article containing the same. More particularly, it relates to an ASA - type resin composition suitable for small transparent products, capable of providing an excellent balance of physical properties between injection - molding demolding properties and transparency, a method for preparing the same, and a molded article containing the same. Background art

[0004] Due to environmental problems, acrylate - styrene - acrylonitrile graft copolymers (hereinafter referred to as "ASA resins") have received attention as transparent materials that can replace existing transparent materials (such as PVC resins and PC resins) used for medical containers, food containers, etc. ASA resins have excellent weather resistance, anti - aging properties, chemical resistance, and processability, and are widely used in various fields such as automobiles, household appliances, leisure goods, building materials, gardening supplies, and construction materials.

[0005] However, ASA resins have poor demolding properties when injection - molding small transparent products, and often crack during the injection process.

[0006] Therefore, attempts have been made to study improving the demolding properties by adding additives to ASA resins, but in this case, the transparency rapidly decreases, making it difficult to replace existing transparent materials.

[0007] Therefore, there is a need to develop an ASA - type resin composition that can provide an excellent balance of physical properties between injection - molding demolding properties and transparency while imparting injection - molding demolding properties to ASA resins.

[0008] [Prior art documents]

[0009] [Patent documents]

[0010] KR 2011 - 0082121 A Summary of the invention

[0011] Technical problem

[0012] Accordingly, the present invention is proposed in view of the above problems, and an object of the present invention is to provide an ASA resin composition having injection molding demolding properties suitable for small transparent products and an excellent balance of physical properties between injection molding demolding properties and transparency, and a method for preparing the ASA resin composition.

[0013] Another object of the present invention is to provide a molded article manufactured using the ASA resin composition.

[0014] The above objects and other objects can be achieved by the present invention described below.

[0015] Technical Solution

[0016] I) According to one aspect of the present invention, there is provided an ASA resin composition comprising: a base resin containing an acrylate graft copolymer (A) and a methacrylate copolymer (B), a saturated carboxylic acid compound (C) and an unsaturated amide compound (D), wherein, based on 100 parts by weight of the base resin, the total content of the saturated carboxylic acid compound (C) and the unsaturated amide compound (D) is 0.51 to 1.44 parts by weight.

[0017] II) According to I), the saturated carboxylic acid compound may be a compound having one or more -COOH groups at its terminal, having a C5 to C30 alkyl group and a refractive index (80 °C) of 1.35 to 1.45.

[0018] III) According to I) or II), the unsaturated amide compound may be a compound having one or more -CON groups at its terminal, having a C5 to C50 alkyl group and a refractive index (80 °C) of 1.5 to 1.6.

[0019] IV) According to I) to III), the -CON group may be CONH 2 , -CONHR 1 or -CONR 1 R 2 and R 1 and R 2 may be an alkyl group having 1 to 5 carbon atoms.

[0020] V) According to I) to IV), the weight ratio of the saturated carboxylic acid compound to the unsaturated amide compound may be 1:0.5 to 1:1.5 (saturated carboxylic acid compound: unsaturated amide compound).

[0021] VI) Based on 100 parts by weight of the base resin according to I) to V), the total amount of the saturated carboxylic acid compound and the unsaturated amide compound may be 1.5 parts by weight or less. Herein, the base resin may contain an acrylate graft copolymer and a methacrylate copolymer.

[0022] VII) According to I) to VI), the weight ratio of the acrylate graft copolymer (A) and the methacrylate copolymer (B) contained in the base resin may be 1:0.5 to 1:1.5 (A:B).

[0023] VIII) According to I) to VII), the content of the acrylate graft copolymer (A) may be 40% by weight or more.

[0024] IX) According to I) to VIII), the acrylate graft copolymer (A) may contain a small particle size acrylate graft copolymer (A1) and a large particle size acrylate graft copolymer (A2).

[0025] X) According to I) to IX), the weight ratio of the small particle size acrylate graft copolymer (A1) and the large particle size acrylate graft copolymer (A2) contained in the acrylate graft copolymer (A) may be 1:3.5 to 1:10 (A1:A2).

[0026] XI) According to I) to X), the small particle size acrylate graft copolymer (A1) may contain 35 to 45% by weight of a rubber polymer having an average particle size of 50 to 100 nm, 40 to 50% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide, and / or the weight average molecular weight may be 50,000 to 150,000 g / mol.

[0027] XII) According to I) to XI), the large particle size acrylate graft copolymer (A2) may contain 35 to 45% by weight of a rubber polymer having an average particle size of 150 to 300 nm, 40 to 50% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide, and / or the weight average molecular weight may be 50,000 to 150,000 g / mol.

[0028] XIII) According to I) to XII), based on 100 parts by weight of the base resin, the content of the saturated carboxylic acid compound may be 0.1 to 1.0 part by weight.

[0029] XIV) According to I) to XIII), based on 100 parts by weight of the base resin, the content of the unsaturated amide compound may be 0.1 to 1.0 part by weight.

[0030] XV) According to I) to XIV), when a removable mold core is continuously injection-molded 200 times using an injection molding machine (clamping force: 220 tons, LS Corporation) under injection molding conditions of a temperature of 250 to 280 °C and a pressure of 25 to 35 bar, the weight of the gas deposited on the mold core is measured, and then the amount of mold fouling of the ASA resin composition is calculated by the following Equation 1, the amount of mold fouling of the ASA resin composition can be 40 mg or less.

[0031] [Equation 1]

[0032] Amount of mold fouling (mg) = Weight of the mold core after 200 injections - Initial weight of the mold core

[0033] XVI) According to I) to XV), the force value measured by installing an injection molding demolding property (ejector force) measuring device in the take-out step of a cup-shaped mold injection molding machine for the ASA resin composition can be 1600 N or less.

[0034] XVII) According to I) to XVI), the haze of the ASA resin composition measured according to ASTM D1003 can be less than 3.0%.

[0035] XVIII) According to another aspect of the present invention, there is provided a method for preparing an ASA resin composition, the method comprising: kneading and extruding a base resin containing an acrylate graft copolymer (A) and a methacrylate copolymer (B), a saturated carboxylic acid compound (C), and an unsaturated amide compound (D) at 200 to 300 °C and 100 to 500 rpm, wherein, based on 100 parts by weight of the base resin, the total amount of the saturated carboxylic acid compound (C) and the unsaturated amide compound (D) is 0.51 to 1.44 parts by weight.

