Resin composition, molding material, resin molded body, and additive for polyester-based elastomer

Abstract

Provided are: a resin composition, a molding material, and a resin molded body having exceptional flexibility, oil resistance, and tensile elongation; and an additive for a polyester-based elastomer. This resin composition contains a polyester-based elastomer (A), and a (meth)acrylic copolymer (B) that is a block copolymer and / or a graft copolymer. This molding material uses the resin composition. This resin molded body is obtained by molding the molding material. The acrylic copolymer (B) is preferably a block copolymer and / or a graft copolymer containing, in the same molecule, a polymer (B1) that contains 60 mass% or more of units derived from methyl methacrylate and a polymer (B2) that has a glass transition temperature of 0°C or lower.

Description

Resin composition, molding material, resin molded body, and additive for polyester elastomer

[0001] The present invention relates to a resin composition, a molding material using the resin composition, a resin molded article obtained by molding the molding material, and an additive for polyester elastomers.

[0002] Thermoplastic polyester elastomers (hereinafter referred to as "polyester elastomers") are polyester block copolymers that have crystalline aromatic polyester units such as polybutylene phthalate units as hard segments and aliphatic polyether units such as poly(alkylene oxide) glycol and / or aliphatic polyester units such as polylactone as soft segments. They have excellent mechanical properties such as mechanical strength, impact resistance, elastic recovery, and flexibility, as well as low-temperature and high-temperature properties. Furthermore, they are thermoplastic and easy to mold. Therefore, they are widely used in a wide range of applications, including tubes, hoses, automobile parts, constant velocity joint boots (CVJ), boot parts, grip parts, button and switch parts, door lock parts, shift Applications are expanding to include levers, fuel cap tethers, air ducts, bellows, emblems, grommets, gaskets, trim, edges, anti-vibration rubber, electrical and electronic components, electrical and electronic component seals, machine parts, hinge parts, waterproof packing, insulating covers, grips, cushioning parts, sound-absorbing gears, cables, wire coatings, curled cords, hydraulic hoses, spiral tubes, printer tractor belts, conveyor belts, ski and snowboard boot components, fibers, films, non-woven fabrics, nail polish cases, hot curlers, hair dryer brushes, hair brushes, zipper pulls, toothbrushes, bobbin cases, diaphragms, mandrels, 3D printer filaments, and stationery.

[0003] On the other hand, although polyester-based elastomers have excellent mechanical strength and impact resistance and a certain degree of flexibility, their applications have sometimes been limited due to their high elastic modulus and relatively hardness compared to other thermoplastic elastomers. Various methods have been proposed for imparting flexibility to polyester-based elastomers. For example, as disclosed in Patent Document 1, a composition has been proposed in which a polyester-based elastomer is blended with a hydrogenated derivative of a styrene-butadiene block copolymer (styrene-ethylene-butylene-styrene block copolymer: SEBS). Furthermore, as disclosed in Patent Document 2, a composition has been proposed in which a polyester-based elastomer is blended with a core-shell acrylic copolymer.

[0004] JP-A-1-193352 JP-A-55-36249

[0005] However, the composition described in Patent Document 1 has low oil resistance because the styrene-ethylene-butylene-styrene block copolymer (SEBS) easily absorbs oil, which can cause problems when applied to components that come into contact with machine oil, gear oil, sebum, hand cream, sunscreen cream, etc. On the other hand, the composition described in Patent Document 2 has better oil resistance than those blended with SEBS, but has problems such as reduced tensile elongation and impaired moldability.

[0006] An object of the present invention is to solve these problems, that is, to provide a resin composition, a molding material, a resin molded product, and an additive for a polyester-based elastomer, which are excellent in flexibility, oil resistance, and tensile elongation.

[0007] As a result of extensive investigations aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by blending a specific (meth)acrylic copolymer with a polyester elastomer.

[0008] [1] A resin composition comprising a polyester elastomer (A) and a (meth)acrylic copolymer (B) which is a block copolymer and / or a graft copolymer.

[0009] [2] The resin composition according to [1], wherein the acrylic copolymer (B) is a block copolymer and / or a graft copolymer containing, in the same molecule, a polymer (B1) containing 60% by mass or more of units derived from methyl methacrylate and a polymer (B2) having a glass transition temperature of 0°C or less.

[0010] [3] The resin composition according to [1] or [2], wherein the (meth)acrylic copolymer (B) contains sulfur.

[0011] [4] The resin composition according to any one of [1] to [3], wherein the (meth)acrylic copolymer (B) has a mass average molecular weight of 200,000 or more.

[0012] [5] The resin composition according to any one of [1] to [4], wherein the (meth)acrylic copolymer (B) contains a graft copolymer.

[0013] [6] The resin composition according to any one of [2] to [5], wherein the polymer (B1) contains 0.1 mass % or more of a repeating unit derived from an acrylate.

[0014] [7] The resin composition according to any one of [2] to [6], wherein the polymer (B2) contains 50 mass% or more of repeating units derived from an acrylate.

[0015] [8] The resin composition according to any one of [2] to [7], wherein the polymer (B2) contains 1 mass % or more of repeating units derived from an aromatic vinyl.

[0016] [9] The resin composition according to any one of [2] to [8], wherein the content of the polymer (B2) in 100% by mass of the acrylic copolymer (B) is 25% by mass or more and 90% by mass or less.

[0017]

[10] The resin composition according to any one of [1] to [9], wherein the (meth)acrylic copolymer (B) contains a repeating unit derived from a macromonomer (b1) represented by the following general formula (1):

[0018]

[0019] (In formula (1), R ０ ~R ｎare each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. １ ~X ｎ are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0020]

[11] The resin composition according to any one of [1] to

[10] , wherein the content of the (meth)acrylic copolymer (B) is 10% by mass or more and 90% by mass or less.

[0021]

[12] The resin composition according to

[10] , wherein the polyester elastomer (A) contains a hard segment (A1) and a soft segment (A2), and the hard segment (A1) contains polybutylene terephthalate.

[0022]

[13] The resin composition according to

[12] , wherein the soft segment (A2) comprises an aliphatic polyether, and the aliphatic polyether comprises at least one selected from the group consisting of polytetramethylene ether glycol, polypropylene oxide, polyethylene oxide, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and tetrahydrofuran, a copolymer of propylene oxide and tetrahydrofuran, and a copolymer of ethylene oxide, propylene oxide and tetrahydrofuran.

[0023]

[14] The resin composition according to any one of [1] to

[13] , further comprising a core-shell polymer (C) different from the (meth)acrylic polymer (B).

[0024]

[15] The resin composition according to

[14] , wherein the core-shell polymer (C) is a particulate polymer including a core portion and a shell portion made of rubber, and the rubber is a silicone-acrylic composite rubber.

[0025]

[16] An additive for polyester elastomers, comprising a (meth)acrylic copolymer (B) which is a block copolymer and / or a graft copolymer.

[0026]

[17] A molding material using the resin composition according to any one of [1] to

[15] .

[0027]

[18] A resin molded product obtained by molding the molding material according to

[17] .

[0028] The resin composition, molding material, resin molded product, and additive for polyester elastomers of the present invention, which contain a polyester elastomer and a specific (meth)acrylic copolymer as constituent components, are excellent in flexibility, oil resistance, and tensile elongation. For this reason, the resin composition, molding material, resin molded product, and polyester elastomer additive of the present invention are useful in a wide range of applications, such as tubes, hoses, automobile parts, constant velocity joint boots (CVJ), boot parts, grip parts, button and switch parts, door lock parts, shift levers, fuel cap tethers, air ducts, bellows, emblems, grommets, gaskets, trim, edges, vibration-proof rubber, electrical and electronic parts, electrical and electronic part seals, machine parts, hinge parts, waterproof packing, insulating covers, grips, cushion parts, silencer gears, cables, wire coatings, curled cords, hydraulic hoses, spiral tubes, printer tractor belts, conveyor belts, ski and snowboard boot components, fibers, films, nonwoven fabrics, nail polish cases, hot curlers, hair dryer brushes, hair brushes, zipper pulls, toothbrushes, bobbin cases, diaphragms, mandrels, 3D printer filaments, and stationery. Furthermore, it is now possible to replace components that have conventionally used vulcanized rubber with the resin composition of the present invention, which is a thermoplastic resin, thereby eliminating the need for a complicated vulcanization process, etc., and reducing the number of processes, thereby improving productivity and reducing product costs. Furthermore, unlike vulcanized rubber, which cannot be recycled, the use of the resin composition of the present invention makes recycling possible.

[0029] Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited to the following description and can be carried out in various modified forms within the scope of the gist thereof. In the present invention, "(meth)acrylic" means one or both of "acrylic" and "methacrylic". Furthermore, "(meth)acrylate" means one or both of "methacrylate" and "acrylate". The same applies to "(meth)acryloyl".

[0030] In the present invention, the term "monomer" refers to an unpolymerized compound (a monomer component before polymerization), and the terms "repeating unit" and "structural unit" refer to structural units constituting a polymer derived from a monomer formed by polymerization of the monomer. Furthermore, structural units constituting a polymer are referred to as "units derived from ~ monomer" or "~ monomer units." A "repeating unit" or "structural unit" may be a unit formed directly by a polymerization reaction, or may be a unit in which a portion of the unit is converted into a different structure by processing the polymer. In the present invention, a macromonomer refers to a polymer having a functional group capable of undergoing a polymerization reaction. A macromonomer is also known as a macromer. In the present invention, "mass %" indicates the content of a specific component contained in a total amount of 100% by mass. In the present invention, unless otherwise specified, a numerical range expressed using "~" in this specification means a range including the numerical values ​​before and after "~" as the lower and upper limits, and "A to B" means greater than or equal to A and less than or equal to B.

[0031] [Resin Composition] The resin composition of the present invention contains, as essential components, a polyester elastomer (A) and a (meth)acrylic copolymer (B), which will be described later. The resin composition of the present invention may also contain, as necessary, a core-shell polymer (C) different from the (meth)acrylic copolymer (B) and other components. By including the polyester elastomer (A) as an essential component in the resin composition of the present invention, a resin molded article obtained by molding the resin composition and molding material of the present invention has excellent mechanical properties such as flexibility, oil resistance, and tensile elongation, and is also easy to mold. By including the (meth)acrylic copolymer (B) as an essential component, the resin composition of the present invention has an excellent balance of performance such as flexibility, oil resistance, and tensile elongation. Furthermore, by including the core-shell polymer (C), the resin composition of the present invention can further improve flexibility and impart impact resistance, thereby improving mechanical strength.

[0032] [Polyester-Based Elastomer (A)] The resin composition of the present invention contains a polyester-based elastomer (A) as an essential component. The polyester-based elastomer (A) preferably contains a hard segment (A1) and a soft segment (A2), with the hard segment (A1) primarily composed of a crystalline aromatic polyester such as polybutylene terephthalate, and the soft segment (A2) preferably being a block copolymer primarily composed of an aliphatic polyether and / or an aliphatic polyester, particularly an aliphatic polyether. Here, the hard segment (A1) is a polymer segment having a crystalline melting point of 100°C or higher, e.g., 150°C to 230°C, as measured by differential scanning calorimetry (DSC), and the soft segment (A2) is a polymer segment having a glass transition temperature (Tg) of less than 0°C, e.g., −30°C to −100°C, as measured by differential scanning calorimetry (DSC).

[0033] The content of the polyester elastomer (A) in the resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, relative to 100% by mass of the total resin composition. When the resin composition of the present invention contains 10% by mass or more of the polyester elastomer (A), the properties of the polyester elastomer (A) are easily exhibited. Furthermore, the content of the polyester elastomer (A) in the resin composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. When the resin composition of the present invention contains 90% by mass or less of the polyester elastomer (A), the amount of the (meth)acrylic copolymer (B) described below is ensured, and the flexibility, tensile elongation, oil resistance, and other properties imparted by the (meth)acrylic copolymer (B) are effectively exhibited. The resin composition of the present invention may contain only one type of polyester elastomer (A), or may contain two or more types of hard segments (A1) and soft segments (A2) described below, which differ in monomer composition, content ratio, physical properties, and the like.

[0034] [Hard Segment (A1)] The hard segment (A1) contained in the polyester-based elastomer (A) used in the present invention is a polyester formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol, and is preferably composed primarily of polybutylene terephthalate derived from a raw material containing terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol as main components.

