JP2019006915A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

To provide a thermoplastic methacrylic acid ester resin composition excellent in impact resistance as well as transparency and fluidity, and a molded article thereof.SOLUTION: There is provided a copolymer (A) obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound, a vinyl cyanide compound, and a macro monomer, in which the macro monomer has polymethacrylic acid ester as a main skeleton and a vinyl group at one terminal of the polymethacrylic acid ester. There is provided a thermoplastic resin composition containing the copolymer (A) and a methacrylic acid ester resin (B) obtained by polymerizing a vinyl monomer mixture containing methacrylic acid ester (m2). There is provided a thermoplastic resin composition further containing a graft copolymer (C) by graft polymerization of a vinyl monomer mixture (m3) containing the aromatic vinyl compound, the vinyl cyanide compound to an ethylene α-olefin copolymer (D). There is provided a molded article by molding the thermoplastic resin.SELECTED DRAWING: None

Description

  The present invention provides a copolymer capable of providing a thermoplastic methacrylate ester resin composition having excellent impact resistance, transparency and fluidity, a thermoplastic resin composition containing the copolymer and molding thereof Related to goods.

  Improving the impact resistance of resin materials not only expands the applications of resin materials, but also makes it possible to respond to the reduction in thickness and size of molded products. Various techniques have been proposed so far for improving the impact resistance of resin materials. Among these, a technique for improving the impact resistance while maintaining the characteristics of the hard resin material by combining the rubber polymer and the hard resin material has already been industrialized. Examples of such materials include thermoplastic resins such as acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylic ester (ASA) resin, acrylonitrile-ethylene / α-olefin-styrene (AES) resin, and the like. .

  For example, Patent Document 1 discloses a method of using a methyl methacrylate resin as a hard resin material and adding an AES resin thereto.

  However, in the method described in Patent Document 1, since the compatibility between the AES resin and the methyl methacrylate resin is low, the transparency characteristic of the methyl methacrylate resin is remarkably lowered and the impact resistance is improved. The effect is also low.

  Patent Document 2 discloses a method in which an AES resin is added to a methyl methacrylate resin, and a random copolymer (MAS) resin of methyl methacrylate, acrylonitrile, and styrene is further added thereto.

  In the method of Patent Document 2, the MAS resin functions as a compatibilizer between the AS resin and the methyl methacrylate resin, and the refractive index of EPDM, which is a rubber component of the AES resin, and the methyl methacrylate resin are close. Although the impact resistance and transparency can be improved by adding a resin as compared with the case where the resin is not added, the effect is not sufficiently satisfactory.

JP 2005-132970 A Japanese Patent Laid-Open No. 9-272783

  The present invention relates to a copolymer that can be made into a thermoplastic resin composition excellent in impact resistance and fluidity without lowering the transparency of a methacrylic ester resin, and an impact resistance including the copolymer. It aims at providing the thermoplastic resin composition excellent in the property, transparency, and fluidity, and its molded article.

As a result of intensive studies to solve the above problems, the present inventors polymerized a vinyl monomer mixture (m1) containing an aromatic vinyl compound, a vinyl cyanide compound and a specific polymethacrylic ester macromonomer. The resulting copolymer (A) can effectively improve the impact resistance without lowering the transparency of the methacrylic ester resin, and a thermoplastic resin composition having good fluidity. The present invention has been completed.
That is, the gist of the present invention is as follows.

[1] A copolymer (A) obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound, a vinyl cyanide compound and a macromonomer, and the macromonomer is a polymethacrylate ester. A copolymer (A) which is a macromonomer having a main skeleton and a vinyl group at one end of the polymethacrylate.

[2] The number average molecular weight of the macromonomer is 1,000 to 20,000, and the content of the aromatic vinyl compound in 100% by mass of the vinyl monomer mixture (m1) is 45 to 72% by mass. The vinyl cyanide compound content is 15 to 23% by mass, the macromonomer content is 5 to 40% by mass, and the copolymer (A) has a mass average molecular weight of 30,000 to 1,000,000. The copolymer (A) according to [1], which is 000.

[3] The copolymer according to [1] or [2], which is an improver for a methacrylate ester resin (B) obtained by polymerizing a vinyl monomer mixture (m2) containing a methacrylate ester. (A).