[0036] XVIII) According to still another aspect of the present invention, there is provided a molded article containing the above ASA resin composition.

[0037] XX) According to XIX), the molded article may include small transparent products, such as small medical transparent products and small transparent food containers.

[0038] XXI) According to XIX) or XX), the small medical transparent products may include syringes and catheter connectors.

[0039] Advantageous Effects

[0040] The ASA resin composition of the present invention can provide an excellent balance of physical properties between injection molding demolding properties suitable for small transparent products and transparency.

[0041] That is, it can simultaneously improve the injection molding demolding properties and transparency of molded articles manufactured using the ASA resin composition of the present invention, and can reduce the amount of mold fouling.

[0042] Therefore, the ASA resin composition of the present invention can be widely applied to molded articles, such as small medical transparent products including syringes and catheter connectors, and transparent food containers. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 FIG. is a cross-sectional view of a cup mold injection molding machine for measuring the injection molding demolding property (ejection force) of the present invention. DETAILED DESCRIPTION OF THE INVENTION

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

[0045] The terms and words used in this specification and the appended claims should not be construed as limited to the ordinary meaning or dictionary meaning, but should be construed as having meanings and concepts that match the technical spirit of the present invention, so as to describe the present invention in the best way.

[0046] The present inventors confirmed that by including a predetermined injection lubrication improver, the injection molding demolding properties suitable for small transparent products and the physical property balance between the injection molding demolding properties and transparency were achieved. Based on these findings, the present inventors conducted further research to complete the present invention.

[0047] The ASA resin composition of the present invention contains an injection lubrication improver.

[0048] In the present invention, unless otherwise specified, the term "injection lubrication improver" refers to a compound that can improve the demolding properties of the ASA resin composition by preventing the occurrence of cracking during the injection process without adversely affecting the composition of the ASA resin composition.

[0049] Hereinafter, each component of the ASA resin composition of the present invention will be described in detail.

[0050] Base resin

[0051] The base resin constituting the ASA resin composition may be composed of an acrylate graft copolymer (A) and a methacrylate copolymer (B).

[0052] For example, the weight ratio of the acrylate graft copolymer (A) and the methacrylate copolymer (B) contained in the base resin can be 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, even when an injection lubrication improver is included, the injection molding demolding property and the physical property balance between the excellent injection molding demolding property and transparency can be provided.

[0053] Hereinafter, each component of the base resin of the ASA resin composition of the present invention will be described in detail.

[0054] (A) Acrylate graft copolymer

[0055] The acrylate graft copolymer (A) may contain a small particle size acrylate graft copolymer (A1) and a large particle size acrylate graft copolymer (A2). In this case, compared with using only the small particle size acrylate graft copolymer, the impact strength can be improved. In addition, compared with using only the large particle size acrylate graft copolymer, the whitening related to alcohols can be improved.

[0056] (A1) Small particle size acrylate graft copolymer

[0057] The small particle size acrylate graft copolymer (A1) may contain an acrylate rubber having an average particle size of 50 to 100 nm, preferably 60 to 95 nm, and more preferably 75 to 90 nm. Within this range, excellent mechanical strengths such as impact strength can be obtained.

[0058] In the present invention, the average particle size is measured by the dynamic light scattering method. Specifically, the average particle size is the intensity value measured in the Gaussian mode using a Nicomp 380 particle size analyzer (manufacturer: PSS). As a specific measurement example, a sample is prepared by diluting 0.1 g of latex (total solid content: 35 to 50 wt%) 1000 to 5000 times with water. Then, the average particle size of the sample is measured in the measurement mode of dynamic light scattering method / intensity 300 kHz / intensity-weight Gaussian analysis using an automatically diluted flow cell. At this time, the set values are as follows: temperature: 23 °C, measurement wavelength: 632.8 nm, channel width: 10 μsec.

[0059] For example, based on a total of 100 wt% of all components constituting the base resin, the content of the small particle size acrylate graft copolymer (A1) can be 1 to 10 wt%, 3 to 10 wt%, 3 to 9 wt%, or 4 to 9 wt%. Within this range, transparency equal to or better than that of a conventional ASA resin composition can be achieved, and excellent appearance quality can be obtained.

[0060] For example, based on a total of 100% by weight of a small particle size acrylate graft copolymer (A1), it may contain 35 to 45% by weight of an acrylate rubber polymer having an average particle size of 50 to 100 nm, 40 to 50% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide, preferably 35 to 45% by weight or 12 to 18% by weight of an acrylate rubber polymer having an average particle size of 60 to 95 nm, 40 to 50% by weight or 58 to 63% by weight of an aromatic vinyl compound, and 5 to 10% by weight or 5 to 9% by weight of a vinyl cyanide. Within this range, excellent mechanical strengths such as impact strength can be achieved.

[0061] In the present invention, a polymer containing a certain compound refers to a polymer obtained by polymerizing the compound, and the units in the polymer are derived from the compound.

[0062] The acrylate rubber may contain an alkyl acrylate compound.

[0063] In the present invention, for example, the alkyl acrylate compound may include an alkyl acrylate containing an alkyl group having 1 to 15 carbon atoms, preferably one or more 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 containing a linear alkyl group having 1 to 4 carbon atoms, and still more preferably butyl acrylate.

[0064] In the present invention, for example, the aromatic vinyl compound may contain one or more selected from the group consisting of 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 the group consisting of styrene and α-methylstyrene, and still more preferably styrene. In this case, due to appropriate fluidity, excellent processability and mechanical strengths such as impact resistance can be achieved.

[0065] In the present invention, for example, the vinyl cyanide may contain one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, preferably acrylonitrile.

[0066] For example, the weight-average molecular weight of the small-particle-size acrylate graft copolymer (A1) can preferably be from 50,000 to 150,000 g / mol, more preferably from 50,000 to 130,000 g / mol, and still more preferably from 70,000 to 130,000 g / mol. Within this range, excellent impact strength and hardness can be achieved.

