JP2018095666A - Thermoplastic resin composition and molded article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in balance among mechanical characteristics, moldability, weather resistance and resistance to yellowing in dark, and is also excellent in adhesion to a silicone sealing material, and to provide a molded article of the thermoplastic resin composition.SOLUTION: The thermoplastic resin composition is provided that is obtained by blending 3-8 pts.wt. of a copolymer (III) composed of an ethylene-(meth)acrylate-carbon monooxide with 100 pts.wt. of a resin composition composed of 20-70 pts.wt. of a graft copolymer (I) obtained by graft polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer and 80-30 pts.wt. of a vinyl-based copolymer (II) obtained by copolymerization of an aromatic vinyl-based monomer, a vinyl cyanate-based monomer and other vinyl-based monomer copolymerizable with the monomers, in the presence of an acrylic rubbery polymer obtained by copolymerization of an acrylate-based monomer and a polyfunctional monomer.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition having excellent balance of mechanical properties, molding processability, weather resistance and dark yellowing resistance, and excellent adhesion to a silicone sealant, and a molded product thereof.

Conventionally, rubber-reinforced thermoplastic resins such as ABS resin are used for housing / building material parts, household appliances, OA equipment, miscellaneous goods, automotive interior / exterior, etc. due to excellent moldability, good mechanical property balance, and surface appearance. It is used for many typical exterior parts.

  In particular, in recent years, ABS resins have been widely used in residential applications such as bathroom interior materials.

  Now, in general, in housing applications, silicone sealing materials are often used to seal and bond parts, but the sealing material may peel off from the molded product, or the molded product and sealing material There is a problem that water or the like enters a gap between the bonding surfaces. The types of silicone sealant include deacetic acid type, deoxime type, and dealcohol type, and the deoxime type is widely used for reasons such as low cost and low irritating odor. However, it is known that the adhesion between the deoxime-type silicone sealant and the ABS resin is not so good, and the above-mentioned problems are likely to occur.

  As means for improving such problems, a resin composition (Patent Document 1) or a polybutylene terephthalate (PBT) resin in which an ABS resin is blended with a copolymer of ethylene, (meth) acrylic acid ester, and carbon monoxide. A technique for improving adhesiveness by a resin composition (Patent Document 2) in which is added is disclosed.

  However, it is generally known that ABS resin is a resin that easily undergoes yellowing such as light yellowing due to ultraviolet rays, and yellowing in a dark place that easily proceeds in a high-temperature and high-humidity environment. Although measures may be taken by blending an antioxidant with the ABS resin in advance, this is not sufficient.

  In addition, as a technology for improving weather resistance and adhesion of silicone sealants, it is possible to use polyorganosiloxane and alkyl (meth) acrylate rubber, which have a specific relationship between the amount of vinyl cyanide compound in acetone and insoluble matter. Although a resin composition (Patent Document 3) comprising a graft copolymer and a vinyl copolymer is disclosed, it cannot be said that the adhesiveness of the silicone sealing material is still sufficient.

JP 2004-115607 A JP 2004-115606 A JP 2004-189983 A

  An object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties, molding processability, weather resistance and dark yellowing resistance and excellent adhesion to a silicone sealant, and a molded product thereof. And

  As a result of intensive studies to solve the above problems, the present inventors have identified a graft copolymer, a vinyl copolymer, and a copolymer composed of ethylene, (meth) acrylic acid ester, and carbon monoxide. By blending with the composition, it was found that the mechanical properties, molding processability, weather resistance and dark yellowing resistance were excellent, and that the adhesiveness to the silicone sealing material was excellent, and the present invention was achieved.

That is, this invention is comprised by the following (1)-(4).
(1) An aromatic vinyl monomer and a vinyl cyanide monomer in the presence of an acrylic rubbery polymer obtained by copolymerizing an acrylate monomer and a polyfunctional monomer. 30 to 60 parts by weight of graft copolymer (I) obtained by graft polymerization of a monomer mixture containing, aromatic vinyl monomer and vinyl cyanide monomer, and others copolymerizable therewith From 100 parts by weight of a resin composition consisting of 70 to 40 parts by weight of a vinyl copolymer (II) obtained by copolymerizing the above vinyl monomers, from ethylene, (meth) acrylate and carbon monoxide. A thermoplastic resin composition comprising 3 to 8 parts by weight of the copolymer (III).
(2) The thermoplastic resin composition according to (1), wherein the other vinyl monomer copolymerizable with the vinyl copolymer (II) is an unsaturated carboxylic acid alkyl ester monomer.
(3) The thermoplastic resin assembly according to (1) or (2), wherein a melt flow rate (220 ° C., 98N condition) according to ISO 1130 is 15 to 40 g / 10 min.
(4) A molded product obtained by molding the thermoplastic resin composition according to any one of (1) to (3).

  According to the present invention, it has a good balance of mechanical properties, moldability, weather resistance, and yellowing resistance in dark places, and also has excellent adhesion to a silicone sealant, so it is widely used in residential applications such as bathroom interior materials. Can be used.

  Hereinafter, the thermoplastic resin composition of the present invention and the molded product thereof will be specifically described.

  The graft copolymer (I) composing the thermoplastic resin composition of the present invention is an acrylic rubbery polymer (A) obtained by copolymerizing an acrylate monomer and a polyfunctional monomer. Is a graft copolymer obtained by graft polymerization of a monomer mixture containing an aromatic vinyl monomer (B) and a vinyl cyanide monomer (C).

  Consists of an acrylic rubbery polymer (A) obtained by copolymerizing an acrylic ester monomer (a) and a polyfunctional monomer (b) that can be used in the graft copolymer (I) As the acrylate ester monomer (a), those having an alkyl group having 1 to 10 carbon atoms are preferable, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, Examples include octyl acrylate. Two or more of these may be used. Among these, n-butyl acrylate is preferable.

