TW201817798A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

A thermoplastic resin composition comprising: 100 parts by mass of a methacrylic polymer (A) containing 85-100 mass% of a monomeric unit derived from methyl methacrylate; 0.1-100 parts by mass of an epoxy group-containing polymer (B) containing 1-50 mass% of a monomeric unit derived from a (meth)acrylic acid ester having an epoxy group, and 50-99 mass% of a monomeric unit derived from at least one monomer selected from the group consisting of ethylene, [alpha]-olefins having three or more carbon atoms, and styrene; and 0.01-25 parts by mass of crosslinked rubber particles (C) containing a resin having a polyfunctional monomeric unit derived from a polyfunctional monomer having two or more carbon-carbon double bonds and a monomeric unit derived from at least one monomer selected from the group consisting of (meth)acrylic acid alkyl esters, butadiene, isoprene, chloroprene, styrene, [alpha]-alkylstyrene, acrylonitrile, and methacrylonitrile.

Description

Thermoplastic resin composition and formed body thereof

[0001] The present invention is a thermoplastic resin composition containing a methacrylic polymer (A), an epoxy group-containing polymer (B), and a crosslinked rubber particle (C). According to the present invention, it is possible to provide a thermoplastic resin composition and a molded body thereof which can obtain a molded body which maintains high hardness and is excellent in solvent resistance, and which can suppress warpage during molding.

[0002] Since a molded article containing a thermoplastic resin composition is lightweight or has a high degree of freedom in product design, it has been used as a substitute for pottery or metal products in various fields. In recent years, it has been used in water revolving supplies for face wash basins, kitchen sinks, toilets, bathtubs, etc. Water rewinding products are prone to cracks on the surface because various medicines such as cosmetics or lotions adhere to the wet environment. Therefore, it is required that the surface is hardly cracked even if the medicine is adhered in a wet environment (hereinafter referred to as solvent resistance). [0003] In order to solve these problems, for example, a resin composition containing an acrylic resin, a light-shielding additive, and a rubber copolymer, and a thermoplastic resin molded body instead of a sanitary ware have been reported (Patent Document 1). [Prior Art Document] [Patent Document] [0004] [Patent Document 1] Japanese Patent Laid-Open No. 2015-227434

[Problems to be Solved by the Invention] 000 [0005] However, although the sanitary ware pottery described in the aforementioned Patent Document 1 replaces a thermoplastic resin molded body with high hardness, the above-mentioned solvent resistance is not necessarily sufficient. In addition, the resin composition described in the aforementioned Patent Document 1 is liable to warp during molding, and may not be easily molded into a desired shape. Therefore, an object of the present invention is to provide a thermoplastic resin composition and a molded body thereof that can obtain a molded body that maintains high hardness and is excellent in solvent resistance and can suppress warpage during molding. [Means to Solve the Problems] [0006] In order to solve the above problems, as a result of active review by the inventors, it was found that the present invention can solve the above problems. That is, the present invention is as follows. [0007] [1] A thermoplastic resin composition containing 100 parts by mass of a methacrylic polymer (A) containing 85 to 100% by mass of a monomer unit derived from methyl methacrylate, and containing Monomer unit of epoxy (meth) acrylate 1 to 50% by mass, a monomer derived from at least one monomer selected from the group consisting of ethylene, α-olefins having 3 or more carbon atoms, and styrene The epoxy-group-containing polymer (B) in an amount of 50 to 99% by mass is 0.1 part by mass to 100 parts by mass, and contains a polymer selected from the group consisting of alkyl (meth) acrylate, butadiene, isoprene, Monomer units of at least one monomer in the group of chloroprene, styrene, α-alkylstyrene, acrylonitrile, and methacrylonitrile are derived from as many as two or more carbon-carbon double bonds The crosslinked rubber particles (C) of the resin of the multifunctional monomer unit of the functional monomer are 0.01 parts by mass or more and 25 parts by mass or less. [2] The thermoplastic resin composition according to the aforementioned [1], wherein the epoxy-group-containing polymer (B) further contains a monomer unit derived from an alkyl (meth) acrylate, and the aforementioned is derived from (meth) acrylic acid The content of the monomer unit of the alkyl ester is relative to the above-mentioned monomer unit derived from the epoxy-containing (meth) acrylate and the aforementioned origin is selected from the group consisting of ethylene, α-olefins having 3 or more carbon atoms, and styrene. The total amount of the monomer units of the at least one monomer in the group is 100 parts by mass, and is 0.1 to 50 parts by mass. [3] A molded article containing the thermoplastic resin composition as described in [1] or [2] above. [4] A water rewinding article containing a shaped body as described in [3] above. [Effects of the Invention] [0008] According to the present invention, it is possible to provide a thermoplastic resin composition and a molded body thereof that can obtain a molded body that maintains high hardness and is excellent in solvent resistance and can suppress warpage during molding.