[0067] When measuring the weight-average molecular weight, tetrahydrofuran (THF) and the compound are placed into a 1 mL glass bottle to prepare a sample with a concentration of 1 wt%. Then, after filtering the standard sample (polystyrene) and the sample through a filter (pore size: 0.45 μm), the filtered sample is put into a GPC syringe. Then, the molecular weight and molecular weight distribution of the compound can be obtained by comparing the elution time of the sample with the calibration curve of the standard sample. Infinity II 1260 (Agilent Corporation) can be used as the measuring device, the flow rate can be set to 1.00 mL / min, and the column temperature can be set to 40.0 °C.

[0068] For example, the small-particle-size acrylate graft copolymer (A1) can be prepared by emulsion polymerization. In this case, excellent mechanical strength such as impact strength can be achieved.

[0069] The emulsion polymerization can be carried out using the emulsion graft polymerization method commonly practiced in the field to which the present invention pertains, without particular limitation.

[0070] (A2) Large particle size acrylate graft copolymer

[0071] The large-particle-size acrylate graft copolymer (A2) can contain an acrylate rubber having an average particle size of 150 to 300 nm, preferably 180 to 300 nm, and more preferably 180 to 250 nm. Within this range, excellent mechanical strength such as impact strength can be achieved.

[0072] For example, based on all components constituting the base resin in a total of 100 wt%, the content of the large-particle-size acrylate graft copolymer (A2) can be 30 to 50 wt%, 32 to 48 wt%, or 35 to 45 wt%. Within this range, transparency equal to or better than that of conventional ASA resin compositions can be achieved, and excellent appearance quality can be obtained.

[0073] For example, based on a total of 100% by weight of the large particle size acrylate graft copolymer (A2), it may contain 35 to 45% by weight of an acrylate rubber polymer having an average particle size of 150 to 300 nm, 40 to 50% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide, preferably 35 to 45% by weight or 12 to 18% by weight of an acrylate rubber polymer having an average particle size of 180 to 300 nm, 40 to 50% by weight or 58 to 63% by weight of an aromatic vinyl compound, and 5 to 10% by weight or 5 to 9% by weight of a vinyl cyanide. Within this range, excellent mechanical strengths such as impact strength can be obtained.

[0074] In the present invention, a polymer containing a certain compound refers to a polymer obtained by polymerizing the compound, and the units in the polymer are derived from the compound.

[0075] The acrylate rubber may contain an alkyl acrylate compound.

[0076] In the present invention, for example, the alkyl acrylate compound may include an alkyl acrylate containing an alkyl group having 1 to 15 carbon atoms, preferably one or more 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 containing a linear alkyl group having 1 to 4 carbon atoms, and still more preferably butyl acrylate.

[0077] The types of the aromatic vinyl compound and the vinyl cyanide are as described for the small particle size acrylate graft copolymer (A1).

[0078] For example, the weight average molecular weight of the large particle size acrylate graft copolymer (A2) may preferably be 50,000 to 150,000 g / mol, more preferably 50,000 to 130,000 g / mol, and still more preferably 70,000 to 130,000 g / mol. Within this range, excellent impact strength and hardness can be obtained.

[0079] For example, the large particle size acrylate graft copolymer (A2) can be prepared by emulsion polymerization. In this case, excellent mechanical strengths such as impact strength can be obtained.

[0080] The emulsion polymerization can be carried out using an emulsion graft polymerization method commonly practiced in the field to which the present invention pertains, without particular limitation.

[0081] Based on all components constituting the base resin at a total of 100% by weight, the total amount of the small particle size acrylate graft copolymer (A1) and the large particle size acrylate graft copolymer (A2) can be 40% by weight or more, preferably 40 to 65% by weight, more preferably 45 to 55% by weight. Within this range, when an injection lubrication improver is included in the ASA resin composition, excellent injection molding demolding properties and a physical property balance among injection molding demolding properties, transparency, and mold fouling amount can be achieved.

[0082] (B) Methacrylate copolymer

[0083] For example, the methacrylate copolymer (B) can be an alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer.

[0084] For example, the weight average molecular weight of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer can be preferably 150,000 to 300,000 g / mol, more preferably 180,000 to 280,000 g / mol, still more preferably 180,000 to 250,000 g / mol. Within this range, excellent impact strength and hardness can be achieved.

[0085] For example, based on all components constituting the base resin at a total of 100% by weight, the content of the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer (B) can be 30 to 60% by weight, 35 to 60% by weight, 40 to 60% by weight, or 45 to 57% by weight. Within this range, fluidity and appearance quality can be improved while maintaining impact resistance, heat resistance, and hardness.

[0086] For example, the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer (B) can contain an alkyl methacrylate compound, an aromatic vinyl compound, and a vinyl cyanide. In this case, excellent impact resistance can be achieved, and deterioration of heat resistance properties can be suppressed.

[0087] As a preferred example, based on a total of 100% by weight of an alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer, it may contain 55 to 80% by weight of an alkyl methacrylate compound, 25 to 45% by weight of an aromatic vinyl compound, and 5 to 15% by weight of vinyl cyanide. More preferably, it contains 60 to 75% by weight of an alkyl methacrylate compound, 20 to 40% by weight of an aromatic vinyl compound, and 5 to 10% by weight of vinyl cyanide. Even more preferably, it contains 65 to 75% by weight of an alkyl methacrylate compound, 20 to 35% by weight of an aromatic vinyl compound, and 5 to 10% by weight of vinyl cyanide. In this case, due to excellent fluidity, it can have excellent appearance quality.

[0088] The alkyl methacrylate compound (B) 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, and is preferably methyl methacrylate.

[0089] The types of the aromatic vinyl compound and vinyl cyanide are as described in the description of the small particle size acrylate graft copolymer (A1).

[0090] For example, the alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer (B) can be prepared by emulsion polymerization, solution polymerization, or bulk polymerization. In this case, it can have excellent heat resistance and fluidity.

[0091] The emulsion polymerization, solution polymerization, or bulk polymerization can be carried out by the emulsion polymerization, solution polymerization, or bulk polymerization commonly practiced in the field to which the present invention pertains, and is not limited thereto.

[0092] (C) Saturated carboxylic acid compound

[0093] In one embodiment of the present invention, the saturated carboxylic acid compound may be a compound having one or more -COOH groups at its terminal and having a C5 to C30 alkyl group.

