Abs resin modifier, resin composition, molded body, and method for producing resin composition

Abstract

Provided is an ABS resin modifier that improves the impact resistance and chemical resistance of ABS resin. An ABS resin modifier containing a maleimide-based resin (A) having a maleimide-based monomer unit, a styrene-based monomer unit, and an unsaturated dicarboxylic anhydride-based monomer unit, and a polyamide resin (B), the ABS resin modifier having a dispersed phase with an average particle diameter of 100 nm or less.

Description

Technical Field

[0001] This invention relates to ABS resin modifiers, resin compositions containing the ABS resin modifiers, molded articles obtained by molding the resin compositions, and methods for manufacturing the resin compositions. Background Technology

[0002] ABS resin is a thermoplastic resin mainly composed of acrylonitrile, butadiene, and styrene. It is widely used in automobiles, home appliances, office equipment, building materials, and daily necessities due to its excellent mechanical strength, appearance, chemical resistance, and moldability. It is known that adding polyamide resin and compatibilizers to ABS resin can improve chemical resistance and impact resistance (Patent Document 1, Patent Document 2). However, if the polyamide resin content is low, it is difficult to simultaneously achieve good chemical resistance and impact resistance; if the content is high, the dimensional stability due to moisture absorption may deteriorate.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2007-217621

[0006] Patent Document 2: Japanese Patent Application Publication No. 2014-122254 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] The objective of this invention is to provide an ABS resin modifier that can improve the impact resistance and chemical resistance of ABS resin.

[0009] Solution for solving the problem

[0010] (1) An ABS resin modifier containing a maleimide resin (A) and a polyamide resin (B), wherein the maleimide resin (A) has maleimide monomer units, styrene monomer units and unsaturated dicarboxylic anhydride monomer units, and the ABS resin modifier has a dispersed phase having an average particle size of less than 100 nm.

[0011] (2) The ABS resin modifier as described in (1), wherein when the maleimide resin (A) is set to 100% by mass, the maleimide resin (A) contains 1 to 10% by mass of the unsaturated dicarboxylic acid anhydride monomer unit.

[0012] (3) The ABS resin modifier as described in (1) or (2), wherein the nominal tensile strain at break measured at a tensile speed of 50 mm / min is more than 10% after the specimen has been conditioned for 16 hours in a constant temperature bath at 23°C and 50% humidity based on JIS K7161.

[0013] (4) A resin composition comprising any one of (1) to (3) an ABS resin modifier and a resin (C) selected from at least one of ABS resin, SAN resin, ASA resin and AES resin.

[0014] (5) The resin composition as shown in (4), wherein when the total weight of the resin composition is 100%, the polyamide resin (B) contained in the resin composition is less than 20% by weight.

[0015] (6) The resin composition as described in (4) or (5), wherein, based on JIS K7111-1, a notched specimen after 16 hours of conditioning in a constant temperature bath at 23°C and 50% humidity has a Charpy impact strength of 12 KJ / m, measured with the edgewise direction of impact. 2 above.

[0016] (7) A method for manufacturing a resin composition, comprising a step of melt-blending a raw material using an extruder, said raw material containing any one of the ABS resin modifiers (1) to (3) and a resin (C) selected from at least one of ABS resin, SAN resin, ASA resin, and AES resin. (8) A molded article obtained by molding the resin composition (4) to (6).

[0017] The effects of the invention

[0018] By adding the ABS resin modifier of the present invention to at least one resin selected from ABS resin, SAN resin, ASA resin, and AES resin, a resin composition with excellent chemical resistance and impact resistance can be obtained. Detailed Implementation

[0019] <Terminology Explanation>

[0020] In this specification, references such as "A~B" mean A or above and B or below.

[0021] The embodiments of the present invention will be described in detail below.

[0022] The ABS resin modifier of this embodiment contains maleimide-based resin (A) and polyamide resin (B). Preferably, the ABS resin modifier of this embodiment is obtained by melt-blending raw materials containing maleimide-based resin (A) and polyamide resin (B).

[0023] Maleimide resin (A) has maleimide monomer units, styrene monomer units, and unsaturated dicarboxylic anhydride monomer units. Maleimide resin (A) may also have monomer units other than maleimide monomer units, styrene monomer units, and unsaturated dicarboxylic anhydride monomer units, for example, it may also have vinyl cyanide monomer units.

[0024] Maleimide monomer units include, for example, N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide, as well as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, and N-tribromophenylmaleimide. N-phenylmaleimide is preferred. Maleimide monomer units can be used alone or in combination of two or more. For example, a raw material composed of maleimide monomers can be used. Alternatively, it can be obtained by imidizing a raw material composed of unsaturated dicarboxylic anhydride monomer units with ammonia or a primary amine.

[0025] The styrene-based monomer units include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, and α-methyl-p-methylstyrene, etc. Styrene is preferred. Styrene-based monomer units can be used alone or in combination of two or more.

[0026] The unsaturated dicarboxylic acid anhydride monomer units include maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, etc., with maleic anhydride being the preferred choice. Unsaturated dicarboxylic acid anhydride monomer units can be used alone or in combination of two or more.

[0027] The vinyl cyanide monomer unit is acrylonitrile, methacrylonitrile, ethyl acrylonitrile, fumaric acid, etc. Acrylonitrile is preferred. The vinyl cyanide monomer unit can be used alone or in combination of two or more.

[0028] The weight-average molecular weight (Mw) of the maleimide-based resin (A) is preferably 80,000 to 180,000, more preferably 130,000 to 160,000. If the weight-average molecular weight (Mw) is too low, the impact strength of the resin composition obtained using the ABS resin modifier may decrease. If it is too high, the flowability of the resin composition obtained using the ABS resin modifier may decrease, resulting in poor moldability. In addition to adjusting the polymerization temperature, polymerization time, and polymerization initiator dosage, methods for controlling the weight-average molecular weight (Mw) of the maleimide-based resin (A) include adjusting the solvent concentration and chain transfer agent dosage. The weight-average molecular weight of the maleimide-based resin (A) is a polystyrene equivalent value determined by gel permeation chromatography (GPC) under the following conditions.

[0029] Device Name: SYSTEM-21Shodex (manufactured by Showa Denko Corporation)

[0030] Column: Three PL gel MIXED-B columns connected in series

[0031] Temperature: 40℃

[0032] Detection: Differential Refractive Index

[0033] Solvent: Tetrahydrofuran

[0034] Concentration: 2% by mass

[0035] Standard curve: plotted using standard styrene (PS) (manufactured by PL Corporation).

[0036] When the total amount of maleimide-based resin (A) is set at 100% by mass, the amount of styrene monomer units contained in maleimide-based resin (A) is preferably 30-70% by mass, more preferably 40-60% by mass, for example, 30, 35, 40, 45, 50, 55, 60, 65, 70% by mass, or within any two values ​​exemplified herein. If the content of styrene monomer units is too low, the compatibility with ABS resin may sometimes deteriorate, and the effect as an ABS resin modifier may not be fully realized. If the content is too high, the dispersed phase in the ABS resin modifier may sometimes become larger.