[0010] Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. The following embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following. The present invention can be appropriately changed within the scope of the gist thereof. In this specification, the constituent unit of the constituent polymer derived from the monomer (X) may be described as “monomer unit derived from the monomer (X)”. Further, further briefly, for example, a monomer unit derived from methyl methacrylate is described as "methyl methacrylate monomer unit", and a monomer unit derived from alkyl acrylate is also described as "alkyl acrylate Single unit. " In addition, in this specification, unless otherwise specified, the numerical range "Y ~ Z" means "more than Y and less than Z", and (meth) acrylic acid means methacrylic acid or acrylic acid. In addition, the so-called alkyl (meth) acrylate is based on CH ₂ = CHCOOR (R is alkyl) or CH ₂ = C (CH ₃ ) A compound represented by COOR (R is alkyl). [0011] (methacrylic polymer (A)) The methacrylic polymer (A) is a polymer containing 85 to 100% by mass of a monomer unit derived from methyl methacrylate. It is different from the crosslinked rubber particles (C) described later. [0012] Examples of the methacrylic polymer (A) include, for example, a homopolymer made only of methyl methacrylate monomer units, and a polymer other than methyl methacrylate monomer units and methyl methacrylate. Copolymers and the like formed from (meth) acrylic acid alkyl ester monomer units are preferably (meth) acrylic acid alkyl ester monomer units other than methyl methacrylic acid monomer units and methyl methacrylic acid monomer units. The resulting copolymer. These may be used singly or in combination of two or more kinds. Examples of the alkyl (meth) acrylate other than the above methyl methacrylate include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (formyl) (Secondary) acrylate, 2-ethylhexyl (meth) acrylate, etc., preferably methyl acrylate, ethyl (meth) acrylate or n-butyl (meth) acrylate, more preferably methyl acrylate Ester or ethyl (meth) acrylate. [0013] The methacrylic polymer (A) may be a polymer having one (meth) acrylic acid alkyl ester monomer unit other than the above methyl methacrylate monomer unit, or may be a polymer having two or more such monomers Unit of polymer. In addition, the methacrylic polymer (A) may be a "methacrylic acid methyl ester" which contains two or more types of alkyl (meth) acrylate monomer units other than the above-mentioned methyl methacrylate monomer units. -A mixture of alkyl (meth) acrylate copolymers ". [0014] The content of the methyl methacrylate monomer unit is 85 to 100% by mass, preferably 87 to 99.5% by mass, and more preferably 89 to 99% by mass. The content of the alkyl (meth) acrylate monomer units other than the above methyl methacrylate monomer units is 0 to 15% by mass, preferably 0.5 to 13% by mass, and more preferably 1 to 11% by mass. However, the total amount of the alkyl (meth) acrylate monomer units and the methyl methacrylate monomer units other than the above methyl methacrylate monomer units is 100% by mass. When the content of the methyl methacrylate monomer unit and the content of the (meth) acrylic acid alkyl ester monomer unit other than the above methyl methacrylate monomer unit are within the above range, a molded body having excellent heat resistance or mechanical strength can be obtained . [0015] The content of the methacrylic polymer (A) can be determined by measuring the amount of the soluble component after re-precipitating the thermoplastic resin composition of this embodiment when dissolved in acetone (hereinafter referred to as the acetone-soluble portion). . The content of methyl methacrylate monomer units in the methacrylic polymer (A) and the content of alkyl (meth) acrylate monomer units other than the methyl methacrylate monomer units can be obtained by using thermal decomposition gas. It is obtained by analyzing a acetone-soluble part by a phase chromatograph or the like. [0016] The polymerization method for obtaining the methacrylic polymer (A) is not particularly limited, but examples include suspension polymerization, emulsion polymerization, block polymerization, solution polymerization, and the like. [0017] Commercial products may be used as the methacrylic polymer (A), for example, "SUMIPEX" manufactured by Sumitomo Chemical Co., Ltd., "ACRYPET" manufactured by Mitsubishi Chemical Corporation, "PARAPET" manufactured by KURARAY, "DURAPET" manufactured by Asahi Kasei Corporation. [0018] The melt flow rate (MFR) of the methacrylic polymer (A) is preferably 0.5 to 25 g / 10 min, and more preferably 1 to 8 g / 10 min. The MFR is measured based on JIS K 7218 at a measurement temperature of 230 ° C and a load of 37.3N. When the MFR of the methacrylic polymer (A) is within the above range, a molded body having more excellent solvent resistance can be obtained, and warpage during molding can be further suppressed. [0019] (Epoxy-containing polymer (B)) The epoxy-containing polymer (B) contains an epoxy-containing (meth) acrylate monomer unit (hereinafter referred to as a monomer unit) (b1) 1 to 50% by mass of a monomer unit (hereinafter referred to as a monomer unit (hereinafter referred to as a monomer unit (hereinafter referred to as a monomer unit)) derived from at least one monomer selected from the group consisting of ethylene, α-olefins having 3 or more carbon atoms, and styrene. b2)) 50 to 99% by mass of the polymer is preferably a polymer further containing an alkyl (meth) acrylate monomer unit (hereinafter referred to as a monomer unit (b3)) from the viewpoint of solvent resistance. Here, the monomer unit (b3) does not include a monomer unit having an epoxy group. The α-olefin is an olefin having a carbon-carbon double bond at the α-position. [0020] Examples of the epoxy-containing (meth) acrylate in the monomer unit (b1) include glycidyl (meth) acrylate, (meth) acrylic acid [(3,4-epoxycyclohexyl) Alkyl) -1-yl] methyl ester, -3,4-epoxybutyl (meth) acrylate, -6,7-epoxyheptyl (meth) acrylate, etc., and (meth) is preferred Glycidyl acrylate. The epoxy group-containing polymer (B) may be a polymer having one kind of monomer unit (b1), or a polymer having two or more kinds of monomers, or a polymer containing two or more kinds of monomer units (b1). The species are a mixture of different polymers. By containing the monomer unit (b1), a molded body having more excellent solvent resistance can be obtained. [0021] The content of the monomer unit (b1) is 1 to 50% by mass, preferably 1 to 30% by mass, and more preferably 1 to 20% by mass. However, the total amount of the monomer units (b1) and the monomer units (b2) is 100% by mass. The content of the monomer unit (b1) can be determined by analysis using NMR or the