[0094] The refractive index (80 °C) of the saturated carboxylic acid compound may preferably be 1.35 to 1.45 or 1.4 to 1.45. In this case, when used in combination with the unsaturated amide compound described below, it can have an excellent balance of physical properties between injection molding demolding properties and transparency.

[0095] Here, the refractive index can be measured by material methods known in the art. As a specific example, a film of less than 0.2 T is manufactured by extrusion, and the refractive index of the sample relative to air can be measured under room temperature conditions.

[0096] Based on 100 parts by weight of the base resin, the content of the saturated carboxylic acid compound can be 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. Within this range, an excellent physical property balance between injection molding release properties and transparency can be achieved.

[0097] The saturated carboxylic acid compound is not particularly limited as long as it follows the definition of the present invention, and it can be prepared directly or commercially available products can be used.

[0098] (D) Unsaturated amide compound

[0099] In one embodiment of the present invention, the unsaturated amide compound can be a compound having one or more -CON groups at its end and having an alkyl group with 5 to 50 carbon atoms.

[0100] The -CON group can be CONH 2 , -CONHR 1 or -CONR 1 R 2 . Here, R 1 and R 2 can independently be an alkyl group having 1 to 5 carbon atoms.

[0101] The refractive index (80 °C) of the unsaturated amide compound can preferably be 1.5 to 1.6 or 1.53 to 1.58. In this case, when used in combination with the above-mentioned saturated carboxylic acid compound, an excellent physical property balance between injection molding release properties and transparency can be achieved.

[0102] Based on 100 parts by weight of the base resin, the content of the unsaturated amide compound can be 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. Within this range, an excellent physical property balance between injection molding release properties and transparency can be achieved.

[0103] The unsaturated amide compound is not particularly limited as long as it follows the definition of the present invention, and it can be prepared directly or commercially available products can be used.

[0104] ASA resin composition

[0105] For example, the weight ratio (A1:A2) of (A1) and (A2) contained in the ASA resin composition may be 1:3.5 to 1:10, 1:3.5 to 1:9, or 1:4 to 1:8. In this case, even when an injection lubricant improver is added, excellent physical property balance between injection molding demolding property and transparency can be achieved.

[0106] Based on 100 parts by weight of the base resin, the total amount of the saturated carboxylic acid compound (C) and the unsaturated amide compound (D) may preferably be 0.51 to 1.44 parts by weight, more preferably 0.6 to 1.4 parts by weight, still more preferably 0.6 to 1.3 parts by weight. Within this range, excellent physical property balance among injection molding demolding property, transparency, and mold fouling amount can be achieved.

[0107] The mold fouling amount is described in detail below, so its detailed description is omitted here.

[0108] For example, the ASA resin composition may further contain a lubricant or contain a lubricant and additives.

[0109] The additives may include one or more selected from the group consisting of a lubricant, a heat stabilizer, an ultraviolet stabilizer, a fluorescent brightening agent, a chain extender, a pigment, an antibacterial agent, an antifriction agent, and an antiwear agent.

[0110] For example, based on 100 wt% of all components (A1 + A2 + B + C + D + additives) constituting the ASA resin composition, the content of the additives may be 0.01 to 5 wt%, preferably 0.05 to 3 wt%, more preferably 0.1 to 3 wt%, still more preferably 0.1 to 1 wt%. In this case, the desired properties of the ASA resin composition of the present invention can be effectively achieved without deteriorating the inherent properties.

[0111] For example, the lubricant may include one or more selected from the group consisting of an acrylic ester alkyl polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 to 70,000 g / mol, an ethylene-containing copolymer, an olefin wax, and an aliphatic amide compound, preferably one or more selected from the group consisting of an acrylic alkyl ester polymer, a styrene-acrylonitrile copolymer having a weight average molecular weight of 30,000 to 70,000 g / mol, and an olefin wax, more preferably an acrylic alkyl ester polymer. In this case, excellent physical property balance, scratch resistance, colorability, and appearance quality can be achieved.

[0112] The acrylic alkyl ester polymer as the lubricant may include one or more selected from the group consisting of methyl polyacrylate, ethyl polyacrylate, and butyl polyacrylate. In this case, the formation of mold fouling is inhibited, so the appearance of the molded article can be more attractive, and high gloss can be achieved.

[0113] For example, based on all components (A1 + A2 + B) of the base resin in 100 parts by weight of the ASA resin composition, the content of the acrylic alkyl ester polymer as a lubricant may be 1 part by weight or less, preferably 0.1 to 1 part by weight, more preferably 0.3 to 1 part by weight. Within this range, transparency and molding release properties can be improved.

[0114] The acrylic alkyl ester polymer as a lubricant is not particularly limited as long as it is an acrylic alkyl ester lubricant commonly used in the technical field to which the present invention pertains, and the acrylic alkyl ester polymer can be prepared directly or commercially available products can be used.

[0115] The weight-average molecular weight of the styrene-acrylonitrile copolymer as a lubricant may preferably be 40,000 to 67,000 g / mol, more preferably 50,000 to 65,000 g / mol, still more preferably 55,000 to 65,000 g / mol. Within this range, fluidity can be improved, thereby improving processability and appearance quality.

[0116] For example, the melt flow index (190 °C, 5 kg) of the styrene-acrylonitrile copolymer as a lubricant measured according to ISO 1133 may be 20 to 60 g / 10 min, preferably 25 to 55 g / 10 min. Within this range, excellent impact strength, fluidity, and appearance quality can be achieved.

[0117] For example, the heat distortion temperature of the styrene-acrylonitrile copolymer as a lubricant measured according to ASTM D648 may be 82 to 90 °C, preferably 84 to 88 °C. Within this range, excellent impact strength, fluidity, and appearance quality can be achieved.

[0118] For example, based on all components (A1 + A2 + B) of the base resin in 100 parts by weight of the ASA resin composition, the content of the styrene-acrylonitrile copolymer as a lubricant may be 1 part by weight or less, preferably 0.1 to 1 part by weight, more preferably 0.3 to 1 part by weight. Within this range, transparency and molding release properties can be improved.