[0037] When the maleimide-based resin (A) is set to 100% by mass, the amount of unsaturated dicarboxylic acid anhydride monomer units contained in the maleimide-based resin (A) is preferably 1 to 10% by mass, more preferably 1 to 7% by mass, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by mass, or within any two values ​​exemplified herein. If the amount of unsaturated dicarboxylic acid anhydride monomer units is too small, the impact strength of the resin composition may decrease. If the amount is too large, the flowability of the resin composition may decrease, and the moldability may deteriorate. The unsaturated dicarboxylic acid anhydride monomer units are values ​​measured by titration. Furthermore, as described below, by appropriately controlling the amount of unsaturated dicarboxylic acid anhydride monomer units contained in the maleimide-based resin (A), the average particle size of the dispersed phase can be easily controlled.

[0038] When the total amount of maleimide-based resin (A) is set at 100% by mass, the amount of maleimide monomer units contained in maleimide-based resin (A) is preferably 10% to 68% by mass. If the content of maleimide monomer units is less than 10% by mass or more than 68% by mass, the compatibility with ABS resin may sometimes deteriorate, and the effect as an ABS resin modifier cannot be fully realized. The content of maleimide monomer units is particularly preferably 30% to 58% by mass. The content of maleimide monomer units can be, for example, 10, 20, 30, 40, 50, 60, or 68% by mass, or it can be within the range of any two values ​​exemplified herein.

[0039] When the total amount of maleimide resin (A) is set to 100% by mass, the total amount of styrene monomer units, unsaturated dicarboxylic acid anhydride monomer units and maleimide monomer units contained in maleimide resin (A) is preferably 90% by mass or more.

[0040] Maleimide-based resin (A) may also be composed solely of styrene monomer units, unsaturated dicarboxylic anhydride monomer units, maleimide monomer units, and vinyl cyanide monomer units. Alternatively, maleimide-based resin (A) may also be composed solely of styrene monomer units, unsaturated dicarboxylic anhydride monomer units, and maleimide monomer units.

[0041] The glass transition midpoint temperature (Tmg) of the maleimide-based resin (A) is preferably 170–210°C, more preferably 175–205°C. The glass transition midpoint temperature (Tmg) of the maleimide-based resin (A) is a value measured using DSC based on JIS K-7121, and is a value measured under the following conditions: Instrument: Robot DSC6200 manufactured by Seiko Instruments Co., Ltd.

[0042] Heating rate: 10℃ / minute

[0043] As a method for manufacturing maleimide-based resin (A), known methods can be employed. For example, one method involves copolymerizing a monomer mixture consisting of styrene monomers, maleimide monomers, unsaturated dicarboxylic anhydride monomers, and other copolymerizable monomers. Another method involves copolymerizing a monomer mixture consisting of styrene monomers, unsaturated dicarboxylic anhydride monomers, and other copolymerizable monomers, and then reacting a portion of the unsaturated dicarboxylic anhydride monomer units with ammonia or a primary amine to imide them, converting them into maleimide monomer units (hereinafter referred to as the "post-imideation method").

[0044] The polymerization methods for maleimide-based resins (A) include solution polymerization and bulk polymerization. From the perspective of batch addition and equal-side polymerization, the copolymer composition is more uniform, and solution polymerization is preferred. From the viewpoint of minimizing the formation of byproducts and reducing adverse effects, the solvent for solution polymerization is preferably non-polymerizable. Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone; ethers such as tetrahydrofuran and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and N,N-dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. From the viewpoint of easy solvent removal during the devolatilization and recovery of maleimide-based resins, methyl ethyl ketone and methyl isobutyl ketone are preferred. As for the polymerization process, continuous polymerization, batch polymerization, and semi-batch polymerization are all applicable. There are no particular limitations on the polymerization method; from the viewpoint of manufacturing with a simple process and high productivity, free radical polymerization is preferred.

[0045] When using solution polymerization or bulk polymerization, polymerization initiators and chain transfer agents can be used, and the polymerization temperature is preferably in the range of 80–150°C. Examples of polymerization initiators include azo compounds such as azobisisobutyronitrile, azodicyclohexanenitrile, azodimethylpropionitrile, and azodimethylbutyronitrile; peroxides such as benzoyl peroxide, tert-butyl peroxide, 1,1-di(tert-butyl peroxide)cyclohexane, tert-butyl peroxide isopropyl monocarbonate, tert-butyl peroxide-2-ethylhexanoate, di-tert-butyl peroxide, dicumyl peroxide, and ethyl-3,3-di(tert-butyl peroxide)butyrate; one or more of these can be used. From the viewpoint of controlling the polymerization rate and polymerization ratio, azo compounds or organic peroxides with a half-life of 10 hours at 70–120°C are preferred. The amount of polymerization initiator used is not particularly limited, but preferably 0.1 to 1.5 parts by mass relative to 100 parts by mass of all monomer units, more preferably 0.1 to 1.0 parts by mass. If the amount of polymerization initiator used is 0.1 parts by mass or more, a sufficient polymerization rate can be obtained, which is therefore preferred. If the amount of polymerization initiator used is 1.5 parts by mass or less, the polymerization rate can be controlled, so the reaction is easy to control and the target molecular weight is easily obtained. Examples of chain transfer agents include n-octylthiol, n-dodecylthiol, tert-dodecylthiol, α-methylstyrene dimer, ethyl mercaptoside, limonene, and isoprene. The amount of chain transfer agent used is not particularly limited as long as it is within the range where the target molecular weight can be obtained, but preferably 0.1 to 0.8 parts by mass relative to 100 parts by mass of all monomer units, more preferably 0.15 to 0.5 parts by mass. If the amount of chain transfer agent used is 0.1 to 0.8 parts by mass, the target molecular weight can be easily obtained.

[0046] There are two methods for introducing maleimide monomer units into maleimide-based resin (A): copolymerization of maleimide monomers and post-imidization. Post-imidization is preferred because it results in a lower amount of residual maleimide monomers in the maleimide-based resin (A). Post-imidization involves copolymerizing a mixture of styrene monomers, unsaturated dicarboxylic anhydride monomers, and other copolymerizable monomers, followed by reacting a portion of the unsaturated dicarboxylic anhydride monomer units with ammonia or a primary amine to imidize them, converting them into maleimide monomer units. Primary amines include, for example, alkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine, and decylamine, and aromatic amines such as chlorinated or bromine-substituted alkylamines, aniline, toluene, and naphthylamine, with aniline being preferred. These primary amines can be used alone or in combination of two or more. During post-imidization, a catalyst can be used to improve the dehydration and ring-closing reaction in the reaction between the primary amine and the unsaturated dicarboxylic anhydride monomer unit. Examples of catalysts include tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, and N,N-diethylaniline. The post-imidization temperature is preferably 100–250°C, more preferably 120–200°C. If the imidization reaction temperature is above 100°C, the reaction rate is increased, which is preferable in terms of productivity. If the imidization reaction temperature is below 250°C, the decrease in physical properties caused by thermal degradation of the maleimide-based resin (A) can be suppressed, which is also preferable.