[0035] In this case, other components that can be contained in the raw material of the hard segment (A1) include, for example, dicarboxylic acid components such as isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and diols having a molecular weight of 300 or less, such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol. Examples of diol components include any aliphatic diol, alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecanedimethylol, and aromatic diols such as xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-p-terphenyl, and 4,4'-dihydroxy-p-quarterphenyl. The hard segment (A1) may be constituted by a copolymerized polyester using two or more of these dicarboxylic acid components and diol components, or may be constituted by copolymerizing a tri- or higher functional polyfunctional carboxylic acid component, a polyfunctional oxyacid component, and a polyfunctional hydroxy component.

[0036] From the viewpoint of the heat resistance of the polyester-based elastomer (A), the hard segment (A1) preferably contains 50% by mass or more, particularly 80 to 100% by mass of a crystalline aromatic polyester, and the crystalline aromatic polyester is preferably composed of polybutylene terephthalate. In this case, from the viewpoint of the heat resistance of the polyester-based elastomer (A), the crystalline aromatic polyester preferably contains 50% by mass or more, particularly 80 to 100% by mass of polybutylene terephthalate.

[0037] The content of the hard segment (A1) in the polyester elastomer (A) used in the present invention is preferably 10% by mass or more, more preferably 15% by mass or more. When the content of the hard segment (A1) in the polyester elastomer (A) is 10% by mass or more, the heat resistance of the polyester elastomer (A) is improved due to the effect of the hard segment (A1). Furthermore, the content of the hard segment (A1) in the polyester elastomer (A) used in the present invention is preferably 60% by mass or less, more preferably 50% by mass or less. When the content of the hard segment (A1) in the polyester elastomer (A) is 60% by mass or less, the polyester elastomer (A) has excellent flexibility due to the effect of the soft segment (A2).

[0038] [Soft Segment (A2)] The soft segment (A2) in the polyester elastomer used in the present invention is preferably composed mainly of an aliphatic polyether and / or an aliphatic polyester.

[0039] Examples of aliphatic polyethers constituting the soft segment (A2) include polytetramethylene ether glycol, polypropylene oxide, polyethylene oxide, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and tetrahydrofuran, copolymers of propylene oxide and tetrahydrofuran, and copolymers of ethylene oxide, propylene oxide and tetrahydrofuran. Among these, polytetramethylene ether glycol and copolymers of ethylene oxide and propylene oxide are preferred from the viewpoint of the elastic properties of the resulting polyester elastomer (A), and polytetramethylene ether glycol is more preferred. Examples of aliphatic polyesters include poly(ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. Among these, poly(ε-caprolactone), polybutylene adipate, and polyethylene adipate are preferred from the viewpoint of the elastic properties of the resulting polyester elastomer (A).

[0040] The soft segment (A2) preferably contains 50% by mass or more, particularly 80 to 100% by mass of the aliphatic polyether, particularly from the viewpoint of the flexibility of the polyester elastomer (A).

[0041] The number average molecular weight of the soft segment (A2) in the copolymerized state is preferably about 300 to 600 from the viewpoint of handling of the polyester elastomer (A).

[0042] The content of the soft segment (A2) in the polyester elastomer (A) used in the present invention is preferably 40% by mass or more, more preferably 50% by mass or more. When the content of the soft segment (A2) in the polyester elastomer (A) is 40% by mass or more, the polyester elastomer (A) has excellent flexibility due to the effect of the soft segment (A2). Furthermore, the content of the soft segment (A2) in the polyester elastomer (A) used in the present invention is preferably 90% by mass or less, more preferably 85% by mass or less. When the content of the soft segment (A2) in the polyester elastomer (A) is 90% by mass or less, the heat resistance is improved due to the effect of the hard segment (A1).

[0043] [Method for Producing Polyester Elastomer (A)] The polyester elastomer (A) used in the present invention can be produced by a known method. For example, any of the following may be employed: a method in which a lower alcohol diester of a dicarboxylic acid as the hard segment (A1) component and an excess amount of a diol component are subjected to a transesterification reaction with a soft segment (A2) component in the presence of a catalyst, and the resulting reaction product is polycondensed; a method in which a dicarboxylic acid, an excess amount of a diol component, and the soft segment (A2) component are subjected to an esterification reaction with a dicarboxylic acid, an excess amount of a diol component, and the soft segment (A2) component in the presence of a catalyst, and the resulting reaction product is polycondensed; a method in which a hard segment (A1) is produced in advance, and the soft segment (A2) component is added thereto and randomly polymerized by a transesterification reaction; a method in which the hard segment (A1) and the soft segment (A2) are linked with a chain linking agent; or a method in which, when poly(ε-caprolactone) is used for the soft segment (A2), an ε-caprolactone monomer is subjected to an addition reaction with the hard segment (A1).

[0044] [(Meth)acrylic Copolymer (B)] The resin composition of the present invention contains a (meth)acrylic copolymer (B) which is a block copolymer and / or a graft copolymer (hereinafter, may be referred to as "the (meth)acrylic copolymer (B) of the present invention"). The (meth)acrylic copolymer (B) of the present invention contains 50 mass% or more of structural units derived from alkyl (meth)acrylate. The (meth)acrylic copolymer (B) of the present invention is preferably a block copolymer and / or a graft copolymer which contains a polymer (B1) and a polymer (B2) described below in the same molecule, and has at least one of the structure of a block copolymer and a graft copolymer.

[0045] The block and / or graft structure of the (meth)acrylic copolymer (B) of the present invention may be any of diblock, triblock, multiblock, graft, cyclic, star, comb, dendritic, ladder, etc., or may be a structure combining a plurality of these structures. Among these structures, it is preferable to have at least one of the diblock, triblock, and graft structures, since this is expected to provide flexibility and production is relatively easy.

[0046] In the (meth)acrylic copolymer (B) of the present invention, it is preferable to contain polymer (B1) in order to impart miscibility and compatibility with the polyester elastomer (A) and to enable the (meth)acrylic copolymer (B) to be handled as a solid. In the (meth)acrylic copolymer (B) of the present invention, it is preferable to contain polymer (B2) in order to impart flexibility, oil resistance, and tensile elongation. Furthermore, this tends to improve weather resistance and heat aging resistance. Therefore, when the (meth)acrylic copolymer (B) contains both polymer (B1) and polymer (B2) in the same molecule, the flexibility, oil resistance, and tensile elongation of the resin composition, molding material, and resin molded article of the present invention are improved.

[0047] For example, the (meth)acrylic copolymer (B) may be a graft copolymer in which the main chain is constituted by the polymer (B1), and a graft chain made of the polymer (B2) is branched and connected to the main chain made of the polymer (B1). Conversely, the main chain may be the polymer (B2), and the side chain may be the polymer (B2). The (meth)acrylic copolymer (B) may be a block copolymer in which a polymer made of the polymer (B1) and a polymer made of the polymer (B2) are connected in series. Furthermore, the main chain and / or side chain of the graft copolymer may have a structure containing a block copolymer. In particular, the (meth)acrylic copolymer (B) of the present invention preferably contains a graft copolymer containing the polymer (B1) and the polymer (B2) in the same molecule, since this makes it easier to obtain the effect of improving the moldability of the resin composition and molding material of the present invention.

[0048] The (meth)acrylic copolymer (B) of the present invention preferably contains sulfur. From the viewpoint of the tensile elongation of the resin composition, molding material, and resin molded article of the present invention, the sulfur is preferably chemically bonded to the (meth)acrylic copolymer (B). The sulfur content in the (meth)acrylic copolymer (B) is preferably 15 μg / g or more, more preferably 30 μg / g or more, and even more preferably 50 μg / g or more. When the sulfur content in the (meth)acrylic copolymer (B) is 15 μg or more, the tensile elongation of the resin composition, molding material, and resin molded article of the present invention is good. On the other hand, the sulfur content in the (meth)acrylic copolymer (B) is preferably 1000 μg / g or less, more preferably 500 μg / g or less, and even more preferably 200 μg / g or less. When the sulfur content in the (meth)acrylic copolymer (B) is 1000 μg or less, yellowing is suppressed, and the appearance of the resulting resin molded article is good. In the present invention, the sulfur content in the (meth)acrylic copolymer (B) means the amount of elemental sulfur contained in 1 g of the (meth)acrylic copolymer (B) determined using AQF-ion chromatography. The sulfur content in the (meth)acrylic copolymer (B) can be adjusted, for example, by using a sulfur-containing chain transfer agent described below during polymerization.

[0049] The lower limit of the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) of the present invention is preferably 100,000 or more, more preferably 130,000 or more, even more preferably 200,000 or more, and particularly preferably 300,000 or more. If the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 100,000 or more, the flexibility, oil resistance, and tensile elongation of the resin composition, molding material, and resin molded article of the present invention will be good, and furthermore, the weather resistance and heat aging resistance will be better. Furthermore, the upper limit of the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is preferably 5,000,000 or less, more preferably 3,500,000 or less, and even more preferably 2,000,000 or less. When the weight average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 5,000,000 or less, the miscibility and compatibility with the polyester elastomer (A) when producing the resin composition of the present invention is good, and the moldability of the molding material is good. Note that, in the present invention, the weight average molecular weight (Mw) of the (meth)acrylic copolymer (B) means the weight average molecular weight, which is the relative molecular weight determined using gel permeation chromatography (GPC) in terms of polymethyl methacrylate (PMMA).

[0050] The content of the (meth)acrylic copolymer (B) in a total of 100% by mass of the resin composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. When the content of the (meth)acrylic copolymer (B) is 10% by mass or more, flexibility, oil resistance, and tensile elongation, which are the effects of blending the (meth)acrylic copolymer (B), are easily imparted. In addition, weather resistance and heat aging resistance tend to be better. Furthermore, the content of the (meth)acrylic copolymer (B) in a total of 100% by mass of the resin composition of the present invention is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less. When the content of the (meth)acrylic copolymer (B) is 90% by mass or less, the properties of the polyester elastomer (A) are easily exhibited. The resin composition of the present invention may contain only one type of (meth)acrylic copolymer (B), or may contain two or more types of polymers (B1) and (B2) described below that differ in monomer composition, content ratio, physical properties, etc.

[0051] [Polymer (B1)] The polymer (B1) preferably contains 60% by mass or more of methyl methacrylate units relative to its total weight (100% by mass). The polymer (B1) more preferably contains 70% by mass or more of methyl methacrylate units, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. If the lower limit of the methyl methacrylate unit content of the polymer (B1) is 60% by mass or more, particularly 70% by mass or more, relative to the total weight (100% by mass) of the polymer (B1), the polymer (B1) will have good affinity with the polyester elastomer (A), and will have good miscibility and compatibility. Furthermore, the (meth)acrylic copolymer (B) will have good handleability as a solid. On the other hand, the upper limit of the content of methyl methacrylate units is not particularly limited, and the polymer (B1) may be a homopolymer of 100% by mass of methyl methacrylate, or may be 99.9% by mass or less, or 99% by mass or less, or may be 98% by mass or less.

[0052] In addition to methyl methacrylate units, polymer (B1) may contain other comonomer units copolymerizable with methyl methacrylate depending on the purpose of the (meth)acrylic copolymer (B). The other comonomer units copolymerizable with methyl methacrylate preferably contain acrylate units. When polymer (B1) contains acrylate units as comonomer units, depolymerization of polymer (B1) when exposed to high-temperature conditions such as melt molding can be suppressed, improving thermal decomposition resistance. Furthermore, by adjusting the type and content of the comonomer units, functions such as glass transition temperature (Tg), processability, heat resistance, refractive index, weather resistance, mold releasability, and thermal decomposition resistance of polymer (B1) can be controlled.

[0053] The upper limit of the content of comonomer units such as acrylate units in polymer (B1) is preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to 100% by mass of the total mass of polymer (B1), in order to maintain good performance such as heat resistance, hardness, scratch resistance, weather resistance, transparency, and processability. On the other hand, the lower limit of the content of the comonomer units is not particularly limited, and as mentioned above, polymer (B1) may not contain comonomer units, i.e., may be a homopolymer of methyl methacrylate. From the viewpoint of thermal decomposition resistance, the content of comonomer units in polymer (B1) may be 0.1% by mass or more, 1% by mass or more, or 2% by mass or more.