[4] A methacrylic ester resin obtained by polymerizing the copolymer (A) according to any one of [1] to [3] and a vinyl monomer mixture (m2) containing a methacrylic ester ( A thermoplastic resin composition comprising B).

[5] The thermoplastic resin composition according to [4], wherein the content of the methacrylic acid ester in 100% by mass of the vinyl monomer mixture (m2) is 80 to 100% by mass.

[6] The content of the copolymer (A) in the total of 100% by mass of the copolymer (A) and the methacrylic ester resin (B) is 5 to 80% by mass, [4] or [5 ] The thermoplastic resin composition as described in.

[7] Further, the ethylene / α-olefin copolymer (D) includes a graft copolymer (C) obtained by graft polymerization of a vinyl monomer mixture (m3) containing an aromatic vinyl compound and a vinyl cyanide compound. [4] The thermoplastic resin composition according to any one of [6].

[8] The content of the aromatic vinyl compound in the vinyl monomer mixture (m3) 100% by mass is 65 to 82% by mass, and the content of the vinyl cyanide compound is 18 to 35% by mass. [7] The thermoplastic resin composition according to [7].

[9] The ethylene / α-olefin copolymer (D) content in the total of 100% by mass of the ethylene / α-olefin copolymer (D) and the vinyl monomer mixture (m3) is 50 to 50%. 80% by mass, the content of the vinyl monomer mixture (m3) is 20 to 50% by mass, and the graft ratio of the graft copolymer (C) is 25 to 100% [7] or [ [8] The thermoplastic resin composition according to [8].

[10] A crosslinked ethylene / α-olefin copolymer (E) obtained by crosslinking the ethylene / α-olefin copolymer (D) and containing the gel of the crosslinked ethylene / α-olefin copolymer (E) The thermoplastic resin composition according to any one of [7] to [9], wherein the rate is 35 to 75% by mass.

[11] The content of the copolymer (A) in a total of 100% by mass of the copolymer (A), the methacrylic ester resin (B), and the graft copolymer (C) is 5 to 40% by mass. The content of the methacrylic ester resin (B) is 20 to 85% by mass and the content of the graft copolymer (C) is 10 to 40% by mass, according to any one of [7] to [10] The thermoplastic resin composition as described.

[12] A molded product formed by molding the thermoplastic resin composition according to any one of [3] to [11].

  According to the present invention, there are provided a thermoplastic methacrylic ester resin composition having excellent impact resistance, transparency and fluidity, and a molded product thereof.

  Hereinafter, embodiments of the present invention will be described in detail.

  In the present specification, “unit” means a structural portion derived from a compound (monomer, ie, monomer) before polymerization, contained in the polymer. For example, “α-olefin unit” means It means “a structural portion derived from an α-olefin and contained in a polymer”. The content ratio of the monomer unit of each polymer corresponds to the content ratio of the monomer in the monomer mixture used for producing the polymer.

[Copolymer (A)]
The copolymer (A) of the present invention is obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound, a vinyl cyanide compound and a macromonomer, and the macromonomer is a polymethacrylate ester. Is a macromonomer having a main skeleton and a vinyl group at one end of the polymethacrylic acid ester.

<Macromonomer>
Examples of the methacrylic acid ester which is the main skeleton of the macromonomer constituting the copolymer (A) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, and methacrylic acid. i-butyl, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, etc. Although 1 type or 2 types or more are mentioned, Among these, alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate are preferable. Special Methyl methacrylate, ethyl methacrylate are preferred for the same reason as methacrylic acid ester used in the later of the methacrylate-based resin (B).

  The polymethacrylic acid ester which is the main skeleton of the macromonomer is described later in terms of impact resistance and transparency of the thermoplastic resin composition obtained by blending the copolymer (A) of the present invention and its molded product. The methacrylic acid ester constituting the methacrylic acid ester resin (B), that is, the polymethacrylic acid ester contained in the vinyl monomer mixture (m2) is preferably the same structure. Therefore, for example, when the methacrylic acid ester contained in the vinyl monomer mixture (m2) is methyl methacrylate, the methacrylic acid ester which is the main skeleton of the macromonomer is also preferably methyl methacrylate.