[0047] Methods for removing solvents or unreacted monomer volatiles used in solution polymerization from the solution after solution polymerization of maleimide resin (A) or the solution after post-imidization (devouring methods) can employ known methods. For example, a vacuum devouring tank with a heater or a devouring extruder with an exhaust port can be used. The devoured molten maleimide resin (A) can be transferred to a granulation process, extruded linearly through a porous die, and processed into granules using cold cutting, air hot cutting, or underwater hot cutting methods.

[0048] The residual amount of maleimide monomer in the maleimide-based resin (A) is preferably 300 ppm or less, more preferably 250 ppm or less. If the residual amount of maleimide monomer is within this range, the maleimide-based resin (A) exhibits excellent color. The residual amount of maleimide monomer can be adjusted by modifying the polymerization or devolatilization conditions, and is a value obtained quantitatively using a reprecipitation method.

[0049] Polyamide resin (B) is a resin with amide bonds in its main chain, such as nylon-6, nylon-6, 6, nylon-4, 6, nylon-6, 7, nylon-6, 10, nylon-11, and nylon-12. Nylon-11 is preferred. Polyamide resin (B) can be used alone or in combination of two or more types.

[0050] The molecular weight of the polyamide resin (B) is not particularly limited. From a flowability point of view, the melt viscosity at 270°C and a shear rate of 100 sec⁻¹ is preferably 50–200 Pa·s, more preferably 75–175 Pa·s, and even more preferably 100–125 Pa·s. The polyamide resin (B) preferably has a terminal amino group content of 2.0–4.0 mg KOH / g, for example, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0 mg KOH / g, or any value within the range of any two values ​​exemplified herein. As described below, the average particle size of the dispersed phase can be easily controlled by appropriately controlling the type and amount of compounding agents, including the terminal amino group content of the polyamide resin (B), and the manufacturing conditions.

[0051] When the ABS resin modifier is set to 100% by mass, the content of maleimide resin (A) in the ABS resin modifier is preferably 10-50% by mass, more preferably 15-40% by mass, for example, 10, 15, 20, 30, 40, 50% by mass, or within any two values ​​exemplified herein. When the ABS resin modifier is set to 100% by mass, the content of polyamide resin (B) in the ABS resin modifier is preferably 50-90% by mass, more preferably 60-80% by mass, for example, 50, 60, 70, 80, 90% by mass, or within any two values ​​exemplified herein. When the ABS resin modifier is set to 100% by mass, the total content of maleimide resin (A) and polyamide resin (B) in the ABS resin modifier can be 90% by mass or more, preferably 95% by mass or more, more preferably 98% by mass or more. ABS resin modifiers can consist of only maleimide-based resin (A) and polyamide resin (B). If the content of maleimide-based resin (A) is too low, its compatibility with resin (C) may decrease; if the content is too high, its fluidity and moldability may decrease when mixed with resin (C).

[0052] An embodiment of the present invention relates to an ABS resin modifier having a dispersed phase. The ABS resin modifier preferably has a maleimide-based resin (A) and a polyamide resin (B) in the form of an island-shaped dispersion structure, wherein the dispersed phase (island) contains the maleimide-based resin (A) and the matrix phase (sea) contains the polyamide resin (B). The dispersed phase (island) is preferably substantially composed of the maleimide-based resin (A), and the matrix phase (sea) is preferably substantially composed of the polyamide resin (B). The average particle size of the dispersed phase is 100 nm or less, preferably 80 nm or less. Alternatively, the average particle size of the dispersed phase can be 10 nm or more. The average particle size of the dispersed phase is, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 nm, or may be within any two values ​​exemplified herein. If the average particle size of the dispersed phase is greater than 100 nm, the impact resistance and chemical resistance of the resin composition may sometimes decrease. The average particle size of the dispersed phase is calculated as follows: the ABS resin modifier is observed using a transmission electron microscope (TEM), and the diameter (circular equivalent diameter) of each dispersed phase is calculated based on its area. The average number of particles with this diameter is then determined.

[0053] The average particle size of the dispersed phase can be easily controlled by adjusting the amount of unsaturated dicarboxylic anhydride monomer units contained in the maleimide resin (A) and the amount of terminal amino groups in the polyamide resin (B). That is, for the ABS resin modifier according to one embodiment of the present invention, it is believed that the more unsaturated dicarboxylic anhydride monomer units contained in the maleimide resin (A) react with each other with the terminal amino groups contained in the polyamide resin (B), the smaller the average particle size of the dispersed phase will be accordingly. Furthermore, it is believed that the reaction rate varies depending on the mobility and viscosity of the maleimide resin (A) and the polyamide resin (B) as polymer chains, as well as the mixing conditions of the maleimide resin (A) and the polyamide resin (B). One embodiment of the present invention discloses an ABS resin modifier that, by adjusting the content of unsaturated dicarboxylic anhydride monomer units in the maleimide-based resin (A), the amount of terminal amino groups in the polyamide resin (B), the polymer properties related to reactivity, and the mixing conditions of the maleimide-based resin (A) and the polyamide resin (B), can control the average particle size of the dispersed phase within a suitable range. Furthermore, because such an ABS resin modifier exhibits high dispersibility, it is presumed that adding it to ABS resins or similar materials can yield resin compositions with excellent chemical resistance and impact resistance.

[0054] In one embodiment of the present invention, the nominal tensile strain at break of the ABS resin modifier is preferably 10% or more, more preferably 30% or more, more preferably 50% or more, and even more preferably 70% or more. There is no particular upper limit, for example, it can be 200%. Here, the nominal tensile strain at break can be measured based on JIS K7161 at a tensile speed of 50 mm / min, and the specimen can be a specimen that has undergone 16 hours of conditioning in a constant temperature bath at 23°C and 50% humidity.

[0055] The Charpy impact strength of the ABS resin modifier involved in one embodiment of the present invention is preferably 4 KJ / m. 2 The above is preferred, with 5KJ / m 2 The above is preferred, with 6KJ / m 2 Further optimized to 7KJ / m 2 There is no specific upper limit; for example, it can be 20 kJ / m³. 2 Here, Charpy impact strength can be measured based on JIS K7111-1 using notched specimens, with the impact direction being edgewise. Specimens that have undergone 16 hours of conditioning in a constant temperature bath at 23°C and 50% humidity can be used. It should be noted that the measuring equipment can be, for example, a digital impact tester manufactured by Toyo Seiki Co., Ltd.