[0119] For example, the ethylene-containing copolymer may include one or more selected from the group consisting of an ethylene / 1-butene copolymer and an ethylene / n-butyl acrylate / carbon monoxide terpolymer. In this case, excellent heat resistance, fluidity, and appearance quality can be achieved.

[0120] The weight-average molecular weight of the ethylene-containing copolymer can preferably be 40,000 to 67,000 g / mol, more preferably 50,000 to 65,000 g / mol, and still more preferably 55,000 to 65,000 g / mol. Within this range, the fluidity can be improved, thereby improving the processability and appearance quality.

[0121] For example, based on 100 parts by weight of all components (A1 + A2 + B) of the base resin in the ASA resin composition, the content of the ethylene-containing copolymer can be 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight. Within this range, the transparency and molding release properties can be improved.

[0122] For example, the olefin wax can include one or more selected from the group consisting of polyethylene wax and polypropylene wax, preferably polyethylene wax. In this case, excellent heat resistance, fluidity, and appearance quality can be achieved.

[0123] For example, based on 100 parts by weight of all components (A1 + A2 + B) of the base resin in the ASA resin composition, the content of the olefin wax can be 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight. Within this range, the transparency and molding release properties can be improved.

[0124] For example, the aliphatic amide compound can include one or more selected from the group consisting of stearamide, behenamide, ethylene bis(stearamide), N,N'-ethylene bis(12-hydroxystearamide), erucamide, oleamide, and ethylene bisoleamide, preferably ethylene bis(stearamide). In this case, excellent impact strength, fluidity, and appearance quality can be achieved.

[0125] In particular, the thermoplastic resin composition of the present invention preferably does not contain an excessive amount of stearic acid-based lubricants. In this case, as described in Example 2, compared with Comparative Examples 7 and 8 to be described later, molded articles with a beautiful appearance and high gloss can be obtained.

[0126] For example, the stearic acid-based lubricant can include one or more selected from the group consisting of barium stearate, calcium stearate, magnesium stearate, zinc stearate, and stearic acid.

[0127] For example, based on 100 parts by weight of all components (A1 + A2 + B) of the base resin in the ASA resin composition, the content of the aliphatic amide compound can be 1 part by weight or less, preferably 0.1 to 1 part by weight, and more preferably 0.3 to 1 part by weight. Within this range, the transparency and molding release properties can be improved.

[0128] For example, based on 100% by weight of all components (A1 + A2 + B + C + D + lubricant) constituting the ASA resin composition, the content of the lubricant can be 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, more preferably 0.7 to 2.2% by weight. Within this range, excellent impact resistance and fluidity can be achieved.

[0129] For example, as other additives other than the lubricant, based on 100% by weight of all components (A1 + A2 + B + C + D + other additives) constituting the ASA resin composition, the content of one or more additives selected from the group consisting of heat stabilizers, ultraviolet stabilizers, fluorescent brighteners, chain extenders, pigments, antibacterial agents, friction reducers, and anti-wear agents can be 0.1 to 5% by weight, preferably 1 to 3% by weight, respectively. In this case, the desired properties of the ASA resin composition of the present invention can be effectively achieved without deteriorating the inherent properties.

[0130] For example, based on 100% by weight of all components (A1 + A2 + B + C + D + heat stabilizer) constituting the ASA resin composition, the content of the heat stabilizer can be 0.1 to 2% by weight, more preferably 0.2 to 1.5% by weight. Within this range, heat resistance can be improved.

[0131] For example, the heat stabilizer can include one or more selected from the group consisting of phenolic heat stabilizers, phosphite / phosphate heat stabilizers, and thioether heat stabilizers, preferably one or more selected from the group consisting of phenolic heat stabilizers and phosphite / phosphate heat stabilizers.

[0132] For example, the phenolic heat stabilizer can include one or more selected from the group consisting of methyl tetramethylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris(4-tert-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-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione.

[0133] For example, the phosphite / phosphate heat stabilizer can be tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, or a mixture thereof.

[0134] For example, the thioether-based heat stabilizer may include one or more selected from the group consisting of dilauryl thiodipropionate, bis(tetradecyl) thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate, 2-mercaptobenzimidazole, phenothiazine, octadecyl mercaptoacetate, butyl mercaptoacetate, octyl mercaptoacetate, and thiocresol.

[0135] For example, based on 100% by weight of all components (A1 + A2 + B + C + D + UV stabilizer) constituting the ASA resin composition, the content of the UV stabilizer may preferably be 0.1 to 3% by weight, more preferably 0.5 to 1.5% by weight. In this case, the weather resistance can be improved.

[0136] For example, the ultraviolet stabilizer may contain hindered amine light stabilizers (HALS), preferably one or more selected from the group consisting of: 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-hydroxybenzyl malonate, the condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-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, the linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxaspiro[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-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino], more preferably bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), 2-(2H-benzotriazol-2-yl)-4-(-(1,1,3,3-tetramethylbutyl)phenol (2-(2H-benzotriazolyl-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-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino], or a mixture thereof, even more preferably bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (bis(2,2,6,6-tetramethyl-4-piperidyl), poly[[6-(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,(2,6,6 - tetramethyl - 4 - piperidyl)imino]-1,6 - hexanediyl[(2,2,6,6 - tetramethyl - 4 - piperidyl)imino], or a mixture thereof. In this case, weather resistance can be significantly improved without deteriorating impact resistance and fluidity.,

[0137] For example, the pigment can be a carbon black pigment.

[0138] For example, based on 100% by weight of all the components (A1 + A2 + B + C + D + pigment) constituting the ASA - type resin composition, the content of the pigment can preferably be 0.5 to 5% by weight, more preferably 1 to 4.5% by weight, still more preferably 2 to 4.5% by weight. Within this range, excellent physical property balance and colorability can be achieved.

[0139] For example, as the antibacterial agent, inorganic antibacterial agents including zinc - based antibacterial agents and antibacterial agents, or organic antibacterial agents known in the art can be used.

[0140] For example, based on 100% by weight of all the components (A1 + A2 + B + C + D + antibacterial agent) constituting the ASA - type resin composition, the content of the antibacterial agent can preferably be 0.5 to 5% by weight, more preferably 1 to 4.5% by weight, still more preferably 2 to 4.5% by weight. Within this range, excellent physical property balance and antibacterial effect can be achieved.