[0054] Examples of comonomers that form the comonomer units of polymer (B1) include the following a) to i): a) (meth)acrylate ester monomers other than methyl methacrylate, such as methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. b) Hydroxyl group-containing (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, etc. c) Carboxyl group-containing vinyl monomers such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate, etc. d) Acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride, e) Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, glycidyl α-ethyl acrylate and 3,4-epoxybutyl (meth)acrylate, f) Amino group-containing (meth)acrylate vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.g) Amide group-containing vinyl monomers such as (meth)acrylamide, N-t-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide. h) Vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate. i) Polyfunctional vinyl monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, and N,N'-methylenebis(meth)acrylamide.

[0055] These may be used alone or in combination of two or more.

[0056] Among these, in terms of easy availability of the monomer, methyl acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred, with methyl acrylate being more preferred.

[0057] The polymer (B1) preferably contains a structural unit derived from the macromonomer (b1) described below. In this case, the macromonomer (b1) may contain a methyl methacrylate unit.

[0058] The lower limit of the weight average molecular weight (Mw) of the polymer (B1) in the present invention is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, even more preferably 20,000 or more, and particularly preferably 26,000 or more. When the Mw of the polymer (B1) is 3,000 or more, the affinity of the polymer (B1) with the polyester elastomer (A) is improved, and miscibility and compatibility can be expected. Furthermore, the upper limit of the weight average molecular weight (Mw) of the polymer (B1) is preferably 1,000,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, even more preferably 40,000 or less, and particularly preferably 10,000 or less. When the Mw of the polymer (B1) is 1,000,000 or less, the melt viscosity falls within an appropriate range. In the present invention, the mass average molecular weight (Mw) of the polymer (B1) means a mass average molecular weight that is a relative molecular weight determined using gel permeation chromatography (GPC) and converted into polymethyl methacrylate (PMMA).

[0059] The polymer (B1) in the present invention may be a mixture of two or more polymers. In this case, the mass average molecular weight (Mw) is calculated as the value of the entire polymer (B1). When multiple types of polymers (B1) with different mass average molecular weights (Mw) are used in combination, the polymer (B1) with a lower molecular weight plays a role in reducing the syrup viscosity and preventing crosslinking of the copolymer, while the polymer (B1) with a higher molecular weight plays a role in ensuring compatibility with the matrix resin when used as an additive.

[0060] The content of polymer (B1) in the (meth)acrylic copolymer (B) of the present invention is preferably 10% by mass or more and 75% by mass or less, based on the total weight of the (meth)acrylic copolymer (B) (100% by mass). When the lower limit of the content of polymer (B1) is 10% by mass or more, it becomes easier to obtain a (meth)acrylic copolymer (B) having excellent miscibility and compatibility with the polyester elastomer (A). The lower limit of the content of polymer (B1) is more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. On the other hand, when the upper limit of the content of polymer (B1) is 75% by mass or less, it becomes easier to obtain the effect of imparting flexibility by polymer (B2). The upper limit of the content of polymer (B1) is more preferably 70% by mass or less, even more preferably 65% ​​by mass or less.

[0061] [Polymer (B2)] The polymer (B2) imparts functions such as flexibility, oil resistance, tensile elongation, weather resistance, and heat aging resistance to the (meth)acrylic copolymer (B) and the resin composition, molding material, and resin molded article of the present invention using the same.

[0062] The glass transition temperature (Tg) of the polymer (B2) is preferably 0°C or lower, more preferably -10°C or lower, even more preferably -20°C or lower, particularly preferably -35°C or lower, and particularly preferably -40°C or lower. When the glass transition temperature (Tg) of the polymer (B2) is 0°C or lower, the flexibility, oil resistance, and tensile elongation are good. Furthermore, the impact resistance and fluidity during melt molding are improved. The lower limit of the glass transition temperature (Tg) of the polymer (B2) is usually -60°C. In the present invention, the Tg of the polymer (B2) can be calculated by using the Fox equation, employing the values ​​described in known literature such as the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003) as the Tg of the homopolymer of the monomer that is the structural unit of the polymer (B2). Alternatively, the dynamic viscoelasticity of the obtained molded article can be measured, and the value of tan δ can be used as the Tg.

[0063] The content of polymer (B2) contained in the (meth)acrylic copolymer (B) of the present invention is preferably 25% by mass or more and 90% by mass or less, based on 100% by mass of the total weight of the (meth)acrylic copolymer (B). If the lower limit of the content of polymer (B2) is 25% by mass or more, the (meth)acrylic copolymer (B) is more likely to provide the effects of improving flexibility, oil resistance, and tensile elongation. In addition, weather resistance and heat aging resistance tend to be better. The lower limit of the content of polymer (B2) is more preferably 30% by mass or more, and even more preferably 35% by mass or more. On the other hand, if the upper limit of the content of polymer (B2) is 90% by mass or less, the handleability of the (meth)acrylic copolymer (B) is improved. The upper limit of the content of polymer (B2) is more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 75% by mass or less.

[0064] The mass average molecular weight (Mw) of the polymer (B2) is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and particularly preferably 20,000 or more. When the mass average molecular weight (Mw) of the polymer (B2) is 3,000 or more, flexibility, tensile elongation, and impact resistance are good. Furthermore, the mass average molecular weight (Mw) of the polymer (B2) is preferably 2,500,000 or less, more preferably 2,000,000 or less, even more preferably 1,500,000 or less, and particularly preferably 1,000,000 or less. When the mass average molecular weight (Mw) of the polymer (B2) is 2,500,000 or less, the transparency of the resin composition, molding material, and resin molded article of the present invention is good. The mass average molecular weight (Mw) of the polymer (B2) can be calculated from the mass average molecular weight (Mw) of the entire (meth)acrylic copolymer (B) and the weight ratio of the polymer (B1) to the polymer (B2). １ It can be determined by a method such as H-NMR. For example, when the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 100,000 and the proportion of the polymer (B2) in a total of 100 mass% of the (meth)acrylic copolymer (B) is 40 mass%, the mass average molecular weight (Mw) of the polymer (B2) can be calculated as 100,000 × 0.4 = 40,000.

[0065] [Monomer (b2)] Monomer (b2) is a monomer used as a raw material for polymer (B2). Monomer (b2) is not particularly limited as long as it can produce a (meth)acrylic copolymer (B), and various polymerizable monomers can be used as needed. Specifically, it is preferable to mainly use acrylates in terms of setting a low glass transition temperature (Tg) to impart flexibility and tensile elongation, and in terms of oil resistance. Furthermore, mainly using acrylates tends to improve weather resistance and heat aging resistance. That is, polymer (B2) preferably contains 50% by mass or more of acrylate units as the main component. Furthermore, other monomers can be used as needed.

[0066] Since polymer (B2) preferably contains 50% by mass or more of acrylate units, the acrylate used in monomer (b2) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 85% by mass or more, relative to the total weight (100% by mass) of monomer (b2). When the lower limit of the acrylate content is 50% by mass or more, the polymer (B2) imparts to the (meth)acrylic copolymer (B) the effects of improving flexibility, tensile elongation, and oil resistance. Furthermore, weather resistance and heat aging resistance tend to be better. On the other hand, when the acrylate content is low, the effects of improving flexibility, tensile elongation, and oil resistance may be insufficient. The upper limit of the acrylate content in monomer (b2) is not particularly limited, but is preferably less than 100% by mass, more preferably 99% by mass or less, and even more preferably 95% by mass or less, relative to the total weight (100% by mass) of monomer (b2).

[0067] Furthermore, the acrylate used for monomer (b2) can impart excellent flexibility to the resulting resin molded article, so it is preferable that the glass transition temperature (Tg) of the acrylate homopolymer is 0° C. or lower. In the present invention, the Tg of the acrylate homopolymer can be calculated using the Fox formula using values ​​described in known documents such as the Polymer Handbook (POLYMER HANDBOOK FOURTH EDITION 2003).

[0068] Examples of the acrylate used in the monomer (b2) include acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-lauryl acrylate, n-stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and phenoxyethyl acrylate; hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and glycerol acrylate; 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl phthalic acid, and 2-acryloyloxyethyl acrylate; Examples of suitable acrylates include carboxyl group-containing acrylates such as 2-acryloyloxypropyl phthalate, 2-acryloyloxyethyl maleate, 2-acryloyloxypropyl maleate, 2-acryloyloxyethyl succinate, and 2-acryloyloxypropyl succinate; epoxy group-containing acrylates such as glycidyl acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl acrylate; amino group-containing acrylates such as dimethylaminoethyl acrylate and diethylaminoethyl acrylate; and polyfunctional acrylates such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, allyl acrylate, and N,N'-methylenebisacrylamide. These may be used alone or in combination of two or more.

[0069] Among the above-mentioned monomers, 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate are preferred because the Tg of the homopolymer of the monomer is 0° C. or less. Furthermore, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferred because they are easily available.

[0070] Aromatic vinyl can be used as a monomer other than acrylate for the monomer (b2). The aromatic vinyl is used for the purpose of adjusting the refractive index and Tg of the polymer (B2) and adjusting the polymerization rate when producing the polymer (B2) and the (meth)acrylic copolymer (B). The content of the aromatic vinyl used in the monomer (b2) is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 5 to 15% by mass, relative to 100% by mass of the total mass of the monomer (b2). When the content of the aromatic vinyl contained in the monomer (b2) is 1% by mass or more, the polymerization rate can be adjusted, and the tensile elongation of the (meth)acrylic copolymer (B) can be improved. When the content of the aromatic vinyl contained in the monomer (b2) is 30% by mass or less, the refractive index and Tg of the polymer (B2) contained in the (meth)acrylic copolymer (B) can be adjusted. The content of the aromatic vinyl used in the monomer (b2) corresponds to the content of repeating units derived from the aromatic vinyl in the polymer (B2).

[0071] Examples of aromatic vinyls include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, p-t-butylstyrene, vinylethylbenzene, vinyltoluene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene. Among these, styrene is preferred from the viewpoints of practical physical properties and productivity. These can be used alone or in combination of two or more.

[0072] The monomer (b2) of the present invention may contain other monomers copolymerizable with the acrylate and the aromatic vinyl, as needed. Examples of such other monomers include methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, and phenoxyethyl methacrylate; hydroxyl group-containing methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and glycerol methacrylate; 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxypropyl hexahydrophthalic acid, 2-methacryloyl Carboxy group-containing methacrylates such as oxyethyl phthalate, 2-methacryloyloxypropyl phthalate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxypropyl maleate, 2-methacryloyloxyethyl succinate, and 2-methacryloyloxypropyl succinate; epoxy group-containing methacrylates such as glycidyl methacrylate and 3,4-epoxybutyl methacrylate; amino group-containing methacrylates such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; polyfunctional methacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate; and the like. One or more of these can be appropriately selected and used.

[0073] Further, examples of other monomers include carboxy group-containing vinyl monomers such as (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate; acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride; amide group-containing vinyl monomers such as (meth)acrylamide, N-t-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide; and vinyl monomers such as (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate.

[0074] The amount of other monomers other than acrylate and aromatic vinyl is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to 100% by mass of the total of the monomers (b2), and may not be used at all.

[0075] [Method for producing (meth)acrylic copolymer (B)] Examples of methods for producing the (meth)acrylic copolymer (B) of the present invention include living polymerization methods and methods using a macromonomer (b1) described below. Examples of living polymerization methods include living radical polymerization methods and living anionic polymerization methods. Examples of living radical polymerization methods include reversible addition-fragmentation chain transfer polymerization (RAFT), atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), and living radical polymerization using organotellurium as a growing terminal (TERP). The method using macromonomer (b1) is advantageous in that it allows the (meth)acrylic copolymer (B) to be produced relatively easily, and is preferred because it has the advantage of not requiring the removal of catalyst or auxiliary residues or terminal treatment steps required in living polymerization methods.

[0076] [Method for Producing (Meth)acrylic Copolymer (B) Using Macromonomer] In a method for producing a (meth)acrylic copolymer (B) using a macromonomer, the macromonomer may be used as a raw material for either polymer (B1) or polymer (B2). A macromonomer copolymer is obtained by copolymerizing the macromonomer with a comonomer copolymerizable with the macromonomer. This macromonomer copolymer can be used as the (meth)acrylic copolymer (B). Here, as an example, a method for producing a macromonomer copolymer by using macromonomer (b1) as a raw material for polymer (B1) and copolymerizing the macromonomer (b1) with monomer (b2) will be described. In this case, polymer (B2) has monomer (b2) as a monomer unit.