  The macromonomer used by this invention is not limited to what is comprised only with a polymethacrylic acid ester unit, and may contain another vinyl-type monomer unit. Examples of other vinyl monomers include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid esters other than polymethacrylic acid esters, silicone compounds, and the like. The content of the ester unit is preferably 80% by mass or more from the viewpoint of impact resistance and transparency of the resulting thermoplastic resin composition and its molded product.

  Further, the number average molecular weight of the macromonomer is 1,000 to 20,000, particularly 2,000 to 15,000. The resulting thermoplastic resin composition and its molded article have impact resistance, transparency, fluidity. From the viewpoint of sex. When the number average molecular weight of the macromonomer is less than the above lower limit, the molecular chain length of the branch component (macromonomer main skeleton) in the copolymer (A) obtained is too short, and the effect of improving impact resistance and transparency is not satisfactory. On the other hand, when the above upper limit is exceeded, the polymerizability is poor, and it is difficult to introduce a target amount of the macromonomer into the copolymer (A). Here, the number average molecular weight of the macromonomer is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  As a commercially available product of the above macromonomer, for example, “AA-6” manufactured by Toagosei Chemical Industry Co., Ltd., which has methyl methacrylate as the main skeleton and has a vinyl group at one end is mentioned.

  Only one type of macromonomer may be used, or two or more types of different methacrylic acid esters may be mixed and used.

  The content of the macromonomer unit in the copolymer (A) is 5 to 40% by mass, particularly 10 to 30% by mass, and the resulting thermoplastic resin composition and the impact resistance and transparency of the molded product thereof. From the viewpoint of fluidity. That is, the content of the macromonomer in the vinyl monomer mixture (m1) is preferably 5 to 40% by mass, particularly 10 to 30% by mass. If the content of the macromonomer is less than the above lower limit, the effect of improving the impact resistance and transparency by introducing the macromonomer cannot be sufficiently obtained. It tends to be difficult to introduce the macromonomer into the copolymer (A).

<Aromatic vinyl compound>
Examples of the aromatic vinyl compound constituting the copolymer (A) include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, and ethyl styrene. These may be used alone or in combination of two or more.

  The structure of the aromatic vinyl compound is not particularly limited, but when used in combination with the graft copolymer (C) described later, the aromatic vinyl compound unit constituting the graft copolymer (C), that is, the vinyl described below. The same structure as the aromatic vinyl compound contained in the monomer mixture (m3) is preferred from the viewpoint of impact resistance and transparency of the resulting thermoplastic resin composition and its molded product.

  The content of the aromatic vinyl compound unit in the copolymer (A) is 45 to 72% by mass, particularly 52 to 68% by mass, and the resulting thermoplastic resin composition and the impact resistance of the molded product thereof, It is preferable in terms of transparency. That is, the content of the aromatic vinyl compound in the vinyl monomer mixture (m1) is preferably 45 to 72 mass%, particularly preferably 52 to 68 mass%. When the content of the aromatic vinyl compound is less than the above lower limit, the fluidity tends to deteriorate, and when the content exceeds the upper limit, the impact resistance decreases and the transparency tends to deteriorate.

<Vinyl cyanide compound>
Examples of the vinyl cyanide compound constituting the copolymer (A) include acrylonitrile and methacrylonitrile, and one or more of these can be used.

  The structure of the vinyl cyanide compound is not particularly limited, but when used in combination with the graft copolymer (C) described later, the vinyl cyanide compound unit constituting the graft copolymer (C), that is, the vinyl described below The same structure as the vinyl cyanide compound contained in the monomer mixture (m3) is preferable from the viewpoint of impact resistance and transparency of the resulting thermoplastic resin composition and its molded product.

  The content of the vinyl cyanide compound unit in the copolymer (A) is 15 to 23% by mass, particularly 18 to 22% by mass, and the resulting thermoplastic resin composition and the impact resistance of the molded product thereof, It is preferable in terms of transparency. That is, the content of the vinyl cyanide compound in the vinyl monomer mixture (m1) is preferably 15 to 23% by mass, and particularly preferably 18 to 22% by mass. If the content of the vinyl cyanide compound is less than the above lower limit, the impact resistance tends to decrease, and if it exceeds the above upper limit, the fluidity tends to deteriorate and the transparency tends to deteriorate.