[0056] The method for melt-blending maleimide resin (A) with polyamide resin (B) can be a known method, such as melt blending using an extruder. The extruder can be a known device, such as a twin-screw extruder, a single-screw extruder, a multi-screw extruder, or a continuous mixer with a twin-screw rotor. Meshing co-rotating twin-screw extruders are commonly used and are preferred. Alternatively, multiple combinations of these extruders can be used. There are no particular limitations on the extruder and extrusion temperature, but from the viewpoint of controlling the particle size of the dispersed phase of the ABS resin modifier to below 100 nm, it is preferable to use a twin-screw extruder for melt blending at 260°C to 320°C. Related to other manufacturing conditions, the screw speed can be, for example, 150 to 350 rpm, and the extrusion rate can be 15 to 35 kg / hr.

[0057] One embodiment of the present invention relates to a resin composition comprising the above-mentioned ABS resin modifier and a resin (C) selected from ABS resin, SAN resin, ASA resin, and AES resin. Another embodiment of the present invention relates to a resin composition obtained by melt-blending raw materials comprising the above-mentioned ABS resin modifier and a resin (C) selected from ABS resin, SAN resin, ASA resin, and AES resin.

[0058] ABS resin modifiers improve the impact resistance and chemical resistance of resin (C). Resin (C) preferably contains at least one of ABS resin and SAN resin, more preferably both ABS resin and SAN resin, but may also consist solely of ABS resin and SAN resin. For example, powdered ABS resin obtained by emulsion polymerization and granular SAN resin obtained by continuous bulk polymerization can be used as resin (C). Alternatively, a resin obtained by pre-melting powdered ABS resin obtained by emulsion polymerization and granular SAN resin obtained by continuous bulk polymerization using an extruder or similar method can be used.

[0059] When the total amount of the resin composition is set to 100% by mass, the content of the ABS resin modifier in the resin composition is preferably 5 to 20% by mass, more preferably 10 to 15% by mass, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20% by mass, or it can be within the range of any two values ​​exemplified herein.

[0060] When the total resin composition is set at 100% by mass, the polyamide resin contained in the resin composition according to one embodiment of the present invention is preferably less than 20% by mass, more preferably less than 15% by mass, and even more preferably less than 10% by mass, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% by mass, or within the range of any two values ​​exemplified herein. When using the ABS resin modifier according to one embodiment of the present invention, even if the content of polyamide resin in the resin composition is less than before, a resin composition with sufficient chemical resistance and impact resistance can be obtained, and the reduction in hygroscopic dimensional stability caused by a high content of polyamide resin can be prevented.

[0061] ABS resin, ASA resin, and AES resin are graft copolymers formed by graft copolymerizing a rubber-like polymer with at least styrene-based monomers and acrylonitrile-based monomers. For example, when butadiene-based rubbers such as polybutadiene and styrene-butadiene copolymers are used as the rubber-like polymer, it is ABS resin; when acrylic rubbers such as butyl acrylate or ethyl acrylate are used as the rubber-like polymer, it is ASA resin; and when ethylene-based rubbers such as ethylene-α-olefin copolymers are used as the rubber-like polymer, it is AES resin. Two or more of these rubber-like polymers can be used in combination during graft copolymerization.

[0062] As a method for manufacturing graft copolymers such as ABS resin, known methods can be used. For example, manufacturing methods employing emulsion polymerization or continuous bulk polymerization can be cited. The emulsion polymerization method is preferred because it is easier to adjust the content of the rubbery polymer in the final resin composition.

[0063] One method for manufacturing graft copolymers using emulsion polymerization is to perform emulsion graft copolymerization of a rubber-like polymer latex with styrene-based monomers and acrylonitrile-based monomers (hereinafter referred to as "emulsion graft polymerization"). The latex of the graft copolymer can be obtained using emulsion graft polymerization.

[0064] When using emulsion graft polymerization, water, emulsifiers, polymerization initiators, and chain transfer agents are used, and the polymerization temperature is preferably in the range of 30–90°C. Emulsifiers include, for example, anionic surfactants, cationic surfactants, and amphoteric surfactants. Polymerization initiators include, for example, organic peroxides such as cumene hydroperoxide, dicumene peroxide, tert-butyl peroxyacetate, tert-hexyl peroxybenzoate, and tert-butyl peroxybenzoate; persulfates such as potassium persulfate and ammonium persulfate; azo compounds such as azobisisobutyronitrile; reducing agents such as ferric ions; secondary reducing agents such as sodium formaldehyde sulfoxylate; and chelating agents such as disodium ethylenediaminetetraacetate. Chain transfer agents include, for example, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, α-methylstyrene dimer, ethyl mercaptosulfonate, limonene, and terpinene.

[0065] The latex of the graft copolymer can be coagulated and recycled using known methods. For example, a coagulant is added to the latex of the graft copolymer to cause it to coagulate, and then it is washed and dehydrated using a dehydrator, followed by a drying process to obtain a powdered graft copolymer.

[0066] From the viewpoint of impact resistance, the content of the rubbery polymer in the graft copolymer obtained by emulsion graft polymerization is preferably 40-70% by mass, more preferably 45-65% by mass. The content of the rubbery polymer can be adjusted, for example, by adjusting the ratio of styrene monomers and acrylonitrile monomers to the rubbery polymer during emulsion graft polymerization.

[0067] From the viewpoint of impact resistance or chemical resistance, the content of constituent units other than the rubber-like polymer of the graft copolymer obtained by emulsion graft polymerization is preferably 65-85% by mass of styrene monomer units and 15-35% by mass of acrylonitrile monomer units.

[0068] The gel component of the graft copolymer is preferably in particulate form. The gel component is a rubbery polymer particle formed by the graft copolymerization of styrene-based monomers and acrylonitrile-based monomers. It is insoluble in organic solvents such as methyl ethyl ketone (MEK) and toluene, and can be separated by centrifugation. Sometimes, it can form an inclusion structure where styrene-acrylonitrile copolymer is encapsulated within the rubbery polymer particles. If the graft copolymer and styrene-acrylonitrile copolymer are melt-blended, the gel component exists as a dispersed phase in the continuous phase of the styrene-acrylonitrile copolymer in particulate form. The gel component value is obtained as follows: A mass W of the graft copolymer is dissolved in methyl ethyl ketone (MEK), and the insoluble component is centrifuged at 20,000 rpm to allow sedimentation. The supernatant is removed by decantation to obtain the insoluble component. After vacuum drying, the dried insoluble component is obtained. The mass S of this insoluble component is calculated using the formula: gel component (mass%) = (S / W) × 100. Alternatively, the gel composition can be calculated by dissolving the polymer blend obtained by melt blending the graft copolymer with the styrene-acrylonitrile copolymer in methyl ethyl ketone and centrifuging.