[0077] [Method of Producing Macromonomer (b1)] Macromonomer (b1) can be produced by known methods. Examples of methods for producing the macromonomer include a method using a cobalt chain transfer agent (U.S. Patent No. 4,680,352), a method using an α-substituted unsaturated compound such as α-bromomethylstyrene as a chain transfer agent (WO 88 / 04304), a method of chemically bonding a polymerizable group (JP-A No. 60-133007, U.S. Patent No. 5,147,952, and JP-A No. 06-298921), and a method using thermal decomposition (JP-A No. 11-240854). Among these, the method for producing macromonomer (b1) is preferably a method using a cobalt chain transfer agent, as it requires fewer production steps and uses a catalyst with a high chain transfer constant.

[0078] Examples of methods for producing the macromonomer (b1) using a cobalt chain transfer agent include bulk polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization. Among these, the aqueous dispersion polymerization method is preferred from the viewpoint of simplifying the recovery step of the macromonomer (b1).

[0079] The cobalt chain transfer agent used in the present invention is represented by the following general formula (2): Examples of such cobalt chain transfer agents include those described in Japanese Patent No. 3,587,530, JP-A Nos. 6-23209 and 7-35411, U.S. Pat. Nos. 45,269,945, 4,694,054, 4,834,326, 4,886,861, and 5,324,879, International Publication No. 95 / 17435, and Published Japanese Translation of PCT International Publication No. 9-510499.

[0080]

[0081] [In the formula, R １１ ~R １４ are each independently an alkyl group, a cycloalkyl group, or an aryl group. １１ ~X １４ are each independently an F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, an alkyl group, or an aryl group.

[0082] Specific examples of cobalt chain transfer agents include bis(borondifluorodimethyldioximinocyclohexane)cobalt(II), bis(borondifluorodimethylglyoximate)cobalt(II), bis(borondifluorodiphenylglyoximate)cobalt(II), cobalt(II) complexes of vicinaliminohydroxyimino compounds, cobalt(II) complexes of tetraazatetraalkylcyclotetradecatetraenes, N,N'-bis(salicylidene)ethylenediaminocobalt(II) complexes, cobalt(II) complexes of dialkyldiazadioxodialkyldodecadienes, and cobalt(II) porphyrin complexes. Among these, bis(borondifluorodiphenylglyoximate)cobalt(II) (R １１ ~R １４ : phenyl group, X １１ ~X １４ : F atom) are preferred. One or more of these can be appropriately selected and used.

[0083] The amount of the cobalt chain transfer agent used is preferably 5 ppm to 350 ppm relative to 100 parts by mass of the monomer for obtaining macromonomer (b1). When the amount of the cobalt chain transfer agent used is 5 ppm or more, the molecular weight is likely to be sufficiently reduced, and when it is 350 ppm or less, the obtained macromonomer (b1) is less likely to be discolored.

[0084] Examples of solvents used when obtaining macromonomer (b1) by solution polymerization include hydrocarbons such as toluene, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and chloroform, ketones such as acetone, alcohols such as methanol, nitriles such as acetonitrile, vinyl esters such as ethyl acetate, carbonates such as ethylene carbonate, and supercritical carbon dioxide. These may be used alone or in combination of two or more.

[0085] In the present invention, the lower limit of the mass average molecular weight (Mw) of the macromonomer (b1) is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, even more preferably 20,000 or more, and particularly preferably 26,000 or more. If the Mw of the macromonomer (b1) is 3,000 or more, the affinity of the polymer (B1) derived from the macromonomer (b1) with the polyester elastomer (A) is improved, and miscibility and compatibility can be expected. Furthermore, the upper limit of the mass average molecular weight (Mw) of the macromonomer (b1) is preferably 1,000,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, even more preferably 40,000 or less, and particularly preferably 10,000 or less. When the Mw of the macromonomer (b1) is 1,000,000 or less, the melt viscosity of the (meth)acrylic copolymer (B) falls within an appropriate range. In the present invention, the mass average molecular weight (Mw) of the macromonomer (b1) refers to the mass average molecular weight, which is a relative molecular weight determined using gel permeation chromatography (GPC) and converted into polymethyl methacrylate (PMMA).

[0086] [Method for producing macromonomer copolymer] The method for producing a macromonomer copolymer includes a step of polymerizing a polymerizable mixture containing a polymerizable composition (X) described below and a polymerization initiator. The polymerizable composition (X) contains a macromonomer (b1) represented by the following general formula (1) and a comonomer copolymerizable with the macromonomer (b1). The comonomer is appropriately selected from the monomers (b2) that are copolymerizable with the macromonomer (b1).

[0087]

[0088] (In formula (1), R ０ ~R ｎ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. １ ~X ｎ are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0089] <R ０ ~R ｎ In the formula (1), R ０ ~R ｎ The alkyl group, cycloalkyl group, aryl group or heterocyclic group may have a substituent.

[0090] R ０ ~R ｎ Examples of the alkyl group include branched or linear alkyl groups having 1 to 20 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl. Among these, in terms of availability, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl are preferred, with methyl, ethyl, n-propyl, i-propyl, n-butyl, and t-butyl being more preferred, and methyl being particularly preferred.

[0091] R ０ ~R ｎ Examples of the cycloalkyl group include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a t-butylcyclohexyl group, an isobornyl group, and an adamantyl group. Of these, the cyclopropyl group, the cyclobutyl group, and the adamantyl group are preferred because of their ease of availability.

[0092] R ０ ~R ｎ Examples of the aryl group include aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a benzyl group, and a naphthyl group.

[0093] R ０ ~R ｎ Examples of the heterocyclic group include heterocyclic groups having 5 to 18 carbon atoms. Specific examples include a γ-lactone group, an ε-caprolactone group, and a morpholine group. Examples of heteroatoms contained in the heterocycle include an oxygen atom, a nitrogen atom, and a sulfur atom.

[0094] R ０ ~R ｎ Examples of the substituents that may be possessed by R include, independently, a group or atom selected from the group consisting of an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (-COOR'), a carbamoyl group (-CONR'R''), a cyano group, a hydroxy group, an amino group, an amide group (-NR'R''), a halogen atom, an allyl group, an epoxy group, an alkoxy group (-OR'), and a group exhibiting hydrophilicity or ionicity. Examples of R' or R'' include, independently, R ０ ~R ｎ and the like (excluding heterocyclic groups).

[0095] R ０ ~R ｎ Examples of the alkoxycarbonyl group as a substituent of R include a methoxycarbonyl group. ０ ~Rｎ Examples of the carbamoyl group as a substituent of R include an N-methylcarbamoyl group and an N,N-dimethylcarbamoyl group. ０ ~R ｎ Examples of the amide group as a substituent of R include a dimethylamide group. ０ ~R ｎ Examples of the halogen atom as a substituent of R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ ~R ｎ Examples of the alkoxy group as a substituent of R include alkoxy groups having 1 to 12 carbon atoms. A specific example is a methoxy group. ０ ~R ｎ Examples of the hydrophilic or ionic group as a substituent include an alkali salt of a carboxy group or an alkali salt of a sulfoxyl group, a poly(alkylene oxide) group such as a polyethylene oxide group or a polypropylene oxide group, and a cationic substituent such as a quaternary ammonium base.

[0096] R ０ ~R ｎ is preferably at least one selected from an alkyl group and a cycloalkyl group, more preferably an alkyl group. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group is preferred, and from the viewpoint of availability, a methyl group is more preferred.

[0097] <X １ ~X ｎ In the formula (1), X １ ~X ｎ From the viewpoint of ease of synthesis of the macromonomer (b1), X １ ~X ｎ Preferably, 80 mol % or more of the total moles of (100 mol %) are methyl groups.

[0098] <Z> In the formula (1), Z is a terminal group of the macromonomer (b1). Examples of the terminal group of the macromonomer (b1) include a hydrogen atom and a group derived from a radical polymerization initiator, similar to terminal groups of polymers obtained by known radical polymerization.

[0099] The lower limit of the content of methyl methacrylate units in the macromonomer (b1) is not particularly limited, but a content of 60% by mass or more relative to 100% by mass of the total mass of the macromonomer (b1) is advantageous for imparting miscibility and compatibility with the polyester-based elastomer (A). The lower limit of the content of methyl methacrylate units is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. On the other hand, the upper limit of the content of methyl methacrylate units is not particularly limited, and may be 100% by mass of methyl methacrylate units, or may be 99% by mass or less relative to 100% by mass of the total mass of the macromonomer (b1).

[0100] In the method for producing a macromonomer copolymer, the polymerization reaction is preferably carried out using a radical polymerization method. Examples of radical polymerization methods include bulk polymerization methods such as bulk polymerization and cast polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization. Aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization are preferred because they simplify the recovery process of the macromonomer copolymer. Furthermore, suspension polymerization is more preferred because the resulting polymer particles are easy to handle. In suspension polymerization, the macromonomer copolymer is obtained as spherical particles with an average particle size of approximately 5 μm to 1 mm. The resulting spherical particles are easy to handle and have little risk of dust scattering when used in processing operations such as extrusion and molding, making them suitable for use as resin compositions. Furthermore, suspension polymerization is preferred because the resin compositions obtained by suspension polymerization have good moldability. The reason why suspension polymerization is superior to emulsion polymerization is not clear, but it is presumed that the suspension polymerization is superior to emulsion polymerization because, in emulsion polymerization, trace amounts of abnormal polymers and residual emulsifiers are generated, which can cause foreign matter and thickening, whereas suspension polymerization does not have such problems. Details of suspension polymerization will be described later.

[0101] Alternatively, the polymerization reaction in the production of the macromonomer copolymer may be carried out using a bulk polymerization method such as a mass polymerization method or a cast polymerization method, and may include a step of heating the polymerizable mixture to polymerize. Furthermore, in the case of a solution polymerization method, it is also possible to produce the (meth)acrylic copolymer (B) of the present invention by producing the macromonomer (b1) by solution polymerization, and then adding the monomer (b2) and a thermal polymerization initiator to the resulting solution and carrying out a copolymerization reaction.

[0102] In the method for producing a macromonomer copolymer according to the present invention, the polymerizable mixture may contain a sulfur-containing chain transfer agent. Here, the sulfur-containing chain transfer agent refers to a mercaptan compound, such as n-butyl mercaptan or n-octyl mercaptan, that is added as a chain transfer agent to adjust the molecular weight of the copolymer during polymerization. When the polymerizable composition contains a sulfur-containing chain transfer agent, the upper limit of its content is preferably 0.3 parts by mass or less, more preferably 0.2 parts by mass or less, and even more preferably 0.15 parts by mass or less, per 100 parts by mass of the polymerizable composition (X). When the upper limit of the sulfur-containing chain transfer agent content is 0.3 parts by mass or less, broadening of the copolymer composition distribution can be suppressed, and the impact resistance of the resulting resin molded article can be improved. The lower limit of the sulfur-containing chain transfer agent content is not particularly limited, and the polymerizable composition may not contain a sulfur-containing chain transfer agent. However, the content may be 0.05 parts by mass or more from the viewpoint of the tensile elongation of the resulting resin molded article.

[0103] In producing the macromonomer copolymer, polymerization can be carried out so that the mass average molecular weight (Mw) of the resulting macromonomer copolymer is 100,000 or more and 5,000,000 or less. The lower limit of the mass average molecular weight (Mw) of the macromonomer copolymer is preferably 100,000 or more, more preferably 130,000 or more, even more preferably 200,000 or more, and particularly preferably 300,000 or more. If the mass average molecular weight (Mw) of the macromonomer copolymer is 100,000 or more, the flexibility, oil resistance, tensile elongation, weather resistance, and heat aging resistance of the resin composition, molding material, and resin molded article of the present invention will be excellent. On the other hand, the upper limit of the Mw of the macromonomer copolymer is preferably 5,000,000 or less, more preferably 3,500,000 or less, and even more preferably 2,000,000 or less. If the mass average molecular weight (Mw) of the macromonomer copolymer is 5,000,000 or less, the miscibility and compatibility with the polyester elastomer (A) when producing the resin composition of the present invention will be good, and the moldability of the molding material will be good. The above upper and lower limits can be combined arbitrarily. There are no particular restrictions on the method for controlling the mass average molecular weight (Mw) of the macromonomer copolymer to 100,000 or more, but those skilled in the art can control it by adjusting the polymerization method, the type and amount of polymerization initiator, the amount of chain transfer agent, the polymerization temperature, etc., according to well-known techniques.