<Other vinyl monomers>
The copolymer (A) of the present invention contains other vinyl monomer units other than the above macromonomer unit, aromatic vinyl compound unit and vinyl cyanide compound unit as long as the effects of the present invention are not impaired. You may go out. That is, the vinyl monomer mixture (m1) contains, in addition to the macromonomer, aromatic vinyl compound, and vinyl cyanide compound, other vinyl monomers copolymerizable with these, May be included in a range that does not impair.

Examples of other vinyl monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, Methacrylic acid esters such as amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate,
N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, etc. N-cycloalkylmaleimide, N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-arylmaleimide such as N-chlorophenylmaleimide, and maleimide compounds such as N-aralkylmaleimide,
Examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. These may be used alone or in combination of two or more.

<Manufacturing method>
The method for producing the copolymer (A) is not particularly limited, and examples thereof include known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, and miniemulsion polymerization.

<Mass average molecular weight>
The weight average molecular weight of the copolymer (A) of the present invention is a value obtained by dissolving in tetrahydrofuran (THF) using gel permeation chromatography (GPC) and measured in terms of standard polystyrene. It is preferably 1,000,000, particularly 40,000 to 800,000.
When the weight average molecular weight of the copolymer (A) is not less than the above lower limit, transparency tends to be excellent, and when it is not more than the above upper limit, both transparency and fluidity tend to be excellent.

[Methacrylate ester resin (B)]
The methacrylic ester resin (B) contained in the thermoplastic resin composition of the present invention is obtained by polymerizing a vinyl monomer mixture (m2) containing a methacrylic ester.

  Examples of the methacrylic acid ester constituting the methacrylic ester resin (B) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate. , T-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, etc. These may use only 1 type and may use 2 or more types. Among these, it is preferable to use at least one of methyl methacrylate and ethyl methacrylate because the resulting thermoplastic resin composition and the molded product thereof are more excellent in impact resistance and transparency.

  The methacrylic ester resin (B) used in the present invention is not limited to those composed only of methacrylic ester units, and may contain other vinyl monomer units as necessary. . That is, the vinyl monomer mixture (m2) may contain other vinyl monomers other than polymethacrylic acid ester, but the methacrylic acid ester unit in the methacrylic acid ester resin (B). The content is 80 to 100% by mass, particularly 85 to 100% by mass, that is, the content of the methacrylic acid ester in the vinyl monomer mixture (m2) is 80 to 100% by mass, particularly 85 to 100% by mass. It is preferable. When the content of the methacrylic acid ester is not less than the above lower limit, the resulting thermoplastic resin composition and the molded product thereof have excellent transparency.

  Other vinyl monomer units that may be contained in the methacrylic ester resin (B), that is, other vinyl monomers that may be contained in the vinyl monomer mixture (m2) Examples thereof include acrylic acid esters, aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, maleimide compounds such as N-phenylmaleimide, and maleic anhydride, and one or more of these can be used. .

  Among other vinyl monomers that may be contained in the vinyl monomer mixture (m2), the acrylate ester includes alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples thereof include alkyl acrylates having 1 to 4 carbon atoms, and these can be used alone or in combination of two or more. When the vinyl monomer mixture (m2) contains an acrylate ester, an effect that depolymerization hardly occurs can be obtained. In this case, the acrylic ester content in the vinyl monomer mixture (m2) is preferably 20% by mass or less, for example, 0.1 to 20% by mass.

  The maleimide compound contained in the vinyl monomer mixture (m2) is not particularly limited. For example, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, N- N-butylmaleimide, N-i-butylmaleimide, N-alkylmaleimide such as N-tert-butylmaleimide, N-cycloalkylmaleimide such as N-cyclohexylmaleimide, N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N -N-arylmaleimides such as chlorophenylmaleimide, N-aralkylmaleimides and the like can be mentioned, and these can be used alone or in combination of two or more. Especially, since a thermoplastic resin composition excellent in heat resistance and impact resistance is obtained, N-arylmaleimide is preferable, and N-phenylmaleimide is particularly preferable.