  The polyfunctional monomer (b) constituting the acrylic rubber polymer (A) is not particularly limited as long as it has two or more functional groups. Examples of functional groups include allyl groups, (meta ) A group having a carbon-carbon double bond such as an acryloyl group. Examples of the polyfunctional monomer (b) include allyl compounds such as allyl acrylate, allyl methacrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol. Examples thereof include di (meth) acrylic acid ester compounds such as dimethacrylate and propylene glycol dimethacrylate. Two or more of these may be used. Among these, allyl methacrylate is preferable because the degree of gel swelling of the acrylic rubber polymer (A) described later in toluene and the graft ratio of the graft copolymer (I) can be easily adjusted to a desired range.

  The acrylic rubbery polymer (A) in the present invention is an acrylic acid ester monomer with respect to a total of 100% by weight of the acrylic acid ester monomer (a) and the polyfunctional monomer (b). (A) It is preferable to obtain by copolymerizing 97 to 99.5% by weight and 3 to 0.5% by weight of the polyfunctional monomer (b). When the acrylic ester monomer (a) is 97 wt.% Or more and the polyfunctional monomer (b) is 3 wt.% Or less, an acrylic rubber polymer (A) described later in a gel in toluene The degree of swelling increases and the graft ratio of the graft copolymer (I) described later decreases. As a result, the fluidity of the thermoplastic resin composition is improved, and the particles of the graft copolymer (I) can be aggregated, so that the impact strength and surface impact property of the molded product are improved. The acrylate monomer (a) is preferably 98% by weight or more, the polyfunctional monomer (b) is preferably 2% by weight or less, and the acrylate ester monomer (a) is 98.5%. More preferably, the polyfunctional monomer (b) is more than 1.5% by weight and less than 1.5% by weight. On the other hand, when the acrylate monomer (a) is 99.5% by weight or less and the polyfunctional monomer (b) is 0.5% by weight or more, the graft copolymer (I) described later The graft ratio is improved, and the impact strength and surface impact of the molded product are improved. The acrylate monomer (a) is preferably 99.3% by weight or less, more preferably 99.0% by weight or less. Moreover, it is preferable that a polyfunctional monomer (b) is 0.7 weight% or more, More preferably, it is 1.0 weight% or more.

  In the present invention, the volume average particle diameter of the acrylic rubbery polymer (A) is preferably in the range of 0.10 to 0.30 μm. When the volume average particle diameter of the acrylic rubbery copolymer (A) is 0.10 μm or more, the primary particles in the agglomerated particles described later can maintain their original shape, so the impact strength and surface impact of the molded product are improved. To do. 0.15 μm or more is preferable. On the other hand, when the volume average particle diameter of the acrylic rubbery copolymer (A) is 0.30 μm or less, the dispersibility of the graft copolymer (I) in the thermoplastic resin composition is improved. Improves impact resistance and surface impact resistance. It is preferably 0.25 μm or less.

  The volume average particle diameter of the acrylic rubber polymer (A) can be measured by dispersing the acrylic rubber polymer (A) latex in water and using a laser scattering diffraction particle size distribution analyzer. .

  The volume average particle diameter of the acrylic rubbery polymer (A) can be adjusted to a desired range by, for example, the amount of water, emulsifier, polymerization initiator, etc. used in the polymerization.

  The gel swelling degree (α) in toluene of the acrylic rubbery polymer (A) is preferably 10 times or more. The gel swelling degree (α) is an index representing the degree of crosslinking of the acrylic rubber polymer (A). When the gel swelling degree (α) is 10 times or more, the particles of the graft copolymer (I) It becomes easy to aggregate each other, and can improve the fluidity of the thermoplastic resin composition, the impact strength and the surface impact of the molded product. 12 times or more is more preferable.

In addition, the gel swelling degree ((alpha)) in toluene of an acrylic rubber-like polymer (A) can be calculated | required with the following method. First, in the case of the acrylic rubber polymer (A) latex, a latex and sulfuric acid are added to methanol, and then a solid of the acrylic rubber polymer (A) is obtained by dehydration and washing. The obtained solid material of the acrylic rubbery polymer (A) is vacuum-dried at 80 ° C. for 3 hours, then impregnated with toluene for 24 hours, and the weight (y) [g] of the swollen sample is measured. . Subsequently, after vacuum drying at 80 ° C. for 3 hours, the weight (z) [g] of the dried sample is measured. The gel swelling degree (α) is calculated from the following formula from the weight (y) [g] of the swollen sample and the weight (z) [g] of the sample after drying.
Gel swelling degree (times) = (y) / (z).

  Further, the degree of gel swelling in toluene of the acrylic rubbery polymer (A) can be adjusted to a desired range by, for example, the amount of polyfunctional monomer, emulsifier and initiator used for polymerization. For example, regarding the copolymerization ratio of the polyfunctional monomer, the acrylate monomer (a) exceeds 98.5% by weight, and the polyfunctional monomer (b) is less than 1.5% by weight. It is preferable that

  The gel swelling degree content in toluene of the acrylic rubbery copolymer (A) is preferably 80 to 98% by weight. When the gel content swelling degree is 80% by weight or more and 98% by weight or less, the elasticity of the acrylic rubber polymer (A) is improved, and the impact resistance and surface impact property of the molded product can be further improved. it can. 85 to 95% by weight or less is more preferable.