[0104] [Polymerizable composition (X)] The polymerizable composition (X) is one of the raw materials for the (meth)acrylic copolymer (B). The content ratios of the macromonomer (b1) (b1, unit: mass%) and the monomer (b2) (b2, unit: mass%) contained in the polymerizable composition (X), relative to 100 mass% of the total mass of the polymerizable composition (X), are preferably b1:b2=10-75 mass%:90-25 mass%, more preferably b1:b2=15-70 mass%:85-30 mass%, even more preferably b1:b2=20-70 mass%:80-30 mass%, and particularly preferably b1:b2=25-65 mass%:75-35 mass%. The content ratio of the macromonomer (b1) (b1, unit: mass%) and the content ratio of the monomer (b2) (b2, unit: mass%) contained in the polymerizable composition (X) is preferably 10:75 to 90:25, more preferably 15:85 to 70:30, still more preferably 20:80 to 70:30, and particularly preferably 25:75 to 65:35, relative to 100% by mass of the total mass of the polymerizable composition (X). When the lower limit of the content ratio of the macromonomer (b1) contained in the polymerizable composition (X) is 10% by mass or more, or when the upper limit of the content ratio of the monomer (b2) is 90% by mass or less, relative to 100% by mass of the total mass of the polymerizable composition (X), the macromonomer copolymer becomes easy to handle. Furthermore, when the lower limit of the content of the monomer (b2) in the polymerizable composition (X) is 25% by mass or more, or the upper limit of the content of the macromonomer (b1) is 75% by mass or less, relative to 100% by mass of the total mass of the polymerizable composition (X), flexibility, oil resistance, and tensile elongation can be imparted to a resin composition containing the macromonomer copolymer and the resulting resin molded article. Furthermore, weather resistance and heat aging resistance tend to be better.

[0105] [Production of Macromonomer Copolymer by Suspension Polymerization] The case where the polymerization reaction is carried out by the suspension polymerization method will be described in detail below.

[0106] Specific examples of the method for producing a macromonomer copolymer using suspension polymerization include the following methods (1) and (2). (1) A method comprising the following steps i) to v). This method is a method in which the production of the macromonomer (b1) of the present invention and the production of the macromonomer copolymer are carried out separately. (2) A method in which, of the following steps i) to v), the production of the macromonomer (b1) of the present invention and the production of the macromonomer copolymer of the present invention are carried out continuously, instead of the following steps i) to iii).

[0107] i) Syrup Preparation Step A syrup is prepared by dissolving the bead-like macromonomer (b1) produced by suspension polymerization in a solution containing the monomer (b2), and this is used as the polymerizable composition (X).

[0108] When preparing the polymerizable composition (X), a mixture containing the macromonomer (b1) and the monomer (b2) can be heated at a temperature equal to or lower than the boiling point of the monomer (b2) to promote dissolution of the macromonomer (b1). The temperature at which the polymerizable composition (X) is prepared is preferably in the range of 20°C to 100°C, more preferably in the range of 40°C to 80°C. If the radical polymerization initiator used does not react at the temperature at which the polymerizable composition (X) is prepared, the radical polymerization initiator can be mixed with the polymerizable composition (X) to obtain a polymerizable mixture, and then the polymerizable mixture can be heated.

[0109] ii) Radical Polymerization Initiator Dissolving Step: When the radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) obtained in step i) is prepared, the polymerizable composition (X) is once cooled to room temperature or below, and then the radical polymerization initiator is added and dissolved uniformly to obtain a polymerizable mixture. The temperature of the polymerizable composition (X) when the radical polymerization initiator is added is preferably not more than a temperature obtained by subtracting 15°C from the 10-hour half-life temperature of the radical polymerization initiator.

[0110] iii) Aqueous Solution Preparation Step: The polymerizable mixture and the aqueous solution are mixed and then stirred to prepare a suspension in which droplets of the polymerizable mixture are dispersed in the aqueous solution. The aqueous solution is an aqueous solution for dispersing the polymerizable mixture, and may contain a dispersant, an electrolyte, and other auxiliary agents. By appropriately selecting the combination of dispersant and electrolyte, the dispersibility of the droplets of the polymerizable mixture formed in the aqueous solution when the polymerizable mixture is dispersed in the aqueous solution can be controlled.

[0111] The water used in the aqueous solution is preferably deionized water, since this improves the dispersibility of the droplets of the polymerizable mixture.

[0112] Examples of dispersants include alkali metal salts of poly(meth)acrylic acid, copolymers of alkali metal salts of (meth)acrylic acid and (meth)acrylic acid esters, copolymers of alkali metal salts of sulfoalkyl (meth)acrylate and (meth)acrylic acid esters, alkali metal salts of polystyrene sulfonates, copolymers of alkali metal salts of styrene sulfonates and (meth)acrylic acid esters, or copolymers consisting of combinations of these monomers; polyvinyl alcohol with a saponification degree of 70 to 100%, methyl cellulose, starch, and hydroxyapatite. These may be used alone or in combination of two or more. Among these, copolymers of alkali metal salts of sulfoalkyl (meth)acrylate and (meth)acrylic acid esters and copolymers of alkali metal salts of (meth)acrylic acid and (meth)acrylic acid esters are preferred, as they exhibit good dispersion stability during suspension polymerization. The dispersant is used, for example, in an amount of 0.0005 to 0.5 parts by mass per 100 parts by mass of the polymerizable composition (X).

[0113] Examples of the electrolyte include sodium carbonate, sodium sulfate, manganese sulfate, etc. The electrolyte is used in an amount of, for example, 0.01 to 1.0 part by mass per 100 parts by mass of the polymerizable composition (X).

[0114] I) Syrup Preparation Step: The polymerizable composition (X) is prepared by adding a solution containing a monomer (b2) to a bead-like macromonomer (b1) produced by suspension polymerization dispersed in an aqueous solution. The temperature at which the macromonomer (b1) is dissolved in the solution containing the monomer (b2) is preferably in the range of 20°C to 100°C, more preferably in the range of 40°C to 90°C, and even more preferably in the range of 50°C to 80°C. The aqueous solution may be the same as that described in iii) above.

[0115] II) Radical Polymerization Initiator Dissolution Step: When the radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) obtained in step I) is prepared, the polymerizable composition (X) is once cooled to room temperature or below, and then the radical polymerization initiator is added and dissolved uniformly to obtain a polymerizable mixture. The temperature of the polymerizable composition (X) when the radical polymerization initiator is added is preferably not more than a temperature obtained by subtracting 15°C from the 10-hour half-life temperature of the radical polymerization initiator.

[0116] When the polymerization reaction is carried out in the presence of a radical polymerization initiator, known organic peroxides such as 2,4-dichlorobenzoyl peroxide and t-butyl peroxypivalate, and known azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile) can be used as the radical polymerization initiator. The amount of the radical polymerization initiator to be added can be appropriately selected by a person skilled in the art in accordance with well-known techniques. Typically, the amount of the radical polymerization initiator to be added is 0.0001 to 10 parts by mass per 100 parts by mass of the total amount of the polymerizable composition (X).

[0117] iv) Polymerization Reaction Step: The resulting suspension is then heated while being stirred to initiate the polymerization reaction. It is preferable to remove dissolved oxygen from the polymerizable mixture and the aqueous solution before heating by subjecting them to reduced pressure degassing or nitrogen substitution. The polymerization temperature during the polymerization reaction is an important condition for obtaining a macromonomer copolymer in a high yield. The polymerization temperature here refers to the temperature of the suspension. The polymerization temperature is preferably 50°C to 90°C, more preferably 60°C to 85°C, and even more preferably 65°C to 80°C. If the polymerization temperature is too low, the reaction may proceed slowly, resulting in a long polymerization time. If the polymerization temperature is too high, cleavage of the adduct radical, which is a reaction intermediate, takes precedence, tending to reduce the yield of the macromonomer copolymer.

[0118] In the latter stage of the polymerization reaction, the suspension may be heated to increase the reaction rate of the polymerizable composition (X) and eliminate unreacted radical polymerization initiator. The temperature to which the suspension is heated is preferably 80° C. or higher, more preferably 85° C. or higher. The temperature-raising time may be determined by calculating the time required for the radical polymerization initiator to disappear, and is usually about 30 minutes to 2 hours.

[0119] v) Recovery step: After the above steps, the suspension is cooled to room temperature or below, and the resulting copolymer in the form of beads is recovered by a known method such as filtration. If necessary, a washing step for removing impurities such as dispersants and electrolytes, a step for removing beads containing air bubbles, a drying step, etc. may be performed. The finally obtained macromonomer copolymer in the form of beads is referred to as the (meth)acrylic copolymer (B) of the present invention.

[0120] [Core-shell polymer (C)] The resin composition of the present invention may contain a core-shell polymer (C) (hereinafter, sometimes referred to as "core-shell polymer (C) of the present invention") different from the above-mentioned (meth)acrylic copolymer (B). The core-shell polymer (C) of the present invention is also called a rubbery graft polymer or a rubber-containing graft copolymer, and is usually a particulate core-shell type rubbery graft polymer containing a core portion made of rubber (a rubbery polymer) and a shell portion having functions such as compatibility with the matrix, which is produced by graft copolymerizing a copolymerizable comonomer in the presence of rubber (a rubbery polymer having a crosslinked structure). In contrast, among the above-mentioned (meth)acrylic copolymers (B), the (meth)acrylic copolymer (B), which is a graft copolymer, does not contain a rubbery polymer having a crosslinked structure and is clearly distinguishable from the core-shell polymer (C).

[0121] The core-shell polymer (C) of the present invention is used for the purpose of imparting flexibility and impact resistance to the resin composition, molding material, and molded article of the present invention. In particular, it exhibits an effect of improving toughness, which is difficult to improve with the (meth)acrylic copolymer (B), and by incorporating the core-shell polymer (C), impact resistance at low temperatures can be obtained. Furthermore, the acrylic copolymer (B) may cause anisotropy in mechanical properties due to the orientation of the polymer (B2) component in the flow direction during injection molding. In contrast, the core-shell polymer (C) of the present invention has crosslinked rubber particles, which reduces deformation of the rubber domains during injection molding. Therefore, the combined use of the acrylic copolymer (B) and the core-shell polymer (C) has the effect of eliminating anisotropy.

[0122] The core-shell polymer (C) of the present invention can be appropriately selected from commonly available polymers.

[0123] Examples of the rubber constituting the core portion of the core-shell polymer (C) include one or more of acrylic rubber containing acrylate as a constituent unit, butadiene rubber containing butadiene as a constituent unit, butadiene-acrylic composite rubber containing butadiene and acrylate as constituent units, and silicone-acrylic composite rubber containing dimethylsiloxane and acrylate as constituent units.

[0124] Among these, acrylic rubber containing acrylate as a structural unit or silicone-acrylic composite rubber containing dimethylsiloxane and acrylate as structural units is preferred as the rubber constituting the core portion, as this improves the weather resistance of the resin composition. On the other hand, in terms of improving toughness and impact resistance and imparting flexibility, butadiene rubber containing butadiene as a structural unit, butadiene-acrylic composite rubber containing butadiene and acrylate as structural units, or silicone-acrylic composite rubber containing dimethylsiloxane and acrylate as structural units is preferred as the rubber constituting the core portion. Furthermore, silicone-acrylic composite rubber is particularly preferred in terms of achieving both improved toughness and impact resistance, imparted flexibility, and weather resistance. The rubber constituting the core portion can be appropriately selected and used depending on the performance requirements of the molded product. A combination of different rubbers may be used for the core portion.

[0125] The content of rubber in the core-shell polymer (C) (the core portion of the core-shell polymer (C)) is preferably 10 to 99% by mass relative to 100% by mass of the core-shell polymer (C). If the rubber content is 10% by mass or more, the low-temperature impact strength of the resin composition will be sufficient, and if it is 99% by mass or less, the surface appearance of the molded article will be good, which is preferable. From the viewpoint of improving the low-temperature impact strength of the resin composition, the rubber content of the core-shell polymer (C) is more preferably 50 to 95% by mass, and even more preferably 65 to 90% by mass, relative to 100% by mass of the core-shell polymer (C).

[0126] The shell portion (also referred to as the graft portion) of the core-shell polymer (C) can be formed by graft copolymerizing a vinyl monomer for forming the shell portion in the presence of the above-mentioned rubber.