  When the vinyl monomer mixture (m2) contains the maleimide compound, the content is preferably 5 to 20% by mass. When the content of the maleimide compound is within the above range, the resulting thermoplastic resin composition has excellent heat resistance and fluidity.

  Moreover, it does not specifically limit as an aromatic vinyl compound contained in a vinyl-type monomer mixture (m2), For example, styrene, (alpha) -methylstyrene, o-, m- or p-methylstyrene, vinyl xylene, p- Examples thereof include t-butyl styrene and ethyl styrene, and these can be used alone or in combination of two or more.

  When the vinyl monomer mixture (m2) contains an aromatic vinyl compound, the reactivity with the aforementioned N-substituted maleimide and methacrylic acid ester becomes good, and the resulting thermoplastic resin composition is scratch resistant and resistant. In this case, the content of the aromatic vinyl compound in the vinyl monomer mixture (m2) is preferably 1 to 20% by mass.

  It does not restrict | limit especially as a manufacturing method of a methacrylic ester resin (B), Well-known methods, such as emulsion polymerization, suspension polymerization, block polymerization, and solution polymerization, are mentioned. From the viewpoint of heat resistance of the obtained thermoplastic resin composition, suspension polymerization and bulk polymerization are preferred.

[Graft Copolymer (C)]
The graft copolymer (C) contained in the thermoplastic resin composition of the present invention is a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in an ethylene / α-olefin copolymer (D). (M3) is obtained by graft polymerization.
The ethylene / α-olefin copolymer (D) contained in the graft copolymer (C) is a crosslinked ethylene / α-olefin obtained by crosslinking the ethylene / α-olefin copolymer (D). A copolymer (E) may be sufficient.

<Ethylene / α-olefin copolymer (D)>
In the present invention, an ethylene / α-olefin copolymer is used as a rubber component of the graft copolymer (C) in order that the resulting thermoplastic resin composition and its molded product exhibit excellent impact resistance and transparency. It is important to use (D). The ethylene / α-olefin copolymer (D) includes an ethylene unit and an α-olefin unit obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms by a known polymerization method. It is a copolymer.

  The ethylene / α-olefin copolymer (D) may be an ethylene / α-olefin / nonconjugated diene copolymer further containing a nonconjugated diene unit.

  Examples of the α-olefin include one or two of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-icosene and 1-docosene. From the viewpoint of the impact resistance of the resulting thermoplastic resin composition and molded product, α-olefins having 3 to 20 carbon atoms are preferable, and propylene is particularly preferable.

  The ethylene unit content of the ethylene / α-olefin copolymer (D) is 40 to 40% when the total of all the structural units constituting the ethylene / α-olefin copolymer (D) is 100% by mass. 70 mass% is preferable and 45-65 mass% is more preferable. When the ethylene unit content is within the above range, it is preferable in terms of improving impact resistance.

  Non-conjugated dienes include dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-cycloheptadiene, 1, 5-cyclooctadiene etc. are mentioned. Of these, dicyclopentadiene and / or 5-ethylidene-2-norbornene are preferred because the resulting thermoplastic resin composition and the molded article have excellent impact resistance.

  When the ethylene / α-olefin copolymer (D) is an ethylene / α-olefin / non-conjugated diene copolymer containing a non-conjugated diene unit, the content of the α-olefin unit is: When the total of all the structural units constituting the conjugated diene copolymer is 100% by mass, 20.0-59.9% by mass is preferable, and 31.0-54.8% by mass is more preferable. The content of the non-conjugated diene unit in the ethylene / α-olefin / non-conjugated diene copolymer is 100% by mass as the total of all the structural units constituting the ethylene / α-olefin / non-conjugated diene copolymer. When used, 0.1 to 10.0 mass% is preferable, and 0.2 to 4.0 mass% is more preferable. When the content of the α-olefin unit and the non-conjugated diene unit is in the above range, it is preferable in terms of improving impact resistance.

  The method for producing the ethylene / α-olefin copolymer (D) is not limited, but it is usually produced using a metallocene catalyst or a Ziegler-Natta catalyst.