like. When the content of the monomer unit (b1) is within the above range, a molded body having more excellent solvent resistance can be obtained. [0022] Examples of the α-olefin having a carbon number of 3 or more in the monomer unit (b2) include propylene, 1-butene, 1-hexene, 1-octene, and the like, and propylene is preferred. [0023] The monomer in the monomer unit (b2) is preferably ethylene or propylene, and more preferably ethylene. The epoxy group-containing polymer (B) may be a polymer having one kind of monomer unit (b2), or a polymer having two or more kinds of monomers, or a type containing two or more kinds of monomer units (b2). A mixture of different polymers. [0024] The content of the monomer unit (b2) is 50 to 99% by mass, preferably 70 to 99% by mass, and more preferably 80 to 99% by mass. However, the total amount of the monomer units derived from the monomer unit (b1) and the monomer unit (b2) is 100% by mass. The content of the monomer unit (b2) can be obtained by analysis using NMR or the like. When the content of the monomer unit (b2) is within the above-mentioned range, a molded body having more excellent solvent resistance can be obtained. [0025] Examples of the alkyl (meth) acrylate in the monomer unit (b3) are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. N-butyl ester, second butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like are preferably methyl (meth) acrylate or ethyl (meth) acrylate, and more preferably ( (Meth) acrylate. The epoxy group-containing polymer (B) may be a polymer having one monomer unit (b3), or a polymer having two or more kinds of monomers, or may be a type containing two or more kinds of monomer units (b3). A mixture of different polymers. [0026] When the epoxy group-containing polymer (B) is a polymer further containing a monomer unit (b3), the content of the monomer unit (b3) is preferably from 0.1 to 50% by mass, more preferably from 1 to 45 Mass%, and more preferably 3 to 40 mass%. However, the total amount of the monomer unit (b1) and the monomer unit (b2) is 100% by mass. In addition, when the content of the monomer unit (b3) is within the above range, a molded body having more excellent solvent resistance can be obtained. [0027] The polymerization method for obtaining the epoxy group-containing polymer (B) is not particularly limited, and examples thereof include methods such as high-pressure radical polymerization, solution polymerization, and emulsion polymerization. In addition, it is also possible to use epoxy, polyethylene or polypropylene, polystyrene, ethylene-α-olefin copolymers, styrene copolymers, etc. to polymerize monomers (b2) in a solution or melt-knead a polymer containing epoxy. (Meth) acrylate based graft polymerization. [0028] As the epoxy group-containing polymer (B), a commercially available product can be used, and for example, "BOND FAST" manufactured by Sumitomo Chemical Co., Ltd. can be used. [0029] The content of the epoxy group-containing polymer (B) contained in the thermoplastic resin composition is 0.1 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the methacrylic polymer (A). It is preferably from 0.3 to 50 parts by mass, more preferably from 0.5 to 20 parts by mass. When the content of the epoxy group-containing polymer (B) is in the above range, a molded body having more excellent solvent resistance can be obtained, and warpage during molding can be more suppressed. [0030] The content of the epoxy group-containing polymer (B) can be dissolved in toluene when the thermoplastic resin composition of this embodiment is dissolved in an insoluble component (hereinafter referred to as an acetone-insoluble portion), and when dissolved in toluene. The soluble component is measured by reprecipitation (hereinafter referred to as "toluene soluble portion in acetone insoluble portion"). The content of the monomer unit (b1), the content of the monomer unit (b2), and the content of the monomer unit (b3) in the epoxy-containing polymer (B) can be analyzed in acetone-insoluble parts by using NMR and the like. The toluene soluble part was calculated | required. (Crosslinked Rubber Particles (C)) The crosslinked rubber particles (C) contain a material derived from a material selected from alkyl (meth) acrylate, butadiene, isoprene, chloroprene, and styrene. Monomer units of at least one monomer in the group consisting of α-alkylstyrene, acrylonitrile, and methacrylonitrile, and a polyfunctional monomer derived from a polyfunctional monomer having more than two carbon-carbon double bonds Volume of rubber particles of resin. [0032] Examples of the alkyl (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, (formaldehyde) Group) tert-butyl acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Examples of the α-alkylstyrene include α-methylstyrene, third butylstyrene, and the like. [0033] Examples of the polyfunctional monomer having two or more carbon-carbon double bonds include, for example, diallyl maleate, allyl (meth) acrylate, divinylbenzene, trivinylbenzene, and alkanediene Alcohol di (meth) acrylate, triallyl isocyanate, polyethylene glycol di (meth) acrylate, and the like. These may be used alone or in combination of two or more. [0034] The crosslinked rubber particles (C) may be single-layer rubber particles or multilayer rubber particles. The crosslinked rubber particles (C) are preferably rubber particles having two or more layers of a soft layer and a hard layer, respectively. Since the rubber particles can suppress thermal deterioration during molding or deformation of the rubber particles due to heating, The tendency of the molded body to improve heat resistance is better, and therefore it is more preferable to have three or more organic rubber particles each having one or more soft layers and hard layers. [0035] Three or more organic rubber particles each having one or more soft layers and one or more hard layers, as shown in FIG. 1, are preferably provided with an innermost layer 4, an intermediate layer 3, and an outermost layer in order from the particle center to the outside. 2 的 结构。 