[0127] Examples of vinyl monomers for forming the shell portion include: aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and i-butyl methacrylate; alkyl acrylates such as ethyl acrylate, n-butyl acrylate, and methyl acrylate; cyanide vinyl monomers such as acrylonitrile and methacrylonitrile; and aryl (meth)acrylates in which the ester group is a phenyl group or a substituted phenyl group, such as phenyl (meth)acrylate, 4-t-butylphenyl (meth)acrylate, bromophenyl (meth)acrylate, dibromophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, monochlorophenyl (meth)acrylate, dichlorophenyl (meth)acrylate, and trichlorophenyl (meth)acrylate. These may be used alone or in combination of two or more.

[0128] The core-shell polymer (C) is not particularly limited, but may have a multilayer structure of three or more layers including an inner layer as a core portion, a graft layer as a shell portion, and an intermediate layer therebetween.

[0129] The volume average particle diameter of the particulate core-shell polymer (C) is preferably 50 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more. The volume average particle diameter of the core-shell polymer (C) is preferably 1000 nm or less, more preferably 700 nm or less, even more preferably 600 nm or less, and particularly preferably 500 nm or less. If the volume average particle diameter of the core-shell polymer (C) is 50 nm or more, it functions as a rubber and can improve toughness and impact resistance. If the volume average particle diameter of the core-shell polymer (C) is 1000 nm or less, the number of particles per unit mass increases, resulting in good toughness and impact resistance. The method for measuring the volume average particle diameter of the core-shell polymer (C) is not particularly limited, and it can be measured, for example, by the method described in the Examples section below.

[0130] When the resin composition of the present invention contains a core-shell polymer (C), the lower limit of the content of the core-shell polymer (C) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to 100% by mass of the total resin composition of the present invention. By including 5% by mass or more of the core-shell polymer (C), toughness, flexibility, and impact resistance can be effectively imparted to the resin composition, molding material, and molded article of the present invention. Furthermore, molded articles with little anisotropy can be obtained. The upper limit of the content of the core-shell polymer (C) is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, relative to 100% by mass of the total resin composition of the present invention. When the content of the core-shell polymer (C) is 50% by mass or less, good moldability can be ensured for the resin composition and molding material of the present invention.

[0131] The resin composition of the present invention may contain only one type of core-shell polymer (C) of the present invention, or may contain two or more types that differ in the type of rubber in the core portion or the type or composition of the vinyl monomer that constitutes the shell portion.

[0132] [Other Components] The resin composition of the present invention may contain other components in addition to the polyester elastomer (A), (meth)acrylic copolymer (B), and core-shell polymer (C). The other components are added to the resin composition as needed. Examples of the other components include antiblocking agents, release agents, antioxidants, heat stabilizers, impact modifiers, flexibility imparting agents, thermoplastic elastomers other than the polyester elastomer (A), weather resistance improvers, colorants, inorganic pigments, organic pigments, carbon black, ferrite, conductivity imparting agents, ultraviolet absorbers, infrared absorbers, inorganic fillers, inorganic fillers, organic fillers, reinforcing agents, plasticizers, antiplasticizers, neutralizing agents, crosslinking agents, flame retardants, preservatives, insect repellents, fragrances, radical scavengers, and sound-absorbing materials. These other components may be used alone or in combination of two or more.

[0133] [Method for producing resin composition and molding material] The resin composition of the present invention can be produced by mixing raw materials according to a conventional method, and the method is not particularly limited. For example, the raw materials are placed in a single-screw extruder or a twin-screw extruder and heated, melt-kneaded at about 150 to 300°C. Furthermore, the resin composition of the present invention can be processed into pellets after heated, melt-kneaded, and then suitably used as a molding material.

[0134] [Resin Molded Article] The resin composition and molding material of the present invention are shaped into a resin molded article by a known melt molding method such as extrusion molding, injection molding, insert molding, compression molding, blow molding, torpedo injection molding, torpedo extrusion molding, etc. The shape of the resin molded article of the present invention is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, a substantially box shape, a tube shape, a cylinder shape, and a three-dimensional shape having a curved surface portion.

[0135] [Uses of Resin Molded Article] The resin molded article of the present invention can be used in various applications. Examples of uses of the resin molded article include tubes, hoses, automobile parts, constant velocity joint boots (CVJ), boot parts, grip parts, button / switch parts, door lock parts, shift levers, fuel cap tethers, air ducts, bellows, emblems, grommets, gaskets, trim, edges, vibration-isolating rubber, electric and electronic parts, sealing materials for electric and electronic parts, machine parts, hinge parts, waterproof packing, insulating covers, grips, cushion parts, silencer gears, cables, wire coatings, curled cords, hydraulic hoses, spiral tubes, printer tractor belts, conveyor belts, ski and snowboard boot parts, fibers, films, nonwoven fabrics, nail polish cases, hot curlers, hair dryer brushes, hair brushes, zipper pulls, toothbrushes, bobbin cases, diaphragms, mandrels, 3D printer filaments, and stationery.

[0136] [Additive for Polyester Elastomers] The additive for polyester elastomers of the present invention contains the (meth)acrylic copolymer (B) of the present invention, which is the above-mentioned block copolymer and / or graft copolymer, and is added to a polyester elastomer to improve its flexibility, oil resistance, tensile elongation, etc. while making the most of the properties of the polyester elastomer. The additive for polyester elastomers of the present invention may further contain the above-mentioned core-shell polymer (C).

[0137] The (meth)acrylic copolymer (B) in the additive for polyester elastomers of the present invention is the (meth)acrylic copolymer (B) of the present invention described above in the section on the resin composition of the present invention, and the same applies to preferred embodiments thereof. When the additive for polyester elastomers of the present invention further contains a core-shell polymer (C), the core-shell polymer (C) of the present invention described above in the section on the resin composition of the present invention is the core-shell polymer (C) of the present invention, and the same applies to preferred embodiments thereof.

[0138] Furthermore, examples of polyester elastomers to which the additive for polyester elastomers of the present invention is added include the polyester elastomer (A) contained in the resin composition of the present invention described above, and the same applies to preferred embodiments thereof.

[0139] The additive for polyester elastomers of the present invention may be composed only of the (meth)acrylic copolymer (B) of the present invention, or the (meth)acrylic copolymer (B) and core-shell polymer (C) of the present invention, or may contain, together with the (meth)acrylic copolymer (B) of the present invention, or the (meth)acrylic copolymer (B) and core-shell polymer (C) of the present invention, any of the components exemplified as other components that the resin composition of the present invention may contain in addition to the polyester elastomer (A), the (meth)acrylic copolymer (B), and the core-shell polymer (C). The content of the (meth)acrylic copolymer (B) of the present invention in the additive for polyester elastomers of the present invention is preferably 10% by mass or more, more preferably 30% by mass or more, and may even be 100% by mass, relative to 100% by mass of the additive for polyester elastomers of the present invention, from the viewpoint of effectively obtaining the modifying effect of the (meth)acrylic copolymer (B) of the present invention on the polyester elastomer. When the additive for polyester elastomers of the present invention contains the core-shell polymer (C) of the present invention, from the viewpoint of effectively obtaining the effects of the core-shell polymer (C) of the present invention on toughness, flexibility and impact resistance, the content of the core-shell polymer (C) is preferably 5% by mass or more, more preferably 20% by mass or more, relative to 100% by mass of the additive for polyester elastomers of the present invention. Also, from the viewpoint of ensuring the content ratio of the (meth)acrylic copolymer (B) of the present invention, the content of the core-shell polymer (C) is preferably 90% by mass or less, more preferably 70% by mass or less, relative to 100% by mass of the additive for polyester elastomers of the present invention.

[0140] The additive for polyester elastomers of the present invention is added to polyester elastomers to improve their flexibility, oil resistance, tensile elongation, etc. In this case, the amount of the additive for polyester elastomers of the present invention to be added to the polyester elastomer is, relative to the total mass of the (meth)acrylic copolymer (B) and the polyester elastomer (100 mass%), preferably 10 mass% or more, more preferably 20 mass% or more, and even more preferably 30 mass% or more of the (meth)acrylic copolymer (B). Also, the amount is preferably 70 mass% or less, and particularly preferably 50 mass% or less. When the amount of the (meth)acrylic copolymer (B) is equal to or greater than the above-mentioned lower limit, the additive for polyester elastomers of the present invention provides excellent flexibility, oil resistance, and tensile elongation, and also provides excellent improving effects on weather resistance, heat degradation resistance, etc. On the other hand, when the amount of the (meth)acrylic copolymer (B) of the present invention added is equal to or less than the above upper limit, the inherent properties of the polyester elastomer can be fully exhibited.

[0141] The additive for polyester elastomers of the present invention can be uniformly blended into the polyester elastomer by adding a required amount to the polyester elastomer and heating and melt-kneading the mixture at about 150 to 300°C using a single-screw extruder or a twin-screw extruder.

[0142] The additive for polyester elastomers of the present invention may contain only one type of (meth)acrylic copolymer (B) of the present invention, or may contain two or more types that differ in physical properties such as monomer composition, ratio of polymer (B1) to polymer (B2), molecular weight, etc. Similarly, the core-shell polymer (C) may contain only one type, or may contain two or more types that differ in the type of rubber in the core portion or the type and composition of vinyl monomer that constitutes the shell portion.

[0143] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, "parts" means "parts by mass."

[0144] [Evaluation Method] Evaluations in the examples and comparative examples were carried out by the following methods.

[0145] (Weight-average molecular weight (Mw) and number-average molecular weight (Mn) of macromonomer (b1)) The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the macromonomer (b1) obtained in the examples and comparative examples were measured using gel permeation chromatography (GPC). 10 mg of the obtained copolymer was dissolved in 10 mL of tetrahydrofuran, and the solution was filtered through a 0.45 μm filter to prepare a sample for GPC measurement. A gel permeation chromatography measurement device (manufactured by Tosoh Corporation, model name: HLC-8320) was used, with a polymer measurement guard column (manufactured by Tosoh Corporation, product name: TSK-GUARD COLUMN SUPER H-H) and two polymer measurement columns (manufactured by Tosoh Corporation, product name: TSK-GEL SUPER HM-H) connected in series. A differential refractometer (RI) was used as the detector. Measurements were performed under the following conditions. Separation column temperature: 40°C Mobile phase: tetrahydrofuran Mobile phase flow rate: 0.6 mL / min Sample injection amount: 10 μL A calibration curve was prepared using several types of polymethyl methacrylate with known molecular weights (manufactured by Polymer Laboratories, peak molecular weight (Mp) 1,560 to 19,500,000) as standard polymers, and Mw and Mn were determined.

[0146] (Mass Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn) of (Meth)acrylic Copolymer (B) (Macromonomer Copolymer)) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer copolymer, which is the (meth)acrylic copolymer (B) obtained in the Examples and Comparative Examples, were measured using gel permeation chromatography (GPC). 10 mg of the obtained copolymer was dissolved in 10 mL of tetrahydrofuran, and the solution filtered through a 0.45 μm filter was used as a sample for GPC measurement. In the GPC measurement of the copolymer, a high performance liquid chromatography measurement apparatus (manufactured by Tosoh Corporation, model name: HLC-8320) was used, connected in series with a polymer measurement guard column (manufactured by Tosoh Corporation, product name: TSK-GUARD COLUMN SUPER H-H) and one ultra polymer measurement column (manufactured by Tosoh Corporation, product name: TSK-GEL GMHHR-H). A differential refractometer (RI) was used as the detector. The measurement was performed under the following conditions. Separation column temperature: 40°C Mobile phase: tetrahydrofuran Mobile phase flow rate: 0.6 mL / min Sample injection amount: 10 μL A calibration curve was prepared using several types of polymethyl methacrylate (manufactured by Polymer Laboratories, peak molecular weight (Mp) 1,560 to 19,500,000) with known molecular weights as standard polymers, and the mass average molecular weight (Mw) and number average molecular weight (Mn), which are relative molecular weights converted into polymethyl methacrylate, were determined.