In addition, the gel content rate in toluene of an acrylic rubber-like polymer (A) can be calculated | required with the following method. First, in the case of the acrylic rubber polymer (A) latex, a latex and sulfuric acid are added to methanol, and then a solid of the acrylic rubber polymer (A) is obtained by dehydration and washing. The obtained acrylic rubbery polymer (A) was vacuum dried at 80 ° C. for 3 hours and then impregnated with a predetermined amount (x) [g] in toluene for 24 hours. [G] is measured. Subsequently, after vacuum drying at 80 ° C. for 3 hours, the weight (z) [g] of the dried sample is measured. The gel content is calculated from the following formula from the weight (x) [g] of the sample and the weight (z) [g] of the sample after drying.
Gel content (% by weight) = ([z] / [x]) × 100.

  The gel content of the acrylic rubbery polymer (A) can be adjusted to a desired range by, for example, the amounts of polyfunctional monomers, emulsifiers, and initiators used for polymerization.

  As a polymerization method of the acrylic rubbery polymer (A), any method such as an emulsion polymerization method, a suspension polymerization method, a continuous bulk polymerization method, and a solution continuous polymerization method can be used. You may combine them. Among these, an emulsion polymerization method or a bulk polymerization method is preferable. The emulsion polymerization method is most preferred because the volume average particle size can be easily adjusted to a desired range by removing heat during polymerization.

  The emulsifier used in the emulsion polymerization method is not particularly limited, and various surfactants can be used. As the surfactant, anionic surfactants such as a carboxylate type, a sulfate ester type, and a sulfonate type are preferably used. Two or more of these may be used.

  Specific examples of anionic surfactants include caprylate, caprate, laurate, myristate, palmitate, stearate, oleate, linoleate, linolenate, rosinate , Behenate, castor oil sulfate, lauryl alcohol sulfate, dodecyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonate, naphthalene sulfonate condensate, dialkyl sulfosuccinate, polyoxyethylene Examples thereof include lauryl sulfate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkyl phenyl ether sulfate. Examples of the salt mentioned here include alkali metal salts such as ammonium salt, sodium salt, lithium salt and potassium salt.

  The initiator used for polymerization is not particularly limited, and peroxides, azo compounds, persulfates and the like are used.

  Specific examples of the peroxide include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butylisopropyl carbonate, di-t-butyl peroxide, t-butylperoctate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t -Butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate and the like.

  Specific examples of the azo compound include azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propyl. Azoformamide, 1,1′-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 1-t-butylazo- Examples include 2-cyanobutane and 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane.

  Specific examples of the persulfate include potassium persulfate, sodium persulfate, and ammonium persulfate.

  Two or more of these initiators may be used. For the emulsion polymerization method, potassium persulfate, cumene hydroperoxide and the like are preferably used. The initiator can also be used in a redox system.

  From the viewpoint of adjusting the volume average particle diameter of the acrylic rubbery polymer (A), the gel swelling degree in toluene, and the gel content to the above-mentioned preferable range, in the polymerization of the acrylic rubbery polymer (A), 80 to 200 parts by weight of water, 1.5 to 5 parts by weight of emulsifier, and initiator for 100 parts by weight of the total of the acrylic ester monomer (a) and the polyfunctional monomer (b) It is preferable to use 0.05 to 0.5 parts by weight.

  The graft copolymer (I) used in the present invention comprises an aromatic vinyl monomer (B) and a vinyl cyanide monomer (C) in the presence of the acrylic rubbery polymer (A). It is obtained by graft polymerization of a monomer mixture containing That is, the graft copolymer (I) was obtained by graft copolymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer to the acrylic rubber polymer (A). It is a copolymer.

  The blending amount of the acrylic rubber polymer (A) is 20 parts by weight with respect to a total of 100 parts by weight of the acrylic rubber polymer (A) and the monomer mixture constituting the graft copolymer (I). The above is preferable, and 30 parts by weight or more is more preferable. On the other hand, the blending amount of the acrylic rubbery polymer (A) is preferably 70 parts by weight or less, and more preferably 60 parts by weight or less. Further, the blending amount of the monomer mixture is preferably 30 parts by weight or more, and more preferably 40 parts by weight or more. On the other hand, the blending amount of the monomer mixture is preferably 80 parts by weight or less, and more preferably 70 parts by weight or less.

  The monomer mixture constituting the graft copolymer (I) contains an aromatic vinyl monomer (B) and a vinyl cyanide monomer (C), and if necessary, a monomer that can be copolymerized therewith The body (D) may further be included.

  Examples of the aromatic vinyl monomer (B) include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, and t-butylstyrene. Two or more of these may be used. Among these, styrene is preferable.

  Examples of the vinyl cyanide monomer (C) include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. Two or more of these may be used. Among these, acrylonitrile is preferable.

  The other copolymerizable monomer (D) is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include unsaturated carboxylic acid alkyl ester monomers, unsaturated fatty acids, and acrylamides. Monomers, maleimide monomers and the like. Two or more of these may be used.

  Examples of unsaturated carboxylic acid alkyl ester monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Examples include t-butyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, and the like. Two or more of these may be used.

  Examples of the unsaturated fatty acid include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid. Two or more of these may be used.

  Examples of the acrylamide monomer include acrylamide, methacrylamide, N-methylacrylamide and the like. Two or more of these may be used.

  Examples of maleimide monomers include N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like. Is mentioned. Two or more of these may be used.

  The mixing ratio of the monomer mixture is 60 to 80% by weight of the aromatic vinyl monomer (B) and 20 to 20% of the vinyl cyanide monomer (C) in the total amount of the monomer mixture of 100% by weight. The range of 40% by weight and the other copolymerizable monomer (D) is preferably 0 to 20% by weight.