2 structure. Here, the innermost layer exists in the most central layer of the particles, and the outermost layer exists in the layer furthest from the center of the particles. The intermediate layer is a layer existing between the innermost layer and the outermost layer, and may have two or more layers. Among the three or more organic rubber particles, the innermost layer and the outermost layer may be a soft layer or a hard layer, and the middle may be a soft layer or a hard layer, and may also be a laminate of a soft layer and a hard layer. Examples of the structure of three or more organic rubber particles include, for example, a soft layer-hard layer-soft layer-hard layer, a soft layer-hard layer-hard layer, a soft layer-soft layer-hard layer Layer, hard layer-soft layer-hard layer, hard layer-hard layer-soft layer-hard layer, hard layer-soft layer-hard layer-hard layer, etc. Layer-soft layer-hard layer three-layer structure, with a four-layer structure of hard layer-hard layer-soft layer-hard layer or a four-layer structure of hard layer-soft layer-hard layer-hard layer. The organic rubber particles having three or more layers are preferably three-layer organic rubber particles in which the innermost layer and the outermost layer are hard layers, and the middle layer is a soft layer. When the innermost layer and the outermost layer are hard layers, the deformation of the organic rubber particles tends to be suppressed, and when the intermediate layer is a soft layer, the toughness of the organic rubber particles tends to be improved. [0036] Examples of the monomer units included in the resin contained in the hard layer are the above-mentioned multifunctional monomer units, methyl methacrylate monomer units, ethyl methacrylate monomer units, and n-propyl methacrylate. Monomer unit, isopropyl methacrylate monomer unit, n-butyl methacrylate monomer unit, second butyl methacrylate monomer unit, third butyl methacrylate monomer unit, methacrylic acid 2 -Ethylhexyl monomer unit, cyclohexyl methacrylate monomer unit, α-methylstyrene monomer unit, third butylstyrene monomer unit, acrylonitrile monomer unit, methacrylonitrile monomer Body unit, etc. These may contain only one kind, and may use two or more kinds. When the hard layer is formed as the innermost layer, the monomer unit of the resin contained in the hard layer is preferably the above-mentioned multifunctional monomer unit and methyl methacrylate monomer unit or ethyl methacrylate monomer unit. . The content of the above-mentioned multifunctional monomer unit contained in the hard layer formed as the innermost layer is preferably 0.0001% by mass or more and 10% by mass or less. However, the total amount of all monomer units in the resin of the hard layer formed as the innermost layer is 100% by mass. When the hard layer is formed as the outermost layer, the monomer units of the resin contained in the hard layer are preferably methyl methacrylate monomer units or ethyl methacrylate monomer units. [0037] Examples of the monomer units included in the resin contained in the soft layer include the above-mentioned polyfunctional monomer units, n-butyl acrylate monomer units, 2-ethylhexyl acrylate monomer units, and the like having a carbon number of 4 ~ 11 alkyl acrylate monomer units, styrene monomer units, isoprene monomer units, chloroprene monomer units, etc., preferably the above-mentioned multifunctional monomer units, and the carbon number is 4 to 11 The alkyl acrylate monomer unit or styrene monomer unit is more preferably the above-mentioned polyfunctional monomer unit, n-butyl acrylate monomer unit, or styrene monomer unit. The content of the above-mentioned polyfunctional monomer unit in the resin contained in the soft layer is preferably 0.0001% by mass or more and 10% by mass or less. However, the total amount of all monomer units of the resin contained in the soft layer is 100% by mass. [0038] The content of the crosslinked rubber particles (C) contained in the thermoplastic resin composition is 0.001 to 25 parts by mass, and preferably 0.5 to 100 parts by mass of the methacrylic polymer (A). Parts by mass or more and 24 parts by mass, more preferably 1 part by mass or more and 23 parts by mass or less, and still more preferably 7 parts by mass or more and 23 parts by mass or less. When the content of the crosslinked rubber particles (C) is within the above range, a molded body having more excellent solvent resistance and hardness can be obtained, and warpage during molding can be suppressed. The content of the crosslinked rubber particles (C) can be obtained by dissolving the insoluble component in the acetone-insoluble portion of the thermoplastic resin composition of the present embodiment in toluene (hereinafter referred to as the toluene-insoluble portion in the acetone-insoluble portion). Weigh it out. In the case of a thermoplastic resin composition containing an inorganic substance, the content of the crosslinked rubber particles (C) can be determined by removing the amount of the toluene-insoluble portion in the acetone-insoluble portion based on the ash content determined based on JIS K7250-1. [0039] The method for producing the crosslinked rubber particles (C) is not particularly limited, and examples thereof include the method described in Japanese Patent Application Laid-Open No. 55-27576. [0040] The thermoplastic resin composition of this embodiment is a composition containing a methacrylic polymer (A), an epoxy group-containing polymer (B), and a crosslinked rubber particle (C). The thermoplastic resin composition of this embodiment contains an acetone-insoluble portion. The acetone-insoluble portion of the thermoplastic resin composition is preferably 5 parts by mass or more and 25 parts by mass or less, more preferably 6 parts by mass or more and 24 parts by mass or less, and more preferably 7 parts by mass relative to 100 parts by mass of the thermoplastic resin composition. At least 23 parts by mass. When the acetone-insoluble portion is in the above range, a molded body having more excellent solvent resistance and hardness can be obtained. [0041] The thermoplastic resin composition according to this embodiment may contain additives as long as the object of the present invention is not impaired. Examples of the additives include antioxidants, ultraviolet absorbers, inorganic fillers, colorants, and flame retardants. It is preferable to add antioxidants, ultraviolet absorbers, inorganic fillers, and coloring agents. [0042] The antioxidant is not particularly limited, but examples thereof include hindered phenol-based antioxidants and phosphorus-based antioxidants. Specifically, examples include pentaerythritol-methyl [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], 6- [3- (3-third-butyl-4- Hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butylbenzo [d, f] [1,3,2] dioxaphosphacycloheptene Ginseng (2,4-di-third-butylphenyl) phosphite, thiodiethylene [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] Octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate, N, N-hexane-1,6-diylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanamide], 3,3 ', 3 ", 5,5', 5" -hexa-third-butyl-a, a ', a " -(Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecanesulfide) Methyl) -o-cresol, ethylidenebis (oxyethylidene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexaethylidene Bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], 1,3,5-ginseng (3,5-di-third-butyl-4-hydroxybenzyl ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-gins [(4-thirdbutyl-3-hydroxy-2, 6-xylene) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-third-butyl -4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol and the like, preferably pentaerythritol-zircon [3- (3,5-di-third Butyl-4-hydroxyphenyl) propionate] or 6- [3- (3-Third-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10 -Tetra-tert-butylbenzo [d, f] [1,3,2] dioxaphosphacycloheptene. These can be used alone or in combination of two or more. As the content of antioxidant, It is preferably 0.0001 parts by mass or more and 5 parts by mass or less, more preferably 0.001 parts by mass or more and 1 part by mass or less based on 100 parts by mass of the methacrylic polymer (A). [0043] The ultraviolet absorber is not particularly limited, and examples are given. For example, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2,4 -Di-third-butylphenyl-3 ', 5'-di-third-butyl-4'-hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidine Group) sebacate, (1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butane tetracarboxylic acid ester, etc. One of these may be used The content of the ultraviolet absorber is preferably 0.0001 mass based on 100 mass parts of the methacrylic polymer (A). More than 5 parts by mass or less, more preferably 0.001 parts by mass or more and 1 parts by mass or less. [0044] The inorganic filler is not particularly limited, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, sheet glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, Zinc carbonate, zinc oxide, zinc dioxide, calcium hydrogen phosphate, wollastonite, silica, zeolite, alumina, alumina oxide, boehmite, aluminum hydroxide, titanium oxide, titanium dioxide, silicic acid, silica, Silicon dioxide, magnesium oxide, magnesium dioxide, calcium silicate, sodium aluminate silicate, magnesium silicate, barium sulfate, brass, copper, silver, aluminum, nickel, iron, iron oxide, graphite, carbon nanotubes , Calcium fluoride, mica, montmorillonite, swellable fluoromica, flint and so on. These inorganic fillers may also be appropriately surface-treated. These inorganic fillers may be used alone or in combination of two or more. The content of the inorganic filler is preferably 0.0001 to 30 parts by mass, more preferably 0.001 to 10 parts by mass, with respect to 100 parts by mass of the methacrylic polymer (A). [0045] The colorant is not particularly limited, and examples thereof include perylene dyes, perinone dyes, pyrazolone dyes, methine dyes, coumarin dyes, quinophthalone dyes, Quinoline-based dyes, anthraquinone-based dyes, anthraquinone-based dyes, anthrapyridone-based dyes, thioindigo dyes, coumarin-based dyes, isoindolinone-based pigments, diketopyrrolopyrrole-based pigments, condensation couplers Nitrogen-based pigments, benzimidazolone-based pigments, dioxazine-based pigments, copper phthalocyanine-based pigments, quinacridone-based pigments, nickel complex compounds, zinc stearate, magnesium stearate, calcium stearate , Aluminum stearate, polymethylsilsesquioxane, copper halide phthalocyanine, methyl ethyl stearate, ultramarine blue, ultramarine purple, ketjen black, acetylene black, furnace black, carbon black, liquid paraffin , Silicone oil, etc. These may be used singly or in combination of two or more kinds. The content of the colorant is preferably 0.0001 part by mass or more and 5 parts by mass or less, more preferably 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the methacrylic polymer (A). [0046] The flame retardant is not particularly limited, and examples thereof include a cyclic nitrogen compound, a phosphorus-based flame retardant, a silicon-based flame retardant, a cage-like silsesquioxane or a partially cracked structure thereof, and a silicon oxide-based flame retardant. Fuel and so on. These may be used singly or in combination of two or more kinds. The content of the flame retardant is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass based on 100 parts by mass of the methacrylic polymer (A). [0047] The thermoplastic resin composition of this embodiment may also contain a methacrylic polymer (A), an epoxy group-containing polymer (B), and a crosslinked rubber particle as long as the purpose of the present invention is not impaired. (C) Other resins. Examples of such resins include polypropylene, polyethylene, polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), and BAAS resin (butadiene Ene-acrylonitrile-acrylonitrile rubber-styrene copolymer), MBS resin (methyl methacrylate-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylonitrile rubber-styrene copolymer), Polylactic acid, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polytrimethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate Polyalkylene terephthalate resins such as esters, polytetrafluoroethylene (tetrafluoroethylene resin, PTFE), trifluoroethylene chloride resin (PCTFE), tetrafluoroethylene hexafluoride ethylene propylene resin (PFEP) , Fluorinated ethylene resin (PVF), vinylidene fluoride resin (PVDF), difluorinated dichloroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene Copolymer, Tetrafluoroethylene-ethylene copolymer (ETFE), Polyvinylidene fluoride, Polychlorotrifluoroethylene, Chlorotrifluoroethylene-ethylene copolymer (ECTFE) Fluorine resins, polyamines, polyphenylene ether resins, polyphenylene sulfide resins, phenol resins, unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, epoxy resins, cyanate resins , Xylene resin, triazine resin, urea resin, melamine resin, benzoguanamine resin, urethane resin, oxetane resin, ketone resin, alkyd resin, furan resin, styrene-pyridine resin, poly Silicone resin, synthetic rubber, etc. By containing AS resin or BAAS resin, the fluidity of the thermoplastic resin composition can be improved. By containing ABS resin or MBS resin, the impact resistance of the molded body can be improved. By including a polyester resin, the solvent resistance of a molded article can be improved. Containing fluorine-based resin or silicone resin can improve the antifouling effect on the surface of the molded body. These resins may be used singly or in combination of two or more kinds. The content of these resins is preferably 0.0001 mass parts or more and 50 mass parts or less, and more preferably 0.001 mass parts or more and 30 mass parts or less with respect to 100 mass parts of the methacrylic polymer (A). [0048] The molded article containing the thermoplastic resin composition of this embodiment can be obtained by mixing the above-mentioned methacrylic polymer (A), epoxy-containing polymer (B), and crosslinked rubber particles (C). A thermoplastic resin composition is obtained by kneading with an appropriate additive or other resin mentioned above, and obtained by molding the thermoplastic resin composition into a desired shape. The kneading method