  The graft copolymer (C) may be produced by graft polymerization of a vinyl monomer mixture (m3) containing an aromatic vinyl compound and a vinyl cyanide compound to the ethylene / α-olefin copolymer (D). After the ethylene / α-olefin copolymer (D) is crosslinked to produce a crosslinked ethylene / α-olefin copolymer (E), the crosslinked ethylene / α-olefin copolymer (E) is fragrant. A graft copolymer (C) may be produced by graft polymerization of a vinyl monomer mixture (m3) containing an aromatic vinyl compound and a vinyl cyanide compound. At that time, the polymerization method is not particularly limited, but the emulsion polymerization method is preferred because the resulting thermoplastic resin composition and the molded article have excellent impact resistance.

  In the emulsion polymerization, the ethylene / α-olefin copolymer (D) is emulsified and the subsequent crosslinking treatment is carried out in an O / W emulsion system to obtain a crosslinked ethylene / α-olefin copolymer (E). It is necessary to obtain an aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (E) by emulsifying the crosslinked ethylene / α-olefin copolymer (E). It is preferable from the viewpoint of simplicity of the crosslinking treatment that the α-olefin copolymer (D) is emulsified to obtain an aqueous dispersion of the ethylene / α-olefin copolymer (D) and then subjected to a crosslinking treatment. Hereinafter, an aqueous dispersion of the ethylene / α-olefin copolymer (D) obtained by emulsifying the ethylene / α-olefin copolymer (D) is referred to as an aqueous olefin resin dispersion (F).

<Olefin resin aqueous dispersion (F)>
The method for emulsifying the ethylene / α-olefin copolymer (D) is not particularly limited, but the ethylene / α-olefin may be obtained by a known melt-kneading means such as a kneader, a Banbury mixer, or a multi-screw extruder. A method in which a copolymer (D) or an ethylene / α-olefin copolymer (D) and an acid-modified olefin polymer are melt-kneaded, dispersed by applying mechanical shearing force, and added to an aqueous medium containing an emulsifier, ethylene・ Dissolve α-olefin copolymer (D) or ethylene ・ α-olefin copolymer (D) and acid-modified olefin polymer in hydrocarbon solvent such as pentane, hexane, heptane, benzene, toluene, xylene together with emulsifier. A method of adding an aqueous medium to emulsify and then sufficiently stirring to distill off the hydrocarbon solvent is preferable.

  The emulsifier that can be used for emulsifying the ethylene / α-olefin copolymer (D) is not particularly limited as long as it is usually used, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfones. Well-known things, such as an acid salt, are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The amount of the emulsifier added is that the thermal coloring of the resulting thermoplastic resin composition can be suppressed, and the particle diameter of the ethylene / α-olefin copolymer (D) in the aqueous dispersion can be easily controlled. -1-8 mass parts is preferable with respect to 100 mass parts of olefin copolymers (D).

  Examples of the acid-modified olefin polymer include those obtained by modifying an olefin polymer having a mass average molecular weight of 1,000 to 5,000 (polyethylene, polypropylene, etc.) with a compound having a functional group (such as an unsaturated carboxylic acid compound). It is done. Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, and the like. The acid value of the acid-modified olefin polymer is preferably about 10 to 50 mg-KOH / g. An acid-modified olefin polymer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the acid-modified olefin polymer is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (D). When the addition amount of the acid-modified olefin polymer is within the above range, the balance between scratch resistance and impact resistance of the obtained molded product is further improved.

  In addition, as an aqueous medium of the olefin resin aqueous dispersion (F), water or an aqueous solution of a basic substance can be used.

By adjusting the type or amount of the emulsifier used in the above emulsification treatment, the type or amount of the acid-modified olefin polymer, the shearing force applied at the time of kneading, the temperature condition, the water content, etc., the aqueous olefin resin dispersion (F) The volume average particle diameter of the ethylene / α-olefin copolymer (D) dispersed in the polymer can be controlled. The volume average particle diameter of the ethylene / α-olefin copolymer (D) dispersed in the aqueous olefin resin dispersion (F) is dispersed in the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (E). The volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (E) is the same.
The ethylene / α-olefin copolymer (D) dispersed in the aqueous olefin resin dispersion (F) and the crosslinked ethylene / α-olefin copolymer (E) dispersed in the aqueous dispersion are: It has been confirmed by an electron microscope that the average particle diameter of the ethylene / α-olefin copolymer (D) and the crosslinked ethylene / α-olefin copolymer (E) in the thermoplastic resin composition is shown as it is.