[0069] From the viewpoint of impact resistance and appearance of the molded product, the number-average particle size of the gel component of the graft copolymer is preferably in the range of 0.10 to 1.0 μm, more preferably 0.15 to 0.50 μm. The number-average particle size is calculated as follows: particles of a polymer blend are obtained by melt blending the graft copolymer with a styrene-acrylonitrile copolymer; ultrathin sections are cut from these particles; and the particles are observed using a transmission electron microscope (TEM). The calculation is based on the image analysis of the particles dispersed in the continuous phase. The number-average particle size can be adjusted, for example, by adjusting the latex particle size of the rubber-like polymer used in emulsion graft polymerization. The latex particle size of the rubber-like polymer can be adjusted by adjusting the method of adding the emulsifier or the amount of water used during emulsion polymerization. However, to obtain the preferred range, the polymerization time needs to be extended, which reduces productivity. Therefore, the following method can be used: the rubber-like polymer with a particle size of about 0.1 μm is polymerized for a short time, and then the rubber particles are enlarged using chemical or physical agglomeration methods.

[0070] From the viewpoint of impact resistance, the grafting rate of the graft copolymer is preferably 10-100% by mass, more preferably 20-70% by mass. The grafting rate is a value calculated by the content of gel component (G) and rubber-like polymer (RC) using the formula: grafting rate (mass%) = [(G-RC) / RC] × 100. The grafting rate represents the amount of styrene-acrylonitrile copolymer bonded by grafting and the amount of styrene-acrylonitrile copolymer encapsulated within the particles per unit mass of rubber-like polymer particles. The grafting rate can be adjusted, for example, by adjusting the ratio of monomer to rubber-like polymer, the type and amount of initiator, the chain transfer dosage, the emulsifying dosage, the polymerization temperature, the feeding method (one-time / multiple / continuous), and the monomer addition rate during emulsion graft polymerization.

[0071] From the viewpoint of impact resistance and the appearance of the molded product, the toluene swelling ratio of the graft copolymer is preferably 5 to 20 times. Toluene swelling ratio indicates the degree of crosslinking of the rubber-like polymer particles and is calculated as follows: the graft copolymer is dissolved in toluene, the insoluble components are separated by centrifugation or filtration, and the mass of the state after swelling with toluene is calculated as the ratio of the mass of the dried state after vacuum drying to remove toluene. The toluene swelling ratio is affected, for example, by the degree of crosslinking of the rubber-like polymer used in emulsion graft polymerization, and can be adjusted by adding initiators, emulsifiers, adjusting the polymerization temperature, and adding multifunctional monomers such as divinylbenzene during the emulsion polymerization of the rubber-like polymer.

[0072] SAN resin is a copolymer containing styrene monomer units and acrylonitrile monomer units, such as styrene-acrylonitrile copolymers.

[0073] Other copolymerizable monomers for SAN resins include (meth)acrylate monomers such as methyl methacrylate, acrylate monomers such as butyl acrylate and ethyl acrylate, (meth)acrylate monomers such as methacrylic acid, acrylic acid monomers such as acrylic acid, and N-substituted maleimide monomers such as N-phenylmaleimide.

[0074] The constituent units of the SAN resin are preferably 60-90% by mass of styrene monomer units and 10-40% by mass of vinyl cyanide monomer units, more preferably 65-80% by mass of styrene monomer units and 20-35% by mass of vinyl cyanide monomer units. If the constituent units are within the above range, the resulting resin composition exhibits an excellent balance between impact strength and flowability. The contents of styrene monomer units and vinyl cyanide monomer units are values ​​measured using 13C-NMR.

[0075] Known methods can be used to manufacture SAN resin. For example, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be employed. As for the operation of the reaction apparatus, continuous, batch, and semi-batch methods are all applicable. Considering both quality and productivity, bulk polymerization or solution polymerization is preferred, with continuous polymerization being the most preferred. Solvents used in bulk polymerization or solution polymerization include, for example, alkylbenzenes such as benzene, toluene, ethylbenzene, and xylene; ketones such as acetone and methyl ethyl ketone; and aliphatic hydrocarbons such as hexane and cyclohexane.

[0076] In the bulk or solution polymerization of SAN resin, polymerization initiators and chain transfer agents can be used, and the polymerization temperature is preferably in the range of 120–170°C. Examples of polymerization initiators include peroxyacetals such as 1,1-di(tert-butylperoxide)cyclohexane, 2,2-di(tert-butylperoxide)butane, 2,2-di(4,4-di-tert-butylperoxidecyclohexyl)propane, and 1,1-di(tert-pentylperoxide)cyclohexane; hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide; alkyl peroxides such as tert-butyl acetate peroxide and tert-pentyl benzoate peroxide; and tert-butyl peroxide, di-tert-butyl peroxide, di-tert-butyl peroxide, and di-tert-hexyl peroxide. Alkyl peroxides, peroxide esters such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, and tert-butyl peroxyisopropyl monocarbonate; peroxy carbonates such as tert-butyl peroxyisopropyl carbonate and polyether tetra(tert-butyl peroxycarbonate); N,N'-azobis(cyclohexane-1-onitrile), N,N'-azobis(2-methylbutyronitrile), N,N'-azobis(2,4-dimethylpentanonitrile), and N,N'-azobis[2-(hydroxymethyl)propionitrile], etc., may be used, either one or a combination of two or more. Chain transfer agents include, for example, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, α-methylstyrene dimer, ethyl mercaptoside, limonene, and terpinene.

[0077] Deviation methods for removing unreacted monomers or volatile components such as solvents used in solution polymerization from the solution after SAN resin polymerization can be employed using known methods. For example, a vacuum devolatilization tank with a preheater or a devolatilization extruder with an exhaust port can be used. The devolatilized molten SAN resin can then be transferred to a granulation process, where it is extruded in a rope-like manner through a porous die and processed into granules using cold cutting, air hot cutting, or underwater hot cutting methods.

[0078] From the viewpoint of impact resistance and moldability of the resin composition, the weight-average molecular weight of the SAN resin is preferably 50,000 to 250,000, more preferably 70,000 to 200,000. The weight-average molecular weight of the SAN resin is a polystyrene equivalent value determined by gel permeation chromatography (GPC) in THF solvent, and is obtained using the same method as for maleimide-based resins (A). The weight-average molecular weight can be adjusted by modifying the type and amount of chain transfer agent, solvent concentration, polymerization temperature, and the type and amount of polymerization initiator during polymerization.

[0079] As one embodiment of the present invention, a method for manufacturing a resin composition includes a step of melt-blending a raw material containing the above-mentioned ABS resin modifier and a resin (C) selected from ABS resin, SAN resin, ASA resin, and AES resin.