is not particularly limited, and examples include a kneading method using a kneading machine such as an extruder, a heating roller, a kneader, a roll mixer, a Banbury mixer, and the like. The kneading by the extruder is better in terms of productivity. The kneading temperature may be based on the preferred processing temperature of the raw materials to be mixed, but it is preferably 140 to 300 ° C, more preferably 180 to 280 ° C. [0049] The forming method of the formed body in this embodiment is not particularly limited, and examples thereof include injection molding, sheet molding, blow molding, injection blow molding, blow molding, T-die molding, pressure molding, and extrusion molding. For the method of forming in a molten state, a secondary processing method such as air pressure forming or vacuum forming can also be applied. [0050] The uses of the formed body of the present embodiment are not limited to the following, but examples include water revolving articles such as wash basins, kitchen sinks, toilets, bathtubs, housings for lighting, side sun visors, and heat insulation. Paper, instrument covers, headlight covers, taillight covers, pillars, and other automotive parts, vehicle sound insulation walls or windows, building materials, tableware, suitcases, smartphone covers, cosmetics, daily necessities, etc. For entertainment purposes, such as pachinko panels, Kanban, etc., water rewinding supplies are preferred. Water rewinding supplies are items used in places where water is used. [0051] Hereinafter, the present invention will be described in more detail through examples and comparative examples. The evaluation method of physical properties was performed by the following method. (1) Measurement of solvent resistance Injection molding was performed under the following conditions, and a flat plate of 90 mm width × 150 mm length × 5 mm thickness was prepared. (Forming conditions) Molding machine: AUTOSHOT 150D (screw diameter: 44mm) manufactured by FANUC Corporation Screw temperature (in order from the nozzle side): 255/260/250/235/220 ° C Injection speed: 40mm / sec Holding pressure: 800kg / cm ² 10 seconds Mold temperature: 60 ° C Cooling time: 60 seconds [0052] (1-1) Solvent resistance drip test The above prepared flat plate was cut and processed into two pieces by a circular saw machine in an equal manner in the width direction. After the plate was immersed in water at 73 ° C for 120 hours. Subsequently, the surface moisture was wiped out, and it was left to stand in a room at a temperature of 23 ° C / humidity for 5 hours, and then ethanol was dropped on the surface of the test plate, and the surface was observed and evaluated as follows. X: Cracking on the surface Y: No cracking on the surface [0053] (1-2) Solvent resistance repeated test The slab prepared above was immersed in water at 73 ° C for 48 hours. Subsequently, the surface moisture was wiped out, and left in a room at a temperature of 23 ° C./humidity of 55% for 72 hours. Subsequently, a surface of the test plate was covered with a paper towel containing 2 mL of ethanol (made by Japan Paper CRECIA, KIMMIPE S-200 (registered trademark), size: 120 mm × 215 mm), and allowed to stand for 30 minutes to confirm the presence of cracks penetrating the plate. When there is no crack, cover again with a paper towel containing 2 mL of ethanol (made by Japan Paper CRECIA, KIMMIPE S-200 (registered trademark), size: 120mm × 215mm). After standing for 30 minutes, confirm that there is no crack that penetrates the plate. Repeat this step and observe that cracks penetrate the slab in several tests. [0054] From the results of the solvent resistance drop test and the repeated solvent resistance test, the solvent resistance grade was evaluated based on the following criteria. Grade ++ means the best solvent resistance, and grade-means the worst solvent resistance. <Solvent resistance level> ++: The result of the solvent resistance dropping test is Y, and the result of the repeated solvent resistance test is 2 or more times +: The result of the solvent resistance dropping test is Y, and the result of the repeated solvent resistance test is No. 1 time: X is the result of the solvent resistance dropping test. [0055] (2) Warpage measurement The injection molding was performed under the following conditions to prepare a flat plate of 90 mm width × 150 mm length × 3 mm thickness. (Forming conditions) Molding machine: AUTOSHOT 150D (screw diameter: 44mm) manufactured by FANUC Corporation Screw temperature (sequential from the nozzle side): 255/260/250/235/220 ° C Injection speed: 50mm / sec Holding pressure: 800kg / cm ² 10 seconds Mold temperature: 60 ° C Cooling time: 20 seconds [0056] The distance from the four corners of the formed test plate when placed on a flat ground to the ground was measured as the amount of warpage. In the test system, five test plates were measured, and the average value of warpage amount + (3 × standard deviation) was calculated. The smaller the calculated value, the more suppressed the warpage. [0057] (3) Measurement of Maximum Injection Pressure The screw position was adjusted to a helical flow length of 2 mm thick with a thickness of 750 mm or more and 760 mm or less under the following conditions, and injection molding was performed to measure the maximum injection pressure. Forming machine: Si-180V (screw diameter: 28mm) manufactured by Toyo Machinery & Metals Co., Ltd. Screw temperature (in order from the nozzle side): 250/245/240/230/220 ° C Injection speed: 500mm / sec Holding pressure: 50kg / cm ² 10 seconds Mold temperature: 65 ° C Cooling time: 45 seconds [0058] The lower the maximum injection pressure is, the less the forming deformation is, the more the warpage is suppressed. The warpage at the time of molding varies with the size of the molded body, but the smaller the value calculated by the above (2) and the lower the maximum injection pressure, it means that the warpage at the time of molding of molded bodies of various sizes can be suppressed. (4) Measurement of Hardness The pencil hardness was measured based on JIS K 5600-5-4. Those having a hardness of 2H or more are excellent in hardness. (5) MFR measurement Based on JIS K 7210, MFR was measured at a measurement temperature of 230 ° C. and a load of 37.3 N. [Example 1] Based on the method described in Japanese Patent Publication No. 55-27576, by emulsification polymerization, methyl methacrylate, methyl acrylate, and allyl methacrylate were each formed in an innermost layer at 94.0. A copolymer obtained by polymerizing at a ratio of 5% by mass, 5.8% by mass, and 0.2% by mass. The intermediate layer is made of n-butyl acrylate, styrene, and allyl methacrylate at 81.5% by mass, 16.5% by mass, and 2.0% by mass, respectively. The outermost layer is a copolymer obtained by polymerizing methyl methacrylate and methyl acrylate at a ratio of 94.5% by mass and 5.5% by mass, to obtain an innermost layer and an intermediate layer. The proportion of the outermost layer is 35% by mass, 45% by mass, and 20% by mass of the crosslinked rubber particles C1. In order to prevent C1 from blocking, the methacrylic polymer A1, which polymerizes methyl methacrylate and methyl acrylate at a ratio of 90% by mass to 10% by mass, with respect to 67% by mass of C1 and 33% by mass, is in a latex state. Mixing with C1, followed by salting out, to obtain a mixture D1 of crosslinked rubber particles C1 and a methacrylic polymer A1. [0062] In a polymerization reactor equipped with a stirrer, a mixture of 97.5 parts by mass of methyl methacrylate and 2.5 parts by mass of methyl acrylate and a 1,1-bis (third butyl peroxy) ring were continuously supplied, respectively. 