  The volume average particle diameter of the ethylene / α-olefin copolymer (D) or the crosslinked ethylene / α-olefin copolymer (E) used in the present invention is preferably from 0.1 to 1.0 μm, and preferably from 0.2 to 0.00. 9 μm is more preferable, 0.2 to 0.8 μm is further preferable, and 0.3 to 0.7 μm is particularly preferable. When the volume average particle diameter is within the above range, the resulting thermoplastic resin composition and the molded article thereof have excellent impact resistance and surface appearance.

  Here, the specific measuring method of the volume average particle diameter of the ethylene / α-olefin copolymer (D) or the crosslinked ethylene / α-olefin copolymer (E) is as shown in the section of Examples below. It is.

<Crosslinked ethylene / α-olefin copolymer (E)>
The crosslinked ethylene / α-olefin copolymer (E) is obtained by subjecting the ethylene / α-olefin copolymer (D) to a crosslinking treatment and adjusting the gel content. By cross-linking the ethylene / α-olefin copolymer (D), the impact resistance and transparency of the resulting thermoplastic resin composition are improved. Furthermore, the impact resistance and transparency of the resulting thermoplastic resin composition are further improved by adjusting the gel content during the crosslinking treatment. The gel content of the crosslinked ethylene / α-olefin copolymer (E) is preferably 35 to 75% by mass. When the gel content of the cross-linked ethylene / α-olefin copolymer (E) is within the above range, the resulting thermoplastic resin composition and the molded article thereof have excellent impact resistance and transparency.
The specific method for measuring the gel content of the crosslinked ethylene / α-olefin copolymer (E) is as shown in the Examples section below.

  The cross-linking treatment of the ethylene / α-olefin copolymer (D) can be carried out by a known method. Among them, the ethylene / α-olefin copolymer (D) can be added to an organic peroxide and, if necessary, a large amount. The method of adding a functional compound and carrying out a crosslinking treatment is preferred from the viewpoint of the impact resistance of the resulting thermoplastic resin composition and its molded product.

Specific examples include a method of heating the ethylene / α-olefin copolymer (D), the organic peroxide, and a polyfunctional compound used as necessary. Here, the gel content of the resulting crosslinked ethylene / α-olefin copolymer (E) can be adjusted by adjusting the addition amount of organic peroxide and polyfunctional compound, heating temperature, heating time, and the like. The heating temperature varies depending on the type of organic peroxide used, and is preferably −5 ° C. to + 30 ° C., which is the 10-hour half-life temperature of the organic peroxide used. A preferred heating time is 3 to 15 hours.
Examples of other crosslinking treatment methods include known crosslinking treatment methods such as a crosslinking treatment method with ionizing radiation.

  The organic peroxide is for forming a crosslinked structure in the ethylene / α-olefin copolymer (D), and examples thereof include peroxyester compounds, peroxyketal compounds, and dialkyl peroxide compounds. These can be used alone or in combination of two or more.

  Specific examples of the peroxyester compound include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecano Eight, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylper Oxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1- Cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-hexyl Hexanoate, t-butyl peroxy 2-hexyl hexanoate, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy 3,5 5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoyl Benzoate, t-butylperoxybenzoe , Bis (t-butylperoxy) Isofutareito the like.

  Specific examples of the peroxyketal compound include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis. (T-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (T-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and the like. .

  Specific examples of the dialkyl peroxide compound include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane. , T-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, and the like.

  Among these organic peroxides, dicumyl peroxide, t-butylcumyl peroxide, di-t-butylperoxide are preferable because the gel content of the crosslinked ethylene / α-olefin copolymer (E) can be easily adjusted. It is particularly preferable to use a dialkyl peroxide compound such as oxide.

  The amount of the organic peroxide added during the crosslinking treatment is such that the gel content of the crosslinked ethylene / α-olefin copolymer (E) can be adjusted in the range of 35 to 75% by mass, so that the ethylene / α-olefin copolymer is adjusted. (D) It is preferable that it is 0.2-5 mass parts with respect to 100 mass parts.