  The graft ratio (β) of the graft copolymer (I) is preferably 5 to 40%. The graft ratio (β) is an index representing the compatibility of the graft copolymer (I). If the graft ratio is 5% or more, the compatibility of the graft copolymer (I) in the thermoplastic resin composition is It is possible to improve the impact strength and surface impact of the molded product. 8% or more is more preferable. On the other hand, if the graft ratio is 40% or less, the particles of the graft copolymer (I) are easily aggregated in the thermoplastic resin composition, and the impact strength and surface impact property of the molded product can be further improved. it can. 35% or less is more preferable, and 30% or less is more preferable.

The graft ratio (β) of the graft copolymer (I) can be determined by the following method. First, 100 ml of acetonitrile is added to a predetermined amount (m; about 1.5 g) of the graft copolymer (I) which has been vacuum-dried at 80 ° C. for 3 hours, and refluxed in a 70 ° C. hot water bath for 3 hours. The solution is centrifuged at 9000 rpm for 40 minutes, the insoluble matter is filtered, the insoluble matter is vacuum dried at 80 ° C. for 5 hours, and the weight (n) is measured. The graft ratio (β) is calculated from the following formula. Here, L is the rubber content (% by weight) of the graft copolymer (that is, the content (% by weight) of the acrylic rubber-like polymer (A) in the graft copolymer).
Graft ratio (%) = {[(n) − ((m) × L / 100)] / [(m) × L / 100]} × 100.

  The graft ratio of the graft copolymer (I) is adjusted to a desired range by using, for example, the above-mentioned acrylic rubbery polymer (A) and the amount of chain transfer agent, emulsifier, initiator used in the polymerization, etc. Can do.

  As a polymerization method of the graft copolymer (I), any method such as an emulsion polymerization method, a suspension polymerization method, a continuous bulk polymerization method, and a solution continuous polymerization method can be used. Also good. Among these, an emulsion polymerization method or a bulk polymerization method is preferable. The emulsion polymerization method is most preferred because temperature control during the polymerization is easy.

  Examples of the emulsifier used in the emulsion polymerization method of the graft copolymer (I) include those exemplified as the emulsifier used in the emulsion polymerization method of the acrylic rubbery polymer (A). Examples of the polymerization initiator used for the polymerization of the graft copolymer (I) include those exemplified as the initiator used for the polymerization of the acrylic rubbery polymer (A).

  A chain transfer agent can also be used for the purpose of adjusting the degree of polymerization and graft ratio of the graft copolymer (I). Specific examples of the chain transfer agent include mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan and n-octadecyl mercaptan, and terpenes such as terpinolene. Two or more of these may be used. Among these, n-octyl mercaptan and t-dodecyl mercaptan are preferably used.

  From the viewpoint of adjusting the graft ratio of the graft copolymer (I) to the above-mentioned preferable range, in the polymerization of the graft copolymer (I), a total of 100 weights of the acrylic rubbery polymer (A) and the monomer mixture. It is preferable to use 0.05 to 0.5 parts by weight of the chain transfer agent, 0.5 to 5 parts by weight of the emulsifier, and 0.1 to 0.5 parts by weight of the initiator with respect to parts.

  The graft copolymer (I) can be recovered by adding a coagulant to the graft copolymer (I) latex produced by emulsion polymerization. As the coagulant, an acid or a water-soluble salt is used. Specific examples of the coagulant include acids such as sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid, calcium chloride, magnesium chloride, barium chloride, aluminum chloride, magnesium sulfate, aluminum sulfate, ammonium aluminum sulfate, potassium aluminum sulfate, and sodium aluminum sulfate. And water-soluble salts thereof. Two or more of these may be used. In addition, when solidifying with an acid, a method of recovering the graft copolymer (I) after neutralizing the acid with an alkali can also be used.

  By the above method, the acrylic rubbery polymer (A) is graft-copolymerized with a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer. All of the monomer mixture containing a monomer may not be graft copolymerized with the acrylic rubber polymer (A). Therefore, the graft copolymer (I) in the present invention contains a single monomer containing an aromatic vinyl monomer and a vinyl cyanide monomer that is not graft copolymerized with the acrylic rubber polymer (A). The copolymer which consists of a body mixture may be included.

  Examples of the graft copolymer (I) include acrylonitrile / acrylic rubbery polymer / styrene graft copolymer (ASA resin), methyl methacrylate / acrylic rubbery polymer / styrene graft copolymer (MSA resin), methyl Examples thereof include methacrylate, acrylonitrile, acrylic rubbery polymer, styrene graft copolymer (MASA resin), and the like. Of these, acrylonitrile, acrylic rubbery polymer, and styrene graft copolymer (ASA resin) are preferable.

  The vinyl copolymer (II) constituting the thermoplastic resin composition of the present invention is a vinyl copolymer obtained by copolymerizing at least an aromatic vinyl monomer and a vinyl cyanide monomer. is there. The aromatic vinyl monomer is preferably 20 to 85% by weight, vinyl cyanide monomer 1 to 40% by weight, and other copolymerizable monomer (d) 0 to 79% by weight. Here, as the aromatic vinyl monomer, vinyl cyanide monomer and other copolymerizable monomers constituting the vinyl copolymer (II), the graft copolymer described above can be used. The same monomers as the monomers (B), (C) and (D) described in the section of the combined (I) are used.

  The other copolymerizable monomer (D) is preferably an unsaturated carboxylic acid alkyl ester monomer from the viewpoint of color development and weather resistance. Among these, methyl (meth) acrylate is preferable.

  The vinyl copolymer (II) constituting the thermoplastic resin composition of the present invention is not limited in molecular weight, but preferably measured by gel permeation chromatography (GPC) using a tetrahydrofuran solvent. A thermoplastic resin composition having excellent impact resistance and molding processability by using a resin having a weight average molecular weight in the range of 10,000 to 400,000, more preferably in the range of 50,000 to 150,000. A thing is obtained.