[0080] The method for melt-blending ABS resin modifier and at least one resin (C) selected from ABS resin, SAN resin, ASA resin, and AES resin can be a known method, such as melt blending using an extruder. Known extruders can be used, such as twin-screw extruders, single-screw extruders, multi-screw extruders, and continuous mixers with twin-screw rotors. Meshing co-rotating twin-screw extruders are commonly used and are preferred. Alternatively, multiple combinations of these extruders can be used. There are no particular limitations on the extruder and extrusion temperature, but from the viewpoint of efficiently dispersing the resin composition, melt blending at 260°C or higher using a twin-screw extruder is preferred. Related to other manufacturing conditions, the screw speed can be, for example, 150–350 rpm, and the extrusion rate can be 15–35 kg / hr.

[0081] As needed, heat stabilizers such as hindered phenolic compounds, lactone compounds, phosphorus compounds, and sulfur compounds; light stabilizers such as hindered amine compounds and benzotriazole compounds; lubricants, plasticizers, colorants, impact modifiers, hardness modifiers, antistatic agents, flame retardants, and mineral oils can be added to the resin composition. These additives can be used alone or in combination of two or more. These additives can be added during the manufacture of maleimide resins (A), polyamide resins (B), or resins (C), or during the melt mixing of ABS resin modifiers or resin compositions. When the total resin composition is set at 100% by mass, these additives can be, for example, less than 5% by mass, such as 3% by mass or 1% by mass. Alternatively, the resin composition may not contain these additives.

[0082] In one embodiment of the present invention, the melt flow rate of the resin composition is preferably 5 to 15 g / 10 min, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 g / 10 min, or within any two values ​​exemplified herein. Here, the melt flow rate can be measured based on JIS K7210 at 240°C and a load of 98 N.

[0083] In one embodiment of the present invention, the Vicat softening temperature of the resin composition is preferably 100–105°C, for example, 100, 101, 102, 103, 104, or 105°C, or may be within the range of any two values ​​exemplified herein. Here, the Vicat softening temperature can be determined based on JIS K7206 using the 50 method (load 50 N, heating rate 50°C / hour), using a 10 mm × 10 mm specimen with a thickness of 4 mm that has undergone 16 hours of conditioning in a constant temperature bath at 23°C and 50% humidity.

[0084] The Charpy impact strength of the resin composition according to one embodiment of the present invention is preferably 12 KJ / m. 2 That's all. There's no specific upper limit; for example, it could be 30 KJ / m³. 2 The Charpy impact strength of the resin composition can be, for example, 12, 15, 20, 25, or 30 KJ / m. 2 It can also be within the range of any two values ​​exemplified here. Here, Charpy impact strength can be based on JIS K7111-1, using notched specimens that have undergone 16 hours of conditioning in a constant temperature bath at 23°C and 50% humidity, and measured with the edgewise direction of impact.

[0085] In one embodiment of the present invention, the critical strain of the resin composition is preferably 0.9% or more. Here, the critical strain can be determined using the method described in the examples.

[0086] The molded article according to one embodiment of the present invention can be obtained by molding the above-described resin composition.

[0087] The resin composition can be molded into molded articles using known molding methods such as injection molding, sheet extrusion molding, vacuum forming, blow molding, foam molding, and profile extrusion molding. During molding, the thermoplastic resin composition is typically heated to 200–300°C, preferably to 220–280°C. The molded articles can be applied in the automotive, home appliance, OA equipment, residential building materials, and daily necessities industries.

[0088]

Example

[0089] The following examples are used for detailed description, but the present invention is not limited to the following examples.

[0090] <Example of manufacturing maleimide-based resin (A-1)>

[0091] 65 parts by mass of styrene, 7 parts by mass of maleic anhydride, 0.1 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 25 parts by mass of methyl ethyl ketone were added to a 25-liter high-pressure reactor equipped with a stirrer. After purging the system with nitrogen, the temperature was raised to 92°C, and a solution obtained by dissolving 28 parts by mass of maleic anhydride and 0.18 parts by mass of tert-butyl peroxide in 100 parts by mass of methyl ethyl ketone was continuously added over 7 hours. Following this, 0.03 parts by mass of tert-butyl peroxide was added, the temperature was raised to 120°C, and the reaction was continued for 1 hour to obtain a styrene-maleic anhydride copolymer. Next, 31 parts by mass of aniline and 0.6 parts by mass of triethylamine were added to the polymer solution, and the reaction was carried out at 140°C for 7 hours. The polymer solution after the imidization reaction was fed into a vented screw extruder to remove volatile components, yielding granular maleimide resin (A-1). The residual amount of maleimide monomers in the maleimide-based resin (A-1) was 220 ppm. The contents of each constituent unit, as determined by NMR, were 52% by mass of styrene unit, 46% by mass of N-phenylmaleimide unit, and 2% by mass of maleic anhydride unit. The weight-average molecular weight (Mw) was 150,000, and the glass transition midpoint temperature (Tmg) was 203 °C.

[0092] <Example of manufacturing maleimide-based resin (A-2)>

[0093] 42 parts by mass of styrene, 10 parts by mass of acrylonitrile, 4 parts by mass of maleic anhydride, 0.03 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 27 parts by mass of methyl ethyl ketone (MEK) were added to a 25-liter high-pressure reactor equipped with a stirrer. After purging the system with nitrogen, the temperature was raised to 92°C, and over 4.5 hours, a solution of 21 parts by mass of maleic anhydride and 0.15 parts by mass of tert-butyl peroxide dissolved in 85 parts by mass of MEK, along with 20 parts by mass of styrene, was continuously added. Following the addition of maleic anhydride, over 30 minutes, a solution of 0.02 parts by mass of tert-butyl peroxide dissolved in 9 parts by mass of MEK, along with 3 parts by mass of styrene, was continuously added. After the addition, the temperature was raised to 120°C, and the polymerization was stopped after 30 minutes. Subsequently, 23 parts by mass of aniline and 0.4 parts by mass of triethylamine were added to the polymerization solution, and the reaction was carried out at 140°C for 7 hours. The polymer solution after imidization was fed into a vented screw extruder to remove volatile components, yielding granular maleimide resin (A-2). NMR analysis revealed that A-2 contained 52% by mass of styrene, 8% by mass of acrylonitrile, 39% by mass of N-phenylmaleimide, and 1% by mass of maleic anhydride; its weight-average molecular weight (Mw) was 140,000; and its glass transition temperature (Tmg) was 176°C.