[0141] For example, based on 100% by weight of all the components (A1 + A2 + B + C + D + antifriction agent) constituting the ASA - type resin composition, the content of the antifriction agent can preferably be 0.5 to 5% by weight, more preferably 1 to 4.5% by weight, still more preferably 2 to 4.5% by weight. Within this range, excellent physical property balance and antifriction property can be achieved.

[0142] For example, based on 100% by weight of all the components (A1 + A2 + B + C + D + anti - wear agent) constituting the ASA - type resin composition, the content of the anti - wear agent can preferably be 0.5 to 5% by weight, more preferably 1 to 4.5% by weight, still more preferably 2 to 4.5% by weight. Within this range, excellent physical property balance and anti - wear property can be achieved.

[0143] In addition, the present invention provides an ASA - type resin composition comprising 100 parts by weight of a base resin, the base resin comprising 1 to 10% by weight of a small - particle - size acrylate graft copolymer (A1); 35 to 50% by weight of a large - particle - size acrylate graft copolymer (A2); and 40 to 60% by weight of a methacrylate copolymer (B),

[0144] 0.1 to 1 part by weight of a saturated carboxylic acid compound having one or more -COOH groups at its ends, having a C5 to C30 alkyl group and a refractive index (80 °C) of 1.35 to 1.45, and

[0145] 0.1 to 1 part by weight of an unsaturated amide compound having one or more -CON groups at its ends, having a C5 to C50 alkyl group and a refractive index (80 °C) of 1.5 to 1.6.

[0146] Among them, the total amount of the saturated carboxylic acid compound (C) and the unsaturated amide compound (D) is 0.51 to 1.44 parts by weight.

[0147] For example, when using an injection molding machine (clamping force: 220 tons, LS company) to continuously inject a removable mold core 200 times under injection molding conditions of a temperature of 250 to 280 °C and a pressure of 25 to 35 bar, measuring the weight of the gas deposited on the mold core, and then calculating the mold fouling amount by the following Equation 1, the mold fouling amount of the ASA resin composition can be 40 mg or less, 36 mg or less, and 35.5 mg or less. Within this range, an excellent balance of physical properties can be achieved, and the appearance quality can be improved by maintaining transparency.

[0148] [Equation 1]

[0149] Mold fouling amount (mg) = Weight of the mold core after 200 injections - Initial weight of the mold core

[0150] For example, the demolding force measured by installing an injection molding demolding property (ejection force) measuring device in the take-out step of a cup-shaped mold injection molding machine for the ASA resin composition can be 1600 N or less or 1590 N or less. Within this range, excellent demolding properties can be achieved, so cracking rarely occurs after injection, resulting in excellent appearance quality.

[0151] The haze of the ASA resin composition measured according to ASTM D1003dp can be less than 3.0%, preferably 2.9% or less. Within this range, an excellent balance of physical properties can be achieved, and the appearance quality can be improved by maintaining transparency.

[0152] For example, the heat distortion temperature (HDT) of the ASA resin composition measured using an HDT tester 6A-2 (manufacturer: TOYOSEIKI) according to ISO 75-1,2 can be 74 °C or higher, preferably 74 to 76 °C. Within this range, excellent heat resistance can be achieved without affecting mechanical strength.

[0153] Preparation method of ASA resin composition

[0154] For example, the method for preparing an ASA resin composition includes the step of kneading and extruding a base resin containing an acrylate graft copolymer (A) and a methacrylate copolymer (B), a saturated carboxylic acid compound (C), and an unsaturated amide compound (D) at 200 to 300 °C and 100 to 500 rpm. In this case, even when an injection lubrication improver is added, an excellent balance of physical properties among transparency, injection molding demolding properties, and mold fouling amount can be achieved.

[0155] For example, the method includes the following steps: kneading and extruding 100 parts by weight of a base resin containing an acrylate graft copolymer (A) and a methacrylate copolymer (B) at 200 to 300 °C and 100 to 500 rpm; and a total of 0.51 to 1.44 parts by weight of a saturated carboxylic acid compound (C) and an unsaturated amide compound (D). In this case, an excellent balance of physical properties among injection molding demolding properties, transparency, and mold fouling amount can be achieved.

[0156] As a preferred example, the method includes the following steps: kneading and extruding 100 parts by weight of a base resin containing 1 to 10% by weight of a small-particle-size acrylate graft copolymer (A1); 35 to 50% by weight of a large-particle-size acrylate graft copolymer (A2); and 40 to 60% by weight of a methacrylate copolymer (B) at 200 to 300 °C and 100 to 500 rpm, 0.1 to 1 part by weight of a saturated carboxylic acid compound having one or more -COOH groups at its end, having a C5 to C30 alkyl group, and having a refractive index (80 °C) of 1.35 to 1.45, and 0.1 to 1 part by weight of an unsaturated amide compound having one or more -CON groups at its end, having a C5 to C50 alkyl group, and having a refractive index (80 °C) of 1.5 to 1.6, wherein the total input amount of the saturated carboxylic acid compound (C) and the unsaturated amide compound (D) is 0.51 to 1.44 parts by weight based on 100 parts by weight of the base resin. In this case, by including an injection lubrication improver, an excellent balance of physical properties among injection molding demolding properties, transparency, and mold fouling amount can be achieved.

[0157] The method for preparing an ASA resin composition shares all the technical features of the above ASA resin composition. Therefore, the description of the repeated parts will be omitted.

[0158] The step of preparing pellets using an extrusion kneader is preferably carried out at a size of 25 to 75 pi at 200 to 300 °C, more preferably at a size of 20 to 70 pi at 220 to 260 °C. Within this range, stable extrusion can be achieved, and an excellent mixing effect can be obtained. At this time, the temperature is the temperature set in the cylinder, and pi refers to the outer diameter (unit: mm).

[0159] In the present invention, an extrusion kneader commonly used in the technical field to which the present invention pertains can be used without particular limitation. Preferably, a twin-screw extrusion kneader can be used.

[0160] Molded article

[0161] For example, the molded article of the present invention contains the ASA resin composition of the present invention. In this case, compared with a conventional ASA resin composition, even when an injection lubricant improver is added, it can have an excellent balance of physical properties among injection molding demolding properties, transparency, and mold fouling amount.