  Examples of the vinyl copolymer (II) include acrylonitrile / styrene copolymer (AS resin), methyl methacrylate / acrylonitrile / styrene copolymer (MAS resin), and methyl methacrylate / styrene copolymer (MS resin). be able to. Of these, methyl methacrylate / acrylonitrile / styrene copolymer (MAS resin) is preferable.

  The thermoplastic resin composition of the present invention comprises 30 to 60 parts by weight of the graft copolymer (I), 100 parts by weight of the graft copolymer (I) and the vinyl copolymer (II). 70 to 40 parts by weight of the copolymer (II) is blended. When the blending amount of the graft copolymer (I) is less than 30 parts by weight and the blending amount of the vinyl copolymer (II) exceeds 70 parts by weight, the impact resistance of the molded product is lowered. From the viewpoint of further improving the impact resistance of the molded article, it is preferable to blend 35 parts by weight or more of the graft copolymer (I) and 65 parts by weight or less of the vinyl copolymer (II). On the other hand, when the blending amount of the graft copolymer (I) exceeds 60 parts by weight and the blending amount of the vinyl copolymer (II) is less than 40 parts by weight, the fluidity of the thermoplastic resin composition decreases. . It is preferable to blend 60 parts by weight or less of the graft copolymer (I) and 40 parts by weight or more of the vinyl copolymer (II).

  In the present invention, the method for producing the graft copolymer (I) and the vinyl copolymer (II) is not particularly limited, and bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, precipitation polymerization. And combinations thereof. There is no particular limitation on the monomer charging method, and it may be added all at once in the initial stage, or the addition method may be divided into several times in order to impart or prevent the composition distribution of the copolymer. .

  In the present invention, as the initiator used for the polymerization of the graft copolymer (I) and the vinyl copolymer (II), a peroxide or an azo compound is preferably used.

  Specific examples of the peroxide include, for example, benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl cumyl peroxide, t-butyl peroxide. Acetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxide, t-butyl peroctate, 1,1-bis (t-butylperoxy) 3, 3, 5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate and the like. Of these, cumene hydroperoxide and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane are particularly preferably used.

  Specific examples of the azo compound include azobisisobutyronitrile, azobis (2,4dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano- 2-propylazoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t -Butylazo-1-cyanocyclohexane, 2-t-butylazo-2-cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, and the like. Of these, azobisisobutyronitrile is particularly preferably used.

  When using these initiators, they are used alone or in combination of two or more.

  In carrying out the polymerization, chain transfer agents such as mercaptans and terpenes can be used for the purpose of adjusting the degree of polymerization of the graft copolymer (I) and the vinyl copolymer (II). Specific examples of the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and terpinolene. Of these, n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan are preferably used. When using these chain transfer agents, they are used alone or in combination of two or more.

As a copolymer (III) composed of ethylene, (meth) acrylic acid ester, and carbon monoxide, the acrylic group of (meth) acrylic acid ester has a linear or branched ester portion, and the carbon The number is preferably 1 to 18, and examples include methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, isobutyl group, hexyl group, 2-ethylhexyl group, and octyl group. And those having 2 to 8 carbon atoms are more preferred. The composition ratio of the copolymer (III) composed of ethylene, (meth) acrylic acid ester, and carbon monoxide is preferably 10 to 87% by weight of ethylene, more preferably 40 to 80% by weight, (meth). The acrylic acid ester is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, and carbon monoxide is preferably 5 to 40% by weight, more preferably 5 to 20% by weight. It can also be copolymerized with a copolymerizable monomer.

  The content of the copolymer (III) composed of ethylene, (meth) acrylic acid ester, and carbon monoxide is 3 to 8 weights per 100 parts by weight of the graft copolymer (I) and the vinyl copolymer (II). Part, preferably 5 to 7 parts by weight. If the content of the copolymer (III) composed of ethylene, (meth) acrylic acid ester, and carbon monoxide is less than 3 parts by weight, the resulting thermoplastic resin composition has insufficient adhesion to the silicone sealing material. When the amount exceeds 8 parts by weight, the rigidity is lowered, and further delamination occurs.

  The thermoplastic resin composition of the present invention preferably has a melt flow rate of 15 to 40 g / 10 min, more preferably 18 to 35 g / 10 min, measured at a temperature of 220 ° C. and a 98 N load condition in accordance with ISO 1133. More preferably, it is the range of 20-30 g / 10min. When the melt flow rate is 40 g / 10 min or more, there is a tendency for undulation defects to occur when used for the surface layer of a laminated molded product by coextrusion molding, which will be described later. On the other hand, when the melt flow rate is 15 g / 10 min or less, the laminated molded product As a surface layer, the moldability tends to deteriorate.

  Moreover, a well-known impact resistance improving material can be used in the range which does not impair the characteristic of this invention. Examples of impact resistance improvers that can be used include natural rubber, polyethylene such as low density polyethylene and high density polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / methyl acrylate copolymer, and ethylene / ethyl acrylate copolymer. , Ethylene / vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / butyl acrylate / glycidyl Ethylene-based elastomers such as methacrylate copolymers, ethylene / octene-1 copolymers, ethylene / butene-1 copolymers, polyethylene terephthalate / poly (tetramethylene oxide) grease Ruburokku copolymers, polyethylene terephthalate / isophthalate / poly polyester elastomers, such as (tetramethylene oxide) glycol block copolymer, MBS or acrylic core-shell elastomer, a styrene based elastomer are exemplified. These are not necessarily used alone, and two or more kinds can be used in combination.