  The polyfunctional compound is used in combination with an organic peroxide in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (E). For example, divinylbenzene, allyl methacrylate, ethylene glycol Examples include dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate, and the like. One or more of these can be used. Of these, divinylbenzene is preferred from the viewpoint of easily adjusting the gel content.

  Since the polyfunctional compound is easy to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (E) to 35 to 75% by mass, 100 parts by mass of the ethylene / α-olefin copolymer (D) is used. On the other hand, it is preferably used in the range of 10 parts by mass or less.

<Vinyl monomer mixture (m3)>
The vinyl monomer mixture (m3) used for the graft copolymer (C) used in the present invention is a mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound as vinyl monomers.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Two or more types can be used in combination. Among these, it is preferable to use at least one of styrene and α-methylstyrene.
65-82 mass% is preferable, as for the content rate of the aromatic vinyl compound in 100 mass% of vinyl-type monomer mixtures (m3), 73-80 mass% is more preferable, and 75-80 mass% is still more preferable. If the content of the aromatic vinyl compound in the vinyl monomer mixture (m3) is within the above range, the resulting thermoplastic resin composition and its molded article have better impact resistance and transparency. Become.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and one or more of these can be used.
The content of the vinyl cyanide compound in 100% by mass of the vinyl monomer mixture (m3) is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and still more preferably 20 to 25% by mass. If the content of the vinyl cyanide compound in the vinyl monomer mixture (m3) is within the above range, the resulting thermoplastic resin composition and its molded article have excellent impact resistance and transparency. .

  In addition to the above aromatic vinyl compound and vinyl cyanide compound, the vinyl monomer mixture (m3) contains other vinyl monomers copolymerizable therewith within a range not impairing the effects of the present invention. May be included.

Examples of other vinyl monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, Methacrylic acid esters such as amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate,
N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, etc. N-cycloalkylmaleimide, N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-arylmaleimide such as N-chlorophenylmaleimide, and maleimide compounds such as N-aralkylmaleimide,
Examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. These may be used alone or in combination of two or more.

<Use ratio>
The graft copolymer (C) is obtained by graft polymerization of the above-mentioned ethylene / α-olefin copolymer (D) or crosslinked ethylene / α-olefin copolymer (E) with a vinyl monomer mixture (m3). It is.
The proportion of the ethylene / α-olefin copolymer (D) or the crosslinked ethylene / α-olefin copolymer (E) used in the production of the graft copolymer (C) is 50 to 80% by mass. The ratio of the mixture (m3) is preferably 20 to 50% by mass, and more preferably 60 to 80 of ethylene / α-olefin copolymer (D) or crosslinked ethylene / α-olefin copolymer (E). The vinyl monomer mixture (m3) is 20 to 40% by mass. However, the total of the ethylene / α-olefin copolymer (D) or the crosslinked ethylene / α-olefin copolymer (E) and the vinyl monomer mixture (m3) is 100% by mass. If the ratio of the ethylene / α-olefin copolymer (D) or the crosslinked ethylene / α-olefin copolymer (E) is within the above range, the productivity of the graft copolymer (C) is good, The resulting thermoplastic resin composition and its molded article have excellent impact resistance and transparency.

<Graft ratio>
The graft copolymer (C) preferably has a graft ratio of 25 to 100% because the resulting thermoplastic resin composition and the molded article have good impact resistance and transparency. % Is more preferable.
In addition, about the measuring method of the graft ratio of a graft copolymer (C), it shows to the item of an Example mentioned later.

<Method for producing graft copolymer (C)>
The graft copolymer (C) is produced by a known method such as a bulk polymerization method, a solution polymerization method, a bulk suspension polymerization method, a suspension polymerization method, an emulsion polymerization method, and the resulting thermoplastic resin composition and molding thereof. The emulsion polymerization method is preferred because the impact resistance of the product is good.

The graft copolymer (C) obtained by the emulsion polymerization method is in a state of being dispersed in an aqueous medium.
As a method for recovering the graft copolymer (C) from the aqueous dispersion of the graft copolymer (C), (i) the aqueous dispersion is put into hot water in which a coagulant is dissolved, and the slurry state To recover by coagulation (wet method), (ii) to recover the graft copolymer (C) semi-directly by spraying the graft copolymer (C) aqueous dispersion in a heated atmosphere (Spray drying