[0162] The method for manufacturing the molded article of the present invention includes a step of injecting pellets produced by using the preparation method of the ASA resin composition at 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. In this case, an injection molded article with high impact strength can be easily manufactured.

[0163] The injection temperature can preferably be 220 to 280 °C, more preferably 230 to 270 °C. Within this range, an injection molded article with a complex design can be easily manufactured.

[0164] The injection pressure can preferably be 70 to 90 bar, more preferably 75 to 85 bar. Within this range, an injection molded article with a complex design can be easily manufactured.

[0165] The holding pressure can preferably be 35 to 60 bar, more preferably 40 to 55 bar. Within this range, an injection molded article with a complex design can be easily manufactured.

[0166] The molded article can be used for small medical transparent products including syringes and catheter connectors, as well as small transparent food containers.

[0167] When describing the ASA resin composition of the present invention, its preparation method, and the molded article containing the same, it should be noted that other conditions or equipment not explicitly described herein can be appropriately selected within the range commonly adopted in the art without particular limitation.

[0168] 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 or spirit of the present invention. In addition, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention, and these changes and modifications also fall within the scope of the appended claims.

[0169] [Examples]

[0170] The materials used in the examples and comparative examples are as follows.

[0171] *(A1) Small particle size acrylate graft copolymer: An ASA graft copolymer containing acrylate rubber with an average particle size of 80 nm (butyl acrylate: 35 to 45% by weight, styrene: 40 to 50% by weight, and acrylonitrile: 5 to 10% by weight, weight average molecular weight: 50,000 to 150,000 g / mol)

[0172] *(A2) Large particle size acrylate graft copolymer: An ASA graft copolymer containing acrylate rubber with an average particle size of 220 nm (butyl acrylate: 35 to 45% by weight, styrene: 40 to 50% by weight, and acrylonitrile: 5 to 10% by weight, weight average molecular weight: 50,000 to 150,000 g / mol)

[0173] *(B) Methacrylate copolymer: An alkyl methacrylate compound - aromatic vinyl compound - vinyl cyanide copolymer (methyl methacrylate: 71% by weight, styrene: 22% by weight, and acrylonitrile: 7% by weight, weight average molecular weight: 120,000 to 150,000 g / mol)

[0174] *(C) Saturated carboxylic acid compound: A stearic acid compound (LG H&H Co., product name: Elofad TH100) containing one or more -COOH groups at its end, having a C18 alkyl group, and a refractive index (80 °C) of 1.4299

[0175] *(D) Unsaturated amide compound: An erucic acid amide compound (AkzoNobel Co., product name: ArmoslipE) containing one or more -CON groups at its end, having a double bond at the center of its skeleton, containing an alkyl group with 22 carbon atoms, and a refractive index (80 °C) of 1.5614

[0176] Examples 1 to 4 and Comparative Examples 1 to 8

[0177] According to the components and contents shown in Table 1 and Table 2 below, the components are supplied to a twin - screw extruder. Based on a total of 100 parts by weight of the above components (A1), (A2), and (B), the components (C) and (D) are supplied to the twin - screw extruder in the corresponding amounts (parts by weight).

[0178] Then, kneading and extrusion are carried out at a barrel temperature of 240 °C to obtain pellets, and the melt flow index is measured using the obtained pellets.

[0179] Thereafter, injection is carried out using an injection molding machine (Engel Co., 120 MT) at an injection temperature of 240 °C to produce specimens for physical property measurement.

[0180] [Test Example]

[0181] The properties of the specimens fabricated 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.

[0182] Measurement method

[0183] * Injection molding demolding property (ejection force, unit: N): The injection molding demolding property was measured at an injection temperature of 210 °C, a mold temperature of 40 °C, and a holding pressure of 80 MPa. Specifically, after injection only by the holding pressure, the Figure 1 injection molding demolding property (ejection force) measuring device shown in was installed on an injection molding machine for cup-shaped injection molding products, and the injection molding demolding property was measured by measuring the ejection pressure during the ejection process.

[0184] Specifically, the demolding force was monitored by a sensor attached to the injection molding demolding property measuring device, and the data was processed to obtain the result.

[0185] * Haze (unit: %): The haze was measured at 25 °C according to ASTM D1003dp.

[0186] * Mold fouling amount (unit: mg): Under injection molding conditions of a temperature of 250 to 280 °C and a pressure of 25 to 35 bar, a removable mold core was continuously injected 200 times using an injection molding machine (clamping force: 220 tons, LS Corporation). Then, the weight of the gas deposited in the mold core was measured, and the mold fouling amount was calculated by the following Equation 1.

[0187] [Equation 1]

[0188] Mold fouling amount (mg) = Weight of the mold core after 200 injections - Initial weight of the mold core

[0189] * Heat distortion temperature (HDT, °C): The heat distortion temperature was measured using an HDT tester 6A-2 (manufacturer: TOYOSEIKI) according to ISO75-1,2.

[0190] [Table 1]

[0191] Category Example 1 Example 2 Example 3 Example 4 Graft copolymer (A1) 10 5 8 10 Graft copolymer (A2) 35 40 45 40 Methacrylate copolymer (B) 55 55 47 50 Total amount of (C) + (D) (parts by weight) 1.3 1 1.3 0.6 Amount of (C) (parts by weight) 0.8 0.5 0.5 0.3 Amount of (D) (parts by weight) 0.5 0.5 0.8 0.3 Injection molding demolding property (N) 1350 1480 1380 1580 Haze (%) 2.82 2.48 2.74 2.01 Mold fouling amount (mg) 36 25 38 14 HDT (°C) 75.1 75.5 76.3 77.1

[0192] [Table 2]

[0193]

[0194] In 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). Here, 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).

[0195] As shown in Tables 1 and 2, Examples 1 to 4 of the present invention exhibited injection molding demolding properties equal to or superior to those of Comparative Examples 1 to 8. In addition, compared with Comparative Examples 1 to 8, in the case of Examples 1 to 4, transparency was improved and the amount of mold fouling was reduced, thereby preventing deterioration of surface properties that may occur during the molding process. Moreover, even when producing small products, excellent appearance quality was achieved.