  Moreover, it is also possible to add a filler in the range which does not impair the characteristic of this invention. Examples of the filler include fibers, plates, powders, granules, and the like, and any of them may be used in the present invention. Specifically, polyacrylonitrile (PAN) and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia Fibrous or whisker-like fillers such as fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, glass fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, Mica, talc, kaolin, silica, calcium carbonate, glass flakes, glass beads, glass microballoons, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, barium sulfate, calcium polyphosphate Powder such as graphite, and the like granular or platy filler. Two or more of these may be used. Among these, glass fiber is preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resin, and examples thereof include long fiber type, short fiber type chopped strands, and milled fiber. The surface of the filler may be treated with any coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. Further, it may be coated or focused with a thermoplastic resin such as ethylene / vinyl acetate copolymer, or a thermosetting resin such as epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. Good.

  In addition, a known matte improving material can be used as long as the characteristics of the present invention are not impaired. Matte improving materials that can be used include unsaturated nitrile-conjugated diene copolymer rubbers such as acrylonitrile-butadiene copolymer rubber, acrylonitrile-isoprene copolymer rubber, and acrylonitrile-butadiene-isoprene copolymer rubber. And acrylonitrile-butadiene-acrylic acid copolymer rubber and the like, and rubbers obtained by hydrogenating conjugated diene units in these rubbers. Other rubbers that may be used in combination with unsaturated nitrile-conjugated diene copolymer rubbers are rubbers that can be crosslinked with crosslinking agents commonly used in the rubber industry such as sulfur vulcanization systems and organic peroxide vulcanization systems. It is. Specific examples thereof include conjugated diene polymer rubbers such as polybutadiene rubber, styrene-butadiene copolymer rubber (random, block), natural rubber, polyisoprene rubber, polychloroprene rubber, and hydrides thereof, EPDM, and the like. .

  Further, as long as it does not impair the characteristics of the present invention, heat such as hindered phenolic antioxidants, sulfur-containing compound-based antioxidants, phosphorus-containing organic compound-based antioxidants, phenol-based, acrylate-based, etc. Antioxidants, UV absorbers such as benzotriazole, benzophenone, and succinate, decabromobiphenyl ether, tetrabromobisphenol A, chlorinated polyethylene, brominated epoxy oligomer, brominated polycarbonate, antimony trioxide, condensed phosphate Flame retardants and flame retardant aids such as antibacterial agents typified by silver antibacterial agents, antifungal agents, carbon black, titanium oxide, mold release agents, lubricants, pigments and dyes can also be added.

  The thermoplastic resin composition of the present invention can be obtained by melt-mixing each constituent resin component. Although there is no restriction | limiting in particular regarding the melt mixing method, The method of melt-mixing using a monoaxial or biaxial screw with a heating apparatus and the cylinder which has a vent is employable. The heating temperature at the time of melt mixing is usually selected from the range of 200 to 300 ° C., but it is also possible to freely set the temperature gradient at the time of melt mixing within a range that does not impair the object of the present invention. Further, when a biaxial screw is used, it may be rotated in the same direction or in different directions. Either a meshing type screw or a non-meshing type screw may be used.

  The method for molding the thermoplastic resin composition of the present invention is not particularly limited, but is a known method currently used for molding thermoplastic resins such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, gas assist molding and the like. The molding method is not particularly limited.

  By co-extrusion of the thermoplastic resin composition of the present invention and another resin, a laminated molded article having the thermoplastic resin of the present invention as a surface layer can be obtained. Other resins used for coextrusion molding with the thermoplastic resin composition of the present invention are not particularly limited, but are ABS resin, ASA resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin. Examples thereof include resins, polyamide-based resins, and thermoplastic resins containing these as main components. Of these, ABS resins and vinyl chloride resins are preferable from the viewpoints of processability and mechanical properties.

  The use of the molded article of the present invention is, for example, materials such as housing / building materials, electricity, electronics, automobiles, machinery, miscellaneous goods, chemical plants, aircraft, parts for space, etc. From the characteristics of the molded product and the effect thereof, it is effective for use in bonding with other members using a silicone sealant. Here, as another member material, it is a preferable aspect to use the composition of the present invention. The molded product of the present invention is preferably used as a building material / householding part, and is particularly suitable for bathroom interior materials such as bathroom window frames, unit bath frames, bus counters, and bath aprons, but is not limited thereto. It is not a thing.

  In order to describe the present invention more specifically, examples will be given below, but these examples do not limit the present invention in any way, and various modifications are possible. First, evaluation methods in each reference example, example, and comparative example are described below.

(1) Graft ratio 200 ml of acetone was added to a predetermined amount (m; about 1 g) of the graft copolymer (I) obtained as described below, and the mixture was refluxed in a hot water bath at a temperature of 70 ° C. for 3 hours. . p. m. After centrifuging at (10000 G) for 40 minutes, the insoluble matter was filtered. The obtained acetone-insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the mass (n; unit g) was measured. The graft ratio was calculated from the following formula. Here, L is the rubber content of the graft copolymer (a real number greater than 0 and less than 1).
Graft ratio (mass%) = {[(n) − {(m) × L}] / [(m) × L]} × 100.

(2) Weight average molecular weight The weight average molecular weight of methyl ethyl ketone soluble matter of the vinyl copolymer (II) obtained by the following is detected using a water gel permeation chromatography (GPC) apparatus, and a differential refractometer is detected. It was measured as a weight average molecular weight in terms of polystyrene measured under the conditions of MIXED-B (two) manufactured by Polymer Laboratories, distillate tetrahydrofuran, flow rate 1 ml / min, column temperature 40 ° C.

(3) Impact resistance Injection from pellets obtained in each Example and Comparative Example was dried in a hot air dryer at a temperature of 80 ° C. for 3 hours, and the cylinder temperature was set to 250 ° C. and the mold temperature was set to 60 ° C. Using a molding machine, a multipurpose test piece type A1 defined in JIS K 7139 was molded, and a Charpy impact strength was measured based on ISO 179 / 1eA using a type B2 test piece cut out from the multi-purpose test piece type A1.