0.016 parts by mass of hexane and 0.16 parts by mass of n-octyl mercaptan were polymerized at 255 ° C and an average residence time of 43 minutes. Next, the reaction solution (partial polymer) taken out from the polymerization reactor is preheated and then supplied to a devolatilizing extruder to vaporize and recover unreacted monomer components, and obtain granular methacrylic polymer A2 . The MFR of A2 is 2g / 10 minutes. [0063] As the epoxy group-containing polymer (B1), "BOND FAST BF-7M" (glycidyl methacrylate monomer unit: 6 mass%, ethylene monomer unit: 67 mass%, manufactured by Sumitomo Chemical) Methyl acrylate monomer unit: 27% by mass). [0064] A2, B1, and D1 are mixed at a ratio of 100 parts by mass of A1 and A2 to 1.2 parts by mass of B1 and 18.9 parts by mass of C1. Next, for 100 parts by mass of the resin component made of D1, A2, and B1, 0.27 parts by mass of titanium dioxide as an additive was added, and pentaerythritol [3- (3,5-di-third-butyl-4-hydroxyphenyl) propene] was added. Ester] 0.08 parts by mass of 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol 0.03 parts by mass, kneaded at 260 ° C. using a twin-screw extruder (model: TEX30SS-30AW-2V) made by Japan Steel, and pelletized. Using these particles, solvent resistance, warpage, and hardness evaluation were performed. The evaluation results are shown in Table 2. [Examples 2 to 7] Granules were obtained in the same manner as in Example 1 except that the total of A1 and A2 was 100 parts by mass, and the ratio of B1 and C1 was changed to the ratio described in Table 1. The obtained pellets were used for evaluation of solvent resistance, warpage and hardness. The evaluation results are shown in Table 2. [Comparative Examples 1 to 4] Granules were obtained in the same manner as in Example 1 except that the total of A1 and A2 was 100 parts by mass, and the ratio of B1 and C1 was changed to the ratio described in Table 1. The obtained pellets were used for evaluation of solvent resistance, warpage and hardness. The evaluation results are shown in Table 2. [Example 8] Instead of B1, "BOND FAST BF-7L" manufactured by Sumitomo Chemical (glycidyl methacrylate monomer unit: 3% by mass, ethylene monomer unit: 70% by mass, methyl acrylate Monomer unit: 27% by mass) A granule was obtained in the same manner as in Example 7 except that it was an epoxy group-containing polymer B2. The obtained pellets were used for evaluation of solvent resistance, warpage and hardness. The evaluation results are shown in Table 2. [Example 9] Instead of B1, "BOND FAST BF-2C" (glycidyl methacrylate monomer unit: 6 mass%, ethylene monomer unit: 94 mass%) manufactured by Sumitomo Chemical was used as the ring-containing ring. Particles were obtained in the same manner as in Example 7 except for the oxy-polymer B3. The obtained pellets were used for evaluation of solvent resistance, warpage and hardness. The evaluation results are shown in Table 2. [Example 10] Instead of B1, "BOND FAST BF-E" (glycidyl methacrylate monomer unit: 12% by mass, ethylene monomer unit: 88% by mass) manufactured by Sumitomo Chemical was used as the ring-containing compound. Particles were obtained in the same manner as in Example 7 except for the oxy-polymer B4. The obtained pellets were used for evaluation of solvent resistance, warpage and hardness. The evaluation results are shown in Table 2. [0070] [0071] In addition, an empty column in Table 1 indicates that an epoxy group-containing polymer is not contained. [0072] [0073] In addition, an empty column in Table 2 indicates that it has not been measured. In addition, the result of the repeated test of the solvent resistance is "16th or more", which means that cracks did not occur even at the 15th time. [0074] From the results in Table 2, it can be seen that the solvent resistance levels of Comparative Examples 1 and 4 are-, the solubility resistance is poor, the hardness of Comparative Example 2 is lower than that of the example, and the warpage value of Comparative Example 3 is compared with the example. It is small and cannot suppress warpage during molding. [Example 11] In a polymerization reactor equipped with a stirrer, a mixture of 96 parts by mass of methyl methacrylate and 4 parts by mass of methyl acrylate and 1,1-di (third butyl) were continuously supplied, respectively. Polymerization was performed at 0.015 parts by mass of peroxy) cyclohexane and 0.27 parts by mass of n-octyl mercaptan at 255 ° C and an average residence time of 43 minutes. Next, after the reaction solution (partial polymer) taken out from the polymerization reactor is preheated, it is supplied to a devolatilizing extruder to vaporize and recover unreacted monomer components, and obtain granular methacrylic polymer A3. . The MFR of A3 is 11 g / 10 minutes. [0076] A granule was obtained in the same manner as in Example 4 except that A3 was used instead of A2. The obtained pellets were used for evaluation of solvent resistance, warpage and hardness. As a result, the solvent resistance drop test was Y, the solvent resistance repeat test was the first time, and the solvent resistance level was +. The warpage was 1.5, the injection pressure was 228 MPa, and the pencil hardness was 2H. [Comparative Example 5] The same procedure as in Example 7 was performed except that "ACRYFT WK307" (ethylene monomer unit: 75% by mass, methyl methacrylate monomer unit: 25% by mass) manufactured by Sumitomo Chemical was used instead of B1. Particles were obtained in the same way. The obtained pellets were used for evaluation of solvent resistance, warpage and hardness. As a result, the solvent resistance dropping test was X, the solvent resistance repetition test was the ninth time, and the solvent resistance rating was-. The warpage was 1.5, the injection pressure was 227 MPa, and the pencil hardness was 2H. From these results, it was found that the solvent resistance of Comparative Example 5 was poor.