[0196] In particular, in the case of Example 4 using a base resin containing graft copolymers (A-1) and (A-2) and a methacrylate copolymer (B) and a small amount of injection lubrication improver within an appropriate range, compared with Example 1 using a base resin containing graft copolymers (A-1) and (A-2) and a methacrylate copolymer (B) and a large amount of injection lubrication improver (C) within an appropriate range, the injection molding demolding properties and transparency were improved, and the amount of mold fouling was reduced.

[0197] In addition, Comparative Example 1 that did not use compounds (C) and (D) exhibited poor injection molding properties.

[0198] In addition, Comparative Example 2 or Comparative Example 3 that used compound (C) or compound (D) alone exhibited poor transparency. For reference, when the measured haze is less than 3.0, it is judged as passing.

[0199] In addition, Comparative Example 4 in which the amounts of compounds (C) and (D) were less than the scope of the present invention exhibited poor injection molding demolding properties. For reference, when the measured pressure exceeded 1600 N, cracking occurred on the injection molded article during injection.

[0200] In addition, Comparative Examples 5 and 6 in which the amounts of compounds (C) and (D) were greater than the scope of the present invention exhibited poor transparency and mold fouling amount. For reference, when the measured weight is less than 50 mg, it is judged as passing.

[0201] In addition, Comparative Example 7 that used an excessive amount of compound (C) and Comparative Example 8 that used an excessive amount of compound (D) exhibited poor demolding force, transparency, and mold fouling amount.

[0202] In summary, even when an injection lubricant improver is used, by controlling the content of the graft copolymer of acrylate rubber having different average particle diameters and the styrene-based copolymer, the combined synergistic effect improves the injection molding mold release property and transparency and reduces the amount of mold fouling. Therefore, transparency equivalent to or superior to that of conventional transparent materials can be achieved. In addition, since the mold release property during injection is improved, injection cracking can be prevented even when injecting small-sized transparent products. Therefore, the present invention can provide a resin composition having excellent product reliability.

Claims

1. An ASA-based resin composition comprising: a base resin comprising an acrylate graft copolymer (A) and a methacrylate copolymer (B), a saturated carboxylic acid compound (C) and an unsaturated amide compound (D), in, The total content of the saturated carboxylic acid compound (C) and the unsaturated amide compound (D) is 0.51 parts by weight to 1.44 parts by weight based on 100 parts by weight of the base resin.

2. The ASA-based resin composition according to claim 1, wherein The saturated carboxylic acid compound is a compound including one or more -COOH groups at its terminal, having a C5 to C30 alkyl group, and having a refractive index at 80° C. of 1.35 to 1.

45.

3. The ASA-based resin composition according to claim 1, wherein The unsaturated amide compound is a compound including one or more -CON groups at its terminal, having a C5 to C50 alkyl group, and having a refractive index at 80° C. of 1.5 to 1.

6.

4. The ASA-based resin composition according to claim 1, wherein The saturated carboxylic acid compound (C) and the unsaturated amide compound (D) are contained in a weight ratio of 1:0.5 to 1:1.5 (C:D).

5. The ASA-based resin composition according to claim 1, wherein The base resin includes the acrylate graft copolymer (A) and the methacrylate copolymer (B) in a weight ratio of 1:0.5 to 1:1.5 (A:B).

6. The ASA-based resin composition according to claim 5, wherein The acrylate graft copolymer (A) comprises a small-particle acrylate graft copolymer (A1) and a large-particle acrylate graft copolymer (A2) in a weight ratio of 1:3.5 to 1:10 (A1:A2).

7. The ASA-based resin composition according to claim 6, wherein The small particle size acrylate graft copolymer (A1) comprises 35 to 45 wt % of a rubber polymer having an average particle size of 50 to 100 nm, 40 to 50 wt % of an aromatic vinyl compound and 5 to 10 wt % of a vinyl cyanide, and has a weight average molecular weight of 50,000 to 150,000 g / mol.

8. The ASA-based resin composition according to claim 6, wherein The large-particle size acrylate graft copolymer (A2) comprises 35 to 45 wt % of a rubber polymer having an average particle size of 150 to 300 nm, 40 to 50 wt % of an aromatic vinyl compound and 5 to 10 wt % of a vinyl cyanide, and has a weight average molecular weight of 50,000 to 150,000 g / mol.

9. The ASA-based resin composition according to claim 1, wherein The saturated carboxylic acid compound may be included in an amount of about 0.1 to about 1.0 parts by weight based on 100 parts by weight of the base resin.

10. The ASA-based resin composition according to claim 1, wherein The unsaturated amide compound may be included in an amount of about 0.1 to about 1.0 parts by weight based on 100 parts by weight of the base resin.

11. The ASA-based resin composition according to claim 1, wherein When a removable core is continuously injected 200 times under injection molding conditions of a temperature of 250° C. to 280° C. and a pressure of 25 bar to 35 bar using an injection molding machine (clamp force: 220 tons, LS Company), the weight of the gas deposited on the core is measured, and then the mold build-up amount is calculated by the following equation 1, the mold build-up amount of the ASA-based resin composition is 6.2 mg or less, [Equation 1] Mold buildup (mg) = weight of mold core after 200 injections - initial mold core weight.

12. The ASA-based resin composition according to claim 1, wherein The ASA-based resin composition has a demolding force of 1600 N or less measured by installing an ejection force measuring device in a removal step of a cup-shaped mold injection molding machine. 13 . The ASA-based resin composition according to claim 1 , wherein the ASA-based resin composition has a haze measured according to ASTM D1003 of less than 3.0%.

14. A method for preparing an ASA-based resin composition, the method comprising: kneading and extruding a base resin comprising an acrylate graft copolymer (A) and a methacrylate copolymer (B), a saturated carboxylic acid compound (C) and an unsaturated amide compound (D) at 200° C. to 300° C. and 100 rpm to 500 rpm, Wherein, based on 100 parts by weight of the base resin, the total content of the saturated carboxylic acid compound (C) and the unsaturated amide compound (D) is 0.51 parts by weight to 1.44 parts by weight. 15 . A molded product comprising the ASA-based resin composition according to any one of claims 1 to 13 .

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