(4) Flowability The pellets obtained in each Example and Comparative Example were dried for 3 hours in a hot air drier at a temperature of 80 ° C., and melt flow rate at a temperature of 220 ° C. and a load of 98 N in accordance with ISO 1133. Was measured.

(5) Rigidity For the pellets obtained in each Example and Comparative Example, the pellets of the thermoplastic resin composition dried in a hot air dryer at a temperature of 80 ° C. for 3 hours, the cylinder temperature at 250 ° C., and the mold temperature Using an injection molding machine set at 60 ° C., a multipurpose test piece type A1 defined in JIS K 7139 was molded, and the flexural modulus was measured according to ISO178.

(6) Silicone sealing material adhesion evaluation About the pellet obtained by each Example and the comparative example, the cylinder temperature 250 degreeC, the pellet of the thermoplastic resin composition dried for 3 hours in the hot air dryer of the temperature of 80 degreeC. Molding was performed with an injection molding machine set at a mold temperature of 60 ° C. to obtain plate test pieces (length 120 mm, width 100 mm, thickness 3 mm). Next, a silicone sealant is directly applied in the length direction of one side of each test piece without a primer, and the length is 100 mm × width 10 mm × thickness 6 mm. The test piece coated with the sealing material is left at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% Rh for 2 weeks to completely cure the sealing material, and the cured sealing material is pulled in a direction of 180 ° with respect to the surface. It was. At this time, the bonded state (cohesive failure) was evaluated as “◯”, the slightly bonded one was evaluated as “Δ”, and the one peeled off at the interface was evaluated as “×”. In addition, the following silicone sealing materials were used for evaluation.
・ SH780 (deoxime type silicone sealing material) manufactured by Toray Dow Corning Co., Ltd. ・ SE5010 (deoxime type silicone sealing material) manufactured by Toray Dow Corning Co., Ltd. ・ SE960 (dealcohol type silicone sealing material) Toray Made by Dow Corning.

(7) Weather resistance evaluation (ΔE ₁ *)
1 wt% of titanium oxide was added to the pellets obtained in each of the Examples and Comparative Examples, and after white coloring with a single screw extruder, the thermoplastic resin composition was dried in a hot air dryer at a temperature of 80 ° C. for 3 hours. The pellets were molded by an injection molding machine set to a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. to obtain plate test pieces (length 50 mm, width 30 mm, thickness 3 mm). Subsequently, light irradiation was performed for 2000 hours with an open frame carbon arc lamp type weather resistance tester (black panel temperature 63 ° C.), and ΔE ₂ * was evaluated. ΔE ₂ * is calculated from the measurement results of the L * value, a * value, and b * value before and after the test using a CCM (Spectrophotometer Macbeth 7000A) manufactured by Sumika Color Co., Ltd.

(8) Darkness yellowing resistance (ΔE ₂ *)
1 wt% of titanium oxide was added to the pellets obtained in each of the Examples and Comparative Examples, and after white coloring with a single screw extruder, the thermoplastic resin composition was dried in a hot air dryer at a temperature of 80 ° C. for 3 hours. The pellets were molded by an injection molding machine set to a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. to obtain plate test pieces (length 50 mm, width 30 mm, thickness 3 mm). Next, after irradiating light for 36 hours with an open frame carbon arc lamp type weather resistance tester (black panel temperature 63 ° C.), it was left in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 80% for 24 hours to obtain ΔE ₂ *. evaluated. ΔE ₂ * is calculated from the measurement results of the L * value, a * value, and b * value before and after the test using a CCM (Spectrophotometer Macbeth 7000A) manufactured by Sumika Color Co., Ltd.

Reference Example 1 Preparation of Graft Copolymer (I-1) [Step for Obtaining Acrylic Rubber Polymer]
130 parts by weight of pure water and 1 part by weight of a disproportionated potassium rosinate aqueous solution (in terms of solid content) are charged into a reaction vessel, heated to 75 ° C., and stirred with 19.8 parts by weight of n-butyl acrylate. And 0.2 part by weight of allyl methacrylate (mixture 1) were continuously added over 1 hour (first addition step). Subsequently, 8 parts by weight of a 2% by weight potassium persulfate aqueous solution and 1.5 parts by weight of a disproportionated potassium rosinate aqueous solution (in terms of solid content) were continuously added over 6 hours (second addition step). Also, 2 hours after the start of the addition of the aqueous potassium persulfate solution and the disproportionated potassium rosinate aqueous solution, a mixture (mixture 3) of 79.2 parts by weight of n-butyl acrylate and 0.8 parts by weight of allyl methacrylate was taken over 4 hours. (Third addition step). The acrylic rubber-like polymer (A-1) latex was obtained at a polymerization rate of 95% by holding for 1 hour after the addition was completed.

[Process for obtaining graft copolymer]
Subsequently, a mixture of 13.2 parts by weight of pure water, 0.48 parts by weight of anhydrous glucose, 0.26 parts by weight of sodium pyrophosphate and 0.01 parts by weight of ferrous sulfate, 0.4 parts by weight of potassium oleate and pure A mixture of 12.5 parts by weight of water, 50 parts by weight of acrylic rubber polymer (A-1) (in terms of solid content) and 94.3 parts by weight of pure water were charged into a reaction vessel, heated to 58 ° C. and stirred. A mixture (i) of 36.5 parts by weight of styrene, 13.5 parts by weight of acrylonitrile and 0.2 parts by weight of t-dodecyl mercaptan was continuously added over 4 hours. 0.5 hours after the start of continuous addition, the internal temperature was raised to 62 ° C., and a mixture of 0.3 parts by weight of cumene hydroperoxide, 2.0 parts by weight of potassium oleate and 12.5 parts by weight of pure water was paralleled. Then, it was continuously added over 5 hours. Subsequently, at the end of the addition of (i), the temperature was further raised to 65 ° C. to obtain a graft copolymer latex at a polymerization rate of 98%. 100 parts by weight of the latex obtained (in terms of solid content) was poured into 900 parts by weight of water at 85 ° C. with addition of 3 parts by weight of magnesium sulfate with stirring, solidified, and then dehydrated and dried to form a powder graft Copolymer (I-1) was obtained. The graft rate was 30%.