[0147] (Sulfur Content of (Meth)acrylic Copolymer (B)) The sulfur content of the (meth)acrylic copolymer (B) was determined using an AQF-ion chromatograph with the following equipment, conditions, and procedures. Device name: AQF-ion chromatograph IC-2010 (anion), manufactured by Tosoh Corporation; Analytical column: TSK gel Super IC-Anion HS; Guard column: TSK guard column Super IC-A; Column temperature: 40°C; Flow rate: 1.5 mL / min; Gel: TSK suppress IC-A; Detector: Electrical conductivity detector; Measurement method: Absolute calibration curve method; Measurement time: 6 minutes; Automatic sample combustion device: Nitto Seiki Air Analytec automatic sample combustion device AQF-2100H (absorption solution: hydrogen peroxide solution 0.1 wt%, combustion temperature 1000°C); Operation method: Approximately 0.2 g was weighed out into a porcelain port using a balance, and the absorption solution was set. Next, the sample was combusted, and the combustion gas was absorbed into the absorption solution. Sulfate ions were quantified using IC, and sulfate (SO ４ ) was converted to sulfur (S).

[0148] (Volume average particle diameter of core-shell polymer (C) or polyorganosiloxane) The volume average particle diameter of the core-shell polymer (C) or polyorganosiloxane was measured by the following method. A latex of the core-shell polymer (C) or polyorganosiloxane was diluted with deionized water to a concentration of about 3%, and the particle diameter was measured using a CHDF2000 particle size distribution analyzer manufactured by MATEC Corporation in the United States, and the median diameter was used as the volume average particle diameter. The measurement was performed under the following standard conditions recommended by MATEC Corporation. Cartridge: Dedicated capillary cartridge for particle separation (product name: C-202) Carrier liquid: Dedicated carrier liquid (product name: 2XGR500) Carrier liquid property: Nearly neutral Carrier liquid flow rate: 1.4 ml / min Carrier liquid pressure: Approximately 4,000 psi (2,600 kPa) Measurement temperature: 35°C Amount of sample used: 0.1 ml Furthermore, as the standard particle size substance, monodisperse polystyrene with known particle sizes manufactured by DUKE Corporation of the United States was used, with 12 types of particles in the particle size range of 40 to 800 nm.

[0149] (Surface Hardness) Three 10 cm square, 2 mm thick molded pieces obtained in the Examples and Comparative Examples were stacked without any gaps and subjected to surface hardness measurement. A Type D durometer hardness tester (Ueshima Seisakusho, product name: HD-104N) was attached to a constant pressure load machine (Teclock Corporation, product name: GS-710), and the needle was pressed against the sample at a speed of approximately 1.5 mm / sec to read the maximum value indicated by the pointer. The smaller this value (D hardness), the better the flexibility.

[0150] (Tensile Test) The tensile strength and tensile elongation (tensile breaking elongation) of the dumbbell test pieces obtained in the Examples and Comparative Examples were measured using a universal testing machine (manufactured by Toyo Seiki Seisaku-sho, Ltd., trade name: Strograph T) under the conditions of a temperature of 23°C and a pulling speed of 500 mm / min.

[0151] (Oil Resistance Test) The dumbbell test specimens obtained in the Examples and Comparative Examples were immersed in IRM903 (manufactured by Japan Sun Oil Co., Ltd.), a standard oil for rubber immersion tests, for one week, and the oil absorption was calculated according to the following formula (3). The smaller the calculated oil absorption value, the better the oil resistance. Oil absorption (%) = (mass of test specimen after immersion - mass of test specimen before immersion) / mass of test specimen before immersion... formula (3). Furthermore, the tensile strength and tensile elongation at break of the dumbbell test specimens after the immersion test were measured using a universal testing machine (manufactured by Toyo Seiki Seisakusho, trade name: Strograph T). The measurement was performed under conditions of a temperature of 23°C and a tensile speed of 500 mm / min.

[0152] (Heat Aging Resistance Test) The dumbbell test pieces obtained in the Examples and Comparative Examples were kept for 100 hours in a dryer set at 140° C. The removed samples were cooled to room temperature, and then the surface hardness was measured and a tensile test was carried out by the methods described above.

[0153] [Raw Materials] The abbreviations for the compounds used in the Examples and Comparative Examples are as follows: MMA: methyl methacrylate (manufactured by Mitsubishi Chemical Corporation) MA: methyl acrylate (manufactured by Mitsubishi Chemical Corporation) BA: n-butyl acrylate (manufactured by Mitsubishi Chemical Corporation) St: styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Dispersant (1): dispersant produced in Production Example 1 Chain transfer agent (1): chain transfer catalyst produced in Production Example 2 nOM: n-octyl mercaptan (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Perocta O: 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perocta O) V-59: 2,2'-azobis(2-methylbutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-59) Pelprene (registered trademark) P-30B: trade name, manufactured by Toyobo Co., Ltd., polyester-based elastomer. Hard segment (A1): polybutylene terephthalate. Soft segment (A2): polytetramethylene ether glycol. Crystal melting point of hard segment (A1): 160°C. Kraton (registered trademark) G1651H: trade name, manufactured by Kraton Corporation, polystyrene-based thermoplastic elastomer containing hydrogenated polybutadiene.

[0154] [Production Example 1: Synthesis of Dispersant (1)] A reactor equipped with a stirrer, a cooling tube, and a thermometer was charged with 61.6 parts of a 17% by mass aqueous potassium hydroxide solution, 19.1 parts of MMA, and 19.3 parts of deionized water. The liquid in the reactor was then stirred at room temperature, and after confirming the exothermic peak, the mixture was stirred for 4 hours. After this, the reaction liquid in the reactor was cooled to room temperature to obtain an aqueous potassium methacrylate solution.

[0155] Next, 900 parts of deionized water, 70 parts of a 42% by weight aqueous solution of sodium 2-sulfoethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester SEM-Na), 16 parts of the above potassium methacrylate aqueous solution, and 7 parts of MMA were placed in a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, and the mixture was stirred. While the atmosphere inside the polymerization apparatus was replaced with nitrogen, the liquid in the reaction apparatus was heated to 50°C. 0.053 parts of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 2,2'-azobis(2-methylpropionamidine) dihydrochloride) was added as a polymerization initiator to the polymerization apparatus, and the liquid in the reaction apparatus was heated to 60°C. After the addition of the polymerization initiator, 1.4 parts of MMA was added in 5 installments every 15 minutes (total amount of MMA: 7 parts). Thereafter, the liquid in the polymerization reactor was kept at 60° C. for 6 hours while stirring, and then cooled to room temperature to obtain a dispersant (1) in the form of a transparent aqueous solution having a solid content of 8% by mass.

[0156] Production Example 2 Synthesis of Chain Transfer Agent (1) In a synthesis apparatus equipped with a stirrer, 2.00 g (8.03 mmol) of cobalt(II) acetate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade), 3.86 g (16.1 mmol) of diphenylglyoxime (manufactured by Tokyo Chemical Industry Co., Ltd., EP Grade), and 100 mL of diethyl ether that had been deoxygenated in advance by nitrogen bubbling were placed under a nitrogen atmosphere, and the mixture was stirred at room temperature for 2 hours.

[0157] Next, 20 mL of boron trifluoride diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd., EP grade) was added, and the mixture was further stirred for 6 hours. The obtained mixture was filtered, and the collected solid was washed with diethyl ether and dried at 100 MPa or less and 20°C for 12 hours to obtain 5.02 g (7.93 mmol, yield 99% by mass) of chain transfer agent (1) as a brown solid.

[0158] [Production Example 3: Synthesis of Macromonomer (b1-1)] In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water and sodium sulfate (Na ２ SO ４0.1 parts by mass of dispersant (1) (solid content 8% by mass) produced in Production Example 1 and 0.26 parts by mass of dispersant (1) (solid content 8% by mass) produced in Production Example 1 were added and stirred to prepare a uniform aqueous solution. Next, 95 parts by mass of MMA, 5.0 parts by mass of MA, 0.0016 parts by mass of chain transfer agent (1) produced in Production Example 2, and 0.25 parts by mass of Perocta O as a polymerization initiator were added to prepare an aqueous dispersion.

[0159] Next, the atmosphere inside the polymerization reactor was thoroughly purged with nitrogen, and the aqueous dispersion was heated to 81°C and maintained there for 3 hours, and then heated to 90°C and maintained there for 2 hours. The reaction solution was then cooled to 40°C to obtain an aqueous suspension of a macromonomer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain a bead-like macromonomer (b1-1). The obtained macromonomer (b1-1) had a number average molecular weight (Mn) of 21,300 and a mass average molecular weight (Mw) of 39,100.

[0160] [Production Examples 4 and 5: Synthesis of Macromonomers (b1-2) and (b1-3)] Macromonomers (b1-2) and (b1-3) were obtained in the same manner as for the macromonomer (b1-1) synthesized in Production Example 3, except that the amount of chain transfer agent (1) was changed as shown in Table 1. The number average molecular weight (Mn) and mass average molecular weight (Mw) of the obtained macromonomers (b1-2) and (b1-3) are shown in Table 1.

[0161]

[0162] [Production Example 6: Production of (meth)acrylic copolymer (B-1)] In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 40 parts of the macromonomer (b1-1) obtained in Production Example 3, 150 parts of deionized water, 0.26 parts of dispersant (1), and 0.3 parts of sodium sulfate were added and stirred to obtain an aqueous suspension. Next, the temperature inside the polymerization apparatus was raised to 70 ° C, and 49.8 parts of BA and 10.2 parts of St were slowly added. Thereafter, the mixture was maintained at 70 ° C for 1 hour with stirring to dissolve the macromonomer (b1-1) in BA and St, obtaining a dispersion. Next, the polymerization apparatus was cooled to 40 ° C, and 0.3 parts of V-59, a radical polymerization initiator, was added and stirred for 30 minutes to dissolve. Next, the atmosphere inside the polymerization apparatus was thoroughly purged with nitrogen, and the aqueous dispersion was heated to 82 ° C and maintained for 4 hours, and then heated to 90 ° C and maintained for 1 hour. After cooling to 40°C or below, the mixture was filtered through a filter cloth, and the filtrate was washed with deionized water. The filtrate was then dried at 40°C for 12 hours using a hot air circulation dryer, yielding a bead-like macromonomer copolymer, a (meth)acrylic copolymer (B-1). The resulting (meth)acrylic copolymer (B-1) had a number average molecular weight (Mn) of 79,600 and a mass average molecular weight (Mw) of 1,003,900. The sulfur content was 10 μg / g. The Tg of the homopolymer of styrene (St) was 100°C (POLYMER HANDBOOK FOURTH EDITION 2003), and the Tg of the homopolymer of n-butyl acrylate (BA) was -54°C (POLYMER HANDBOOK FOURTH EDITION 2003). The Tg of the polymer (B2) contained in the (meth)acrylic copolymer (B-1) was calculated using the Fox formula to be −37° C. The polymerization formulation, the calculated Tg values, and other measurement results are shown in Table 2.

[0163] [Production Examples 7 to 9: Production of (meth)acrylic copolymers (B-2) to (B-4)] Bead-shaped (meth)acrylic copolymers (B-2) to (B-4) were obtained in the same manner as in Production Example 6, except that the charged composition was changed to the conditions shown in Table 2 and the temperature rise temperature of the aqueous dispersion was changed from 82° C. to 72° C. The number average molecular weight (Mn), mass average molecular weight (Mw), and sulfur content of the obtained copolymers (B-2) to (B-4) were measured, and the calculated Tg of the polymer (B2) contained in each of the copolymers (B-2) to (B-4) are shown in Table 2.

[0164] [Production Examples 10 to 13: Production of (meth)acrylic copolymers (B-5) to (B-8)] Bead-shaped (meth)acrylic copolymers (B-5) to (B-8) were obtained in the same manner as in Production Example 6, except that the feed composition was changed to the conditions shown in Table 2. The number average molecular weight (Mn), mass average molecular weight (Mw), and sulfur content of the obtained copolymers (B-5) to (B-8) were measured, and the calculated Tg of polymer (B2) contained in each copolymer (B-5) to (B-8) are shown in Table 2. Note that although nOM was not used during the production of (meth)acrylic copolymer (B-1), a small amount of sulfur was detected because dispersant (1) contained sulfur.