[0078]

1‧‧‧ Crosslinked rubber particles (C)

2‧‧‧ outermost

3‧‧‧ middle layer

4‧‧‧ innermost

[0009] FIG. 1 is a cross-sectional view of a crosslinked rubber particle (C) according to an embodiment.

Claims (4)

A thermoplastic resin composition containing 100 parts by mass of a methacrylic polymer (A) containing 85 to 100% by mass of monomer units derived from methyl methacrylate, and containing 1) to 50% by mass of monomer units of acrylate, 50 to 99% by mass of monomer units derived from at least one monomer selected from the group consisting of ethylene, α-olefins having 3 or more carbon atoms, and styrene The epoxy-group-containing polymer (B) is 0.1 parts by mass or more and 100 parts by mass or less, and contains a polymer derived from an alkyl (meth) acrylate, butadiene, isoprene, chloroprene, and benzene. Polyfunctional units of at least one monomer in a group of ethylene, α-alkylstyrene, acrylonitrile, and methacrylonitrile, and polyfunctionality derived from a polyfunctional monomer having more than two carbon-carbon double bonds The crosslinked rubber particles (C) of the monomer unit resin are 0.01 parts by mass or more and 25 parts by mass or less. The thermoplastic resin composition according to claim 1, wherein the epoxy-containing polymer (B) further contains a monomer unit derived from an alkyl (meth) acrylate, and the aforementioned monomer derived from an alkyl (meth) acrylate The content of the unit is relative to the above-mentioned monomer unit derived from the epoxy-containing (meth) acrylate and the source derived from the group selected from the group consisting of ethylene, α-olefins having 3 or more carbon atoms, and styrene. The total amount of the monomer units of the at least one monomer is 100 parts by mass, and is 0.1 to 50 parts by mass. A formed body containing the thermoplastic resin composition as claimed in claim 1 or 2. A water rewinding article containing a shaped body as claimed in claim 3.