Reference Example 2 Preparation of Graft Copolymer (I-2) Reference Example 1 except that 50 parts by weight of a polybutadiene latex (in terms of solid content) was used instead of the acrylic rubbery polymer (A-1). In the same manner as described above, a graft copolymer (I-2) was produced. The graft rate was 35%.

Reference Example 3 Preparation of Vinyl Copolymer (II-1) A slurry obtained by suspension polymerization of a monomer mixture consisting of 70% by weight methyl methacrylate, 25% by weight styrene and 5% by weight acrylonitrile was prepared. A vinyl copolymer (II-1) was prepared through washing, dehydration and drying steps. The weight average molecular weight of the obtained vinyl copolymer (II-1) was 105,000.

Reference Example 4 Preparation of Vinyl Copolymer (II-2) A slurry obtained by suspension polymerization of a monomer mixture comprising 72% by weight of styrene and 28% by weight of acrylonitrile was subjected to washing, dehydration and drying steps. Then, a vinyl copolymer (II-2) was prepared. The weight average molecular weight of the obtained vinyl copolymer (II-2) was 120,000.

(Reference Example 5) Copolymer (III) made of ethylene, (meth) acrylic acid ester, carbon monoxide
“Elvalloy” HP-4051 manufactured by Mitsui DuPont Polychemical Co., Ltd. was used.

(Examples 1-7, Comparative Examples 1-7)
The graft copolymer (I), the vinyl copolymer (II), and the copolymer (III) composed of ethylene / (meth) acrylic acid ester / carbon monoxide are shown in the ratios shown in Tables 1 and 2. Further, 0.3 parts by weight of a light stabilizer (manufactured by ADEKA, “Adeka Stub LA-77Y”), 0.3 part by weight of an ultraviolet absorber (manufactured by ADEKA, “Adeka Stub LA-32”) In addition, it was mixed at 23 ° C. with a Henschel mixer. The obtained mixture was melt-kneaded with a 40 mmφ extruder at an extrusion temperature of 230 ° C., and extruded into a gut shape to be pelletized. A test piece was prepared from the obtained pellet using an injection molding machine (molding temperature 250 ° C., mold temperature 60 ° C.), and evaluated by the method described above. Table 1 shows the results of the examples and Table 2 shows the results of the comparative examples.

    Examples 1 to 7, that is, the thermoplastic resin composition of the present invention is excellent in the balance of mechanical properties, fluidity, and adhesiveness of the silicone sealant, and is excellent in weather resistance and dark yellowing. From the comparison between Examples 1 to 4 and Comparative Example 1, when the content of the graft copolymer (I) is less than the range specified in the present invention, the impact resistance is lowered and the fluidity is larger than the expected range. I understand. On the other hand, it can be seen that when the content of the graft copolymer (I) is larger than the range specified in the present invention, the fluidity and rigidity are lowered. From the comparison between Examples 5 and 6 and Comparative Examples 3, 4, and 5, the content of the copolymer (III) composed of ethylene, (meth) acrylic acid ester, and carbon monoxide is within the range specified in the present invention. If the amount is small, the adhesiveness of the silicone sealant deteriorates. If the amount is large, the adhesiveness is good, but the layer is peeled off. From the comparison between Examples 2 and 7 and Comparative Examples 6 and 7, when polybutadiene is used in the graft copolymer (II) instead of the acrylic rubbery polymer, the weather resistance and the yellowing resistance in the dark place are greatly deteriorated. I understand.

It is a thermoplastic resin composition that has a good balance of mechanical properties, molding processability, weather resistance, and yellowing resistance in the dark place, and also has excellent adhesion to silicone sealants, and is particularly preferred for building materials and residential parts. It can be suitably used for bathroom interior materials such as bathroom window frames, unit bath frames, bus counters, and bath apron. It can be suitably used in fields such as automobiles, OA equipment, home appliances, and miscellaneous goods other than for building materials and housing equipment.

Claims (4)

  A monomer containing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of an acrylic rubber polymer obtained by copolymerizing an acrylate monomer and a polyfunctional monomer. 20 to 70 parts by weight of graft copolymer (I) obtained by graft polymerization of the monomer mixture, aromatic vinyl monomer and vinyl cyanide monomer, and other vinyl copolymerizable therewith Copolymer of ethylene, (meth) acrylic acid ester, carbon monoxide with respect to 100 parts by weight of resin composition comprising 80-30 parts by weight of vinyl copolymer (II) obtained by copolymerizing monomers A thermoplastic resin composition comprising 3 to 8 parts by weight of combined (III).   The thermoplastic resin composition according to claim 1, wherein the other vinyl monomer copolymerizable with the vinyl copolymer (II) is an unsaturated carboxylic acid alkyl ester monomer.   The thermoplastic resin assembly according to claim 1 or 2, wherein a melt flow rate (220 ° C, 98N condition) according to ISO 1130 is 15 to 40 g / 10 min. The molded article formed by shape | molding the thermoplastic resin composition of any one of Claims 1-3.