[0165]

[0166] [Production Example 14: Production of Core-Shell Polymer (C-1)] 99.5 parts of 2-ethylhexyl acrylate and 0.5 parts of allyl methacrylate were mixed to obtain 100 parts of a (meth)acrylate monomer mixture. 100 parts of the (meth)acrylate monomer mixture was added to 195 parts of distilled water in which 1.9 parts (solids) of an anionic surfactant "Pelex (registered trademark) SS-L" manufactured by Kao Corporation was dissolved as alkyl diphenyl ether disulfonate sodium. The mixture was pre-stirred at 10,000 rpm with a homomixer and then homogenized at 300 kg / cm. ２The mixture was emulsified and dispersed at a pressure of 1000 kJ / min, yielding a (meth)acrylate emulsion. This mixture was transferred to a separable flask equipped with a condenser and a stirring blade, and heated while purging with nitrogen and stirring. When the temperature reached 50°C, 0.5 parts of tert-butyl hydroperoxide was added. The temperature was then raised to 50°C, and a mixture of 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongalit, and 5 parts of distilled water was added, followed by holding for 5 hours to complete the polymerization. Subsequently, 3.0 parts of Pelex (registered trademark) SS-L was added as solids to yield an acrylic rubber latex (L-1). The conversion of the acrylic rubber latex (L-1) was 99.9%.

[0167] The acrylic rubber latex (L-1) was collected so that the solid content of poly (2-ethylhexyl acrylate) containing allyl methacrylate was 20 parts, and placed in a separable flask equipped with a stirrer. The amount of distilled water in the system was added to 195 parts. Next, a mixture of 69 parts of n-butyl acrylate containing 2.0% allyl methacrylate and 0.32 parts of tert-butyl hydroperoxide was charged and stirred for 20 minutes, followed by nitrogen substitution. The system was heated to 50 ° C., and a mixture of 0.001 parts of ferrous sulfate, 0.003 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongalit, and 5 parts of distilled water was charged to initiate radical polymerization. The internal temperature was then maintained at 70 ° C. for 2 hours to complete the polymerization, resulting in a polyalkyl (meth)acrylate composite rubber latex. To this polyalkyl(meth)acrylate composite rubber latex, a mixed solution of 0.06 parts of tert-butyl hydroperoxide, 10 parts of methyl methacrylate, and 2 parts of n-butyl acrylate was added dropwise at 70°C over 15 minutes, and then the mixture was maintained at 70°C for 4 hours to complete the graft copolymerization to the composite rubber, thereby obtaining a latex of core-shell polymer (C-1). The volume average particle diameter of this core-shell polymer (C-1) was 230 nm.

[0168] To 400 parts of an aqueous solution containing 5 parts of calcium acetate at 50°C, 100 parts of the obtained latex containing the core-shell polymer (C-1) was added as a solid content, and the mixture was then heated to 90°C to coagulate. After repeated washing with water, the solid content was separated and dried at 80°C for 24 hours to obtain a powder of the core-shell polymer (C-1).

[0169] [Production Example 15: Production of Core-Shell Polymer (C-2)] 2 parts of tetraethoxysilane, 0.5 parts of γ-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. 100 parts of the siloxane mixture was added to 200 parts of distilled water in which 1 part each of sodium dodecylbenzenesulfonate and dodecylbenzenesulfonic acid had been dissolved. The mixture was pre-stirred at 10,000 rpm with a homomixer and then stirred at 300 kg / cm using a homogenizer. ２ The mixture was emulsified and dispersed at a pressure of 1000 kJ / min to obtain an organosiloxane latex. The mixture was transferred to a separable flask equipped with a condenser and a stirring blade, heated to 80°C for 5 hours with mixing and stirring, and then maintained at 20°C. After 48 hours, the pH of the latex was neutralized to 7.4 with a 5% aqueous sodium hydroxide solution to complete the polymerization and obtain a polyorganosiloxane latex (S-1). The volume average particle diameter of the resulting polyorganosiloxane was 160 nm.

[0170] 243 parts of the polyorganosiloxane latex (S-1) (81 parts as polyorganosiloxane) was collected and placed in a separable flask equipped with a stirrer, 100 parts of distilled water was added, and the mixture was purged with nitrogen and heated to 50 ° C., and a mixture of 8.9 parts of n-butyl acrylate, 0.1 parts of allyl methacrylate, and 0.56 parts of tert-butyl hydroperoxide was charged and stirred for 30 minutes. Next, 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongalit, and 5 parts of distilled water was charged to initiate radical polymerization, and then the internal temperature was maintained at 70 ° C. for 2 hours to complete the polymerization to obtain a polyorganosiloxane / n-butyl acrylate composite rubber latex.

[0171] A mixed solution of 0.06 parts of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was added dropwise to the composite rubber latex at 70°C over 15 minutes, and then the mixture was maintained at 70°C for 4 hours to complete graft polymerization onto the composite rubber, thereby obtaining a latex of core-shell polymer (C-2). The volume average particle diameter of this core-shell polymer (C-2) was 220 nm.

[0172] To 400 parts of an aqueous solution containing 3 parts of calcium acetate at 50°C, 100 parts of the obtained latex containing the core-shell polymer (C-2) was added as solids, and the mixture was then heated to 90°C to coagulate. After repeated washing with water, the solids were separated and dried at 75°C for 16 hours to obtain a powder of core-shell aggregate (C-2).

[0173] Example 1 A pellet-shaped resin composition was produced using a co-rotating twin-screw extruder (product name: BT-30, 30 mmφ, L / D=24) manufactured by Plastics Engineering Research Institute. Sixty parts of Pelprene P-30B were used as the polyester elastomer (A), and 40 parts of the acrylic copolymer (B-1) obtained in Production Example 6 were used as the (meth)acrylic copolymer (B). These were melt-kneaded at a cylinder temperature of 170 to 195°C and a die temperature of 190°C to obtain a pellet-shaped resin composition (molding material). Subsequently, a 10 cm square, 2 mm thick molded specimen was produced using an injection molding machine (product name: SE-100DU) manufactured by Sumitomo Heavy Industries, Ltd. This molded specimen was used to measure surface hardness. Furthermore, dumbbell test specimens were produced from the resulting molded specimens using a No. 3 dumbbell punching blade conforming to JIS-K6251. These dumbbells were used for tensile testing and oil resistance testing. The evaluation results are summarized in Table 3.

[0174] [Examples 2 to 10, Comparative Example 1] Pellet-shaped resin compositions were produced using the resin compositions shown in Table 3, and molded pieces were prepared by injection molding and evaluated in the same manner as in Example 1. The blending compositions of each resin composition and the evaluation results obtained are shown in Table 3.

[0175]

[0176] Comparing Examples 1 to 10 with Comparative Example 1, it can be seen that Examples 1 to 10 have lower oil absorption and greater tensile elongation. Furthermore, it can be seen that the D hardness of Examples 1 to 10 is equal to or lower than that of Comparative Example 1. Therefore, it was found that the resin composition of the present invention, in which the (meth)acrylic copolymer (B) is blended with the polyester elastomer (A), is superior in flexibility, oil resistance, and tensile elongation to the resin composition in which SEBS is blended with the polyester elastomer (A). Furthermore, the following can be seen from comparing the results of each Example. Comparing Example 1 with Examples 3 and 4, Examples 3 and 4, in which the glass transition temperature Tg of the polymer (B2) contained in the (meth)acrylic copolymer (B) is lower, tend to have lower D hardness, greater flexibility, and greater tensile elongation. Comparing Example 2 with Examples 3 and 4, in which the content of the polymer (B2) in the (meth)acrylic copolymer (B) is higher, tend to have lower D hardness, greater flexibility, and greater tensile elongation. Comparing Examples 1 and 5, and Examples 3 and 4, Examples 4 and 5, in which the mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) is small, tend to have lower D hardness and greater tensile elongation. Comparing Examples 5 and 6 with Example 2, Examples 5 and 6, in which the content of polymer (B2) in the (meth)acrylic copolymer (B) is higher, tend to have lower D hardness, greater flexibility, and greater tensile elongation. Comparing Example 6 with Examples 3 and 4, Example 6, in which the content of polymer (B2) in the (meth)acrylic copolymer (B) is higher, tends to have greater tensile elongation. Comparing Example 7 with Example 5, in which only the (meth)acrylic copolymer (B) is blended with the polyester elastomer (A), tends to have lower oil absorption and greater tensile elongation. Comparing Example 8 with Example 6, in which only the (meth)acrylic copolymer (B) is blended with the polyester elastomer (A), tends to have greater tensile elongation. However, in Examples 7 and 8, which contain the core-shell polymer (C), the impact resistance can be increased by compounding a rubber component.Comparing Examples 6, 9, and 10, Example 10, in which a (meth)acrylic copolymer (B-8) using macromonomer (b1-3) with the smallest mass-average molecular weight (Mw) of the macromonomer (b1) was blended with a polyester-based elastomer (A), tends to have a lower oil absorption. Comparing Example 1 with Example 5, Example 5, in which a (meth)acrylic copolymer (B-5) having a high sulfur content in the (meth)acrylic copolymer (B) was blended with a polyester-based elastomer (A), tends to have a higher tensile elongation. In particular, it is industrially useful in terms of its excellent tensile elongation after the heat aging resistance test. Comparing Examples 2 to 4 with Example 5, Example 5, in which a (meth)acrylic copolymer (B-5) using St as a comonomer was blended with a polyester-based elastomer (A), tends to have a lower oil absorption and a higher tensile elongation.

[0177] The resin composition of the present invention contains a polyester elastomer (A) and a (meth)acrylic copolymer (B) as constituent components, and thereby has improved flexibility, oil resistance, and tensile elongation. The resin molded article of the present invention is obtained by molding a molding material made of the resin composition of the present invention, and therefore has good flexibility and tensile elongation as well as excellent oil resistance, and can therefore be used without problems on members that come into contact with machine oil, gear oil, sebum, hand cream, sunscreen cream, etc.

[0178] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2024-122564 filed on July 29, 2024 and Japanese Patent Application No. 2025-025202 filed on February 19, 2025, both of which are incorporated by reference in their entirety.

Claims

1. A resin composition comprising a polyester elastomer (A) and a (meth)acrylic copolymer (B) which is a block copolymer and / or a graft copolymer.

2. The resin composition according to claim 1, wherein the acrylic copolymer (B) is a block copolymer and / or a graft copolymer containing, in the same molecule, a polymer (B1) containing 60% by mass or more of units derived from methyl methacrylate and a polymer (B2) having a glass transition temperature of 0°C or lower.

3. The resin composition according to claim 1, wherein the (meth)acrylic copolymer (B) contains sulfur.

4. The resin composition according to claim 1, wherein the (meth)acrylic copolymer (B) has a mass average molecular weight of 200,000 or more.

5. The resin composition according to claim 1, wherein the (meth)acrylic copolymer (B) comprises a graft copolymer.

6. The resin composition according to claim 2, wherein the polymer (B1) contains 0.1 mass % or more of repeating units derived from acrylate.

7. The resin composition according to claim 2, wherein the polymer (B2) contains 50% by mass or more of repeating units derived from acrylate.

8. The resin composition according to claim 2, wherein the polymer (B2) contains 1 mass % or more of repeating units derived from an aromatic vinyl.

9. The resin composition according to claim 2, wherein the content of the polymer (B2) in 100% by mass of the acrylic copolymer (B) is 25% by mass or more and 90% by mass or less.

10. The resin composition according to claim 1, wherein the (meth)acrylic copolymer (B) contains a repeating unit derived from a macromonomer (b1) represented by the following general formula (1): (In formula (1), R ０ ~R ｎ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. １ ~X ｎ are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

11. The resin composition according to claim 1, wherein the content of the (meth)acrylic copolymer (B) is 10% by mass or more and 90% by mass or less.

12. The resin composition according to claim 10, wherein the polyester elastomer (A) comprises a hard segment (A1) and a soft segment (A2), and the hard segment (A1) comprises polybutylene terephthalate.

13. The resin composition according to claim 12, wherein the soft segment (A2) comprises an aliphatic polyether, and the aliphatic polyether comprises at least one selected from the group consisting of polytetramethylene ether glycol, polypropylene oxide, polyethylene oxide, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and tetrahydrofuran, a copolymer of propylene oxide and tetrahydrofuran, and a copolymer of ethylene oxide, propylene oxide and tetrahydrofuran.

14. The resin composition according to claim 1, further comprising a core-shell polymer (C) different from the (meth)acrylic polymer (B).

15. The resin composition according to claim 14, wherein the core-shell polymer (C) is a particulate polymer comprising a core portion and a shell portion made of rubber, and the rubber is a silicone-acrylic composite rubber.

16. An additive for polyester elastomers, comprising a (meth)acrylic copolymer (B) which is a block copolymer and / or a graft copolymer.

17. A molding material using the resin composition according to any one of claims 1 to 15.

18. A resin molded product obtained by molding the molding material according to claim 17.

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