[0094] <Example of manufacturing maleimide-based resin (A-3)>

[0095] 65 parts by mass of styrene, 7 parts by mass of maleic anhydride, 0.2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 25 parts by mass of methyl ethyl ketone were added to a 25-liter high-pressure reactor equipped with a stirrer. After purging the system with nitrogen, the temperature was raised to 92°C, and a solution prepared by dissolving 28 parts by mass of maleic anhydride and 0.18 parts by mass of tert-butyl peroxide in 100 parts by mass of methyl ethyl ketone was continuously added over 7 hours. Then, 0.03 parts by mass of tert-butyl peroxide was added, the temperature was raised to 120°C, and the reaction was continued for 1 hour to obtain a styrene-maleic anhydride copolymer. Next, 21 parts by mass of aniline and 0.6 parts by mass of triethylamine were added to the polymer solution, and the reaction was carried out at 140°C for 7 hours. The polymer solution after the imidization reaction was fed to a vented screw extruder to remove volatile components, yielding granular maleimide resin (A-3). The residual amount of maleimide monomers in the maleimide-based resin (A-3) was 200 ppm. The contents of each constituent unit, as determined by NMR, were 52% by mass of styrene unit, 42% by mass of N-phenylmaleimide unit, and 6% by mass of maleic anhydride unit. The weight-average molecular weight (Mw) was 120,000, and the glass transition midpoint temperature (Tmg) was 203 °C.

[0096] <Polyamide resin (B-1)>

[0097] The following materials are used as the polyamide resin (B-1).

[0098] Rilsan KNO manufactured by ARKEMA Co., Ltd. (terminal amino group content: 3.2 mg KOH / g)

[0099] <Polyamide resin (B-2)>

[0100] The following materials are used as the polyamide resin (B-2).

[0101] Rilsan BESVO A MED manufactured by ARKEMA Co., Ltd. (terminal amino group content: 2.5 mg KOH / g)

[0102] <Polyamide resin (B-3)>

[0103] The following materials are used as the polyamide resin (B-3).

[0104] Rilsan BMNO MED manufactured by ARKEMA Co., Ltd. (terminal amino group content: 3.4 mg KOH / g)

[0105] <Polyamide resin (B-4)>

[0106] The following materials are used as the polyamide resin (B-4).

[0107] CM1017 manufactured by TORAY Co., Ltd. (terminal amino group content: 3.4 mg KOH / g)

[0108] <Polyamide resin (B-5)>

[0109] The following materials are used as the polyamide resin (B-5).

[0110] CM1007 manufactured by TORAY Co., Ltd. (terminal amino group content: 3.4 mg KOH / g)

[0111] <Polyamide resin (B-6)>

[0112] The following materials are used as the polyamide resin (B-6).

[0113] UBE Industries, Ltd. 1022B (terminal amino group content: 2.7 mg KOH / g)

[0114] <Manufacturing example of the ABS resin (C-1)>

[0115] The ABS resin (C-1) is prepared by emulsion graft polymerization. 143 parts by mass of polybutadiene latex with an average particle size of 0.3 μm, 0.2 parts by mass of sodium formaldehyde sulfoxylate, 0.01 parts by mass of tetrasodium ethylenediaminetetraacetate, 0.005 parts by mass of ferrous sulfate, and 150 parts by mass of pure water are charged into a reaction kettle equipped with a stirrer, and the temperature is heated to 50 °C. 50 parts by mass of a monomer mixture of 75% by mass of styrene and 25% by mass of acrylonitrile, 1.0 parts by mass of tert-dodecyl mercaptan, and 0.15 parts by mass of cumene hydroperoxide are added thereto in batches and continuously over 4 hours. After the addition in batches is completed, the temperature is raised to 70 °C, and the polymerization is terminated after another 2 hours to obtain an ABS resin (C-1) latex. Magnesium sulfate and sulfuric acid are used as coagulants, and the obtained latex is coagulated so that the pH of the slurry during coagulation becomes 6.8. After washing, dehydration, and drying, powdery ABS resin (C-1) is obtained. According to the raw material mixing ratio during emulsion graft polymerization, the content of polybutadiene in the obtained ABS resin (C-1) is 53% by mass. The structural units other than the rubbery polymer are measured by NMR, with styrene being 75% by mass and acrylonitrile being 25% by mass. The gel component is measured by the centrifugation method and is 72% by mass. The grafting rate is calculated to be 44% based on the gel component and the content of polybutadiene. The toluene swelling ratio is 8.1, and the number average particle size is calculated to be 0.3 μm based on the observation results of TEM.

[0116] <Production Example of SAN Resin (C-2)>

[0117] The SAN resin (C-2) is prepared by continuous bulk polymerization. One completely mixed tank-type stirring tank is used as a reactor, and the polymerization is carried out with a capacity of 20 L. A raw material solution of 60% by mass of styrene, 22% by mass of acrylonitrile, and 18% by mass of ethylbenzene is prepared and continuously supplied to the reactor at a flow rate of 6.5 L / h. In addition, with respect to the raw material solution, the concentration of tert-butyl peroxyisopropyl monocarbonate as a polymerization initiator is made to be 160 ppm, and the concentration of n-dodecyl mercaptan as a chain transfer agent is made to be 400 ppm, and the two are continuously added to the supply line of the raw material solution. The reaction temperature of the reactor is adjusted to 145 °C. The polymer solution continuously taken out from the reactor is continuously supplied to a vacuum devolatilization tank equipped with a preheater to separate unreacted styrene, acrylonitrile, and ethylbenzene. The temperature of the preheater is adjusted so that the temperature of the polymer in the devolatilization tank becomes 225 °C, and the pressure in the devolatilization tank is 0.4 kPa. The polymer is pumped out from the vacuum devolatilization tank using a gear pump, extruded in a line, cooled with cooling water, and cut to obtain granular SAN resin (C-2). The structural units are 74% by mass of styrene units and 26% by mass of acrylonitrile units. In addition, the weight average molecular weight is 145,000.

[0118] <Examples and Comparative Examples>

[0119] Maleimide resin (A) and polyamide resin (B) were mixed according to the mixing ratios shown in Table 1, and melt-blended using a Toshiba Machine TEM-35B twin-screw extruder at 270°C, 250 rpm, and 25 kg / hr. The resulting filament was cut using a pelletizer to obtain granular ABS resin modifier of approximately 2 mm. The particle size, nominal strain at tensile break, flexural modulus, and Charpy impact strength of the dispersed phase of the obtained ABS resin modifier were evaluated using the methods described below. The evaluation results are shown in Table 1. Additionally, the obtained ABS resin modifier was mixed with ABS resin and SAN resin according to the mixing ratios shown in Table 2, and melt-blended using a SHIBAURA MACHINE CO., LTD. TEM-35B twin-screw extruder at 270°C, 250 rpm, and 25 kg / hr. The resulting filament was cut using a pelletizer to obtain granular resin composition of approximately 2 mm. The melt flow rate, Vicat softening temperature, flexural modulus, Charpy impact strength, and chemical resistance of the obtained resin compositions were evaluated using the methods described below. The evaluation results are shown in Table 2.

[0120] <Reference Example>

[0121] As a reference example 1, without adding an ABS resin modifier containing maleimide-based resin (A) and polyamide resin (B), ABS resin and SAN resin were mixed according to the mixing ratio shown in Table 2, and melt-blended using a Toshiba Machine TEM-35B twin-screw extruder at 270°C, 250 rpm, and 25 kg / hr. The resulting filament was cut using a pelletizer to obtain a resin composition in granular form of approximately 2 mm.

[0122] As a reference example 2, without using an ABS resin modifier, maleimide resin (A), polyamide resin (B), ABS resin, and SAN resin were mixed according to the proportions shown in Table 2, and melt-blended using a Toshiba Machine TEM-35B twin-screw extruder at 270°C, 250 rpm, and 25 kg / hr. The resulting filament was then cut using a pelletizer to obtain granular resin compositions of approximately 2 mm.

[0123] (Average particle size of the dispersed phase)

[0124] The cross-section of the ABS resin modifier was observed using a Hitachi High-Tech H-7500 transmission electron microscope, and the obtained images were analyzed using Image-Pro Plus 6.3 image analysis software from Hakuto Corporation. The area of ​​each dispersed phase (5.7 μm x 8.5 μm) was observed at 6000x magnification, and the area of ​​each dispersed phase was measured. The circumscaping diameter was taken as the circumscaping diameter of each dispersed phase, and the average number of circumscaping diameters of each dispersed phase was taken as the average particle size of the dispersed phase.

[0125] (Nominal strain at tensile fracture)

[0126] The nominal strain at tensile fracture was measured according to JIS K7161 at a tensile speed of 50 mm / min. The specimens used were conditioned for 16 hours in a constant temperature bath at 23°C and 50% humidity.

[0127] (Flexural modulus)

[0128] The flexural modulus was determined based on JIS K7171 at a bending speed of 2 mm / min. Specimens were used after 16 hours of conditioning in a constant temperature bath at 23°C and 50% humidity.

[0129] (Mel flow rate)

[0130] Melt flow rate was measured at 240°C and 98N load based on JIS K7210.

[0131] (Vicat softening temperature)

[0132] The Vicat softening temperature was determined based on JIS K7206 using the 50 method (load 50 N, heating rate 50 °C / hour) with a 10 mm × 10 mm specimen and a thickness of 4 mm. The specimens used were those that had undergone 16 hours of conditioning in a constant temperature bath at 23 °C and 50% humidity. It should be noted that the testing equipment used was the HDT & VSPT testing apparatus manufactured by Toyo Seiki Co., Ltd.

[0133] (Charpy impact strength)

[0134] Charpy impact strength is measured based on JIS K7111-1, using notched specimens, with the impact direction measured edgewise. Specimens were used after 16 hours of conditioning in a constant temperature bath at 23°C and 50% humidity. It should be noted that the measuring equipment used is a digital impact tester manufactured by Toyo Seiki Co., Ltd.

[0135] (Chemical resistance)

[0136] For specimens with a shape of 316×20×2mm, a major radius of 250mm, and a minor radius of 150mm, the 1 / 4 ellipse method was used to observe cracking after 23℃ and 48 hours. The critical strain was calculated and evaluated according to the following formula. To eliminate the influence of molding strain, the granules were pressurized at 260℃ and then cut to manufacture the specimens. Magiclean, manufactured by Kao Corporation, was used as the chemical.

[0137] ε=b / 2a 2 {1-(a 2 -b 2 )X 2 / a 4} 1.5 ×t×100

[0138] (In the formula, ε represents the critical strain, a represents the major radius of the specimen, b represents the minor radius of the specimen, t represents the specimen thickness, and X represents the length from the minor radius end of the specimen to the crack initiation point.)

[0139] It should be noted that the smaller the critical strain value, the more likely the specimen will crack even with slight stress. In this invention, values ​​of 0.9 or higher are considered acceptable.

[0140] Table 1

[0141]

[0142] Table 2

[0143]

[0144] By using the ABS resin modifier of the examples, a resin composition with suitable melt flow rate and Vicat softening temperature, while exhibiting excellent impact strength, chemical resistance, and rigidity, can be obtained. On the other hand, in the resin compositions using the ABS resin modifier of the comparative examples and in the reference examples without the addition of ABS resin modifier, one or more of the physical properties, such as impact strength and chemical resistance, are unsatisfactory.

[0145] Industrial availability

[0146] The resin composition using the ABS resin modifier of the present invention has an excellent balance of heat resistance, mechanical strength, chemical resistance and moldability, and is therefore suitable for parts with complex shapes, especially automotive interior materials.

Claims

1. An ABS resin modifier comprising a maleimide-based resin (A) and a polyamide resin (B), When the ABS resin modifier is set to 100% by mass... The content of maleimide-based resin (A) in ABS resin modifiers is 10-50% by mass. The polyamide resin (B) content in the ABS resin modifier is 50-90% by mass. The total content of maleimide resin (A) and polyamide resin (B) in the ABS resin modifier is 95% by mass or more. The maleimide-based resin (A) comprises maleimide monomer units, styrene monomer units, and unsaturated dicarboxylic acid anhydride monomer units. When the maleimide resin (A) is set to 100% by mass, The maleimide resin (A) contains 40-70% by mass of the styrene monomer units. The amount of the unsaturated dicarboxylic acid anhydride monomer units contained in the maleimide resin (A) is 1-10% by mass. The amount of maleimide monomer units contained in the maleimide-based resin (A) is 10% to 58% by mass. The ABS resin modifier has a dispersed phase. The dispersed phase comprises the maleimide-based resin (A). The average particle size of the dispersed phase is less than 100 nm.

2. The ABS resin modifier as described in claim 1, wherein, The nominal tensile strain at fracture was measured to be above 10% after the specimen was conditioned for 16 hours in a constant temperature bath at 23℃ and 50% humidity according to JIS K7161 and then subjected to a tensile speed of 50 mm / min.

3. A resin composition comprising the ABS resin modifier and resin (C) as described in claim 1 or 2. The resin (C) is selected from at least one resin selected from ABS resin, SAN resin, ASA resin, and AES resin.

4. The resin composition of claim 3, wherein, When the total amount of the resin composition is set to 100% by mass, the polyamide resin (B) contained in the resin composition is less than 20% by mass.

5. The resin composition according to claim 3 or 4, wherein, Based on JIS K7111-1, using notched specimens that underwent 16 hours of conditioning in a constant temperature bath at 23℃ and 50% humidity, the Charpy impact strength, measured along the edge as the impact direction, was 12 KJ / m. 2 above.

6. A method for manufacturing a resin composition, comprising a step of melt-blending raw materials using an extruder. The raw material contains the ABS resin modifier and resin (C) as described in claim 1 or 2, wherein the resin (C) is selected from at least one of ABS resin, SAN resin, ASA resin, and AES resin.

7. A molded article obtained by molding the resin composition according to any one of claims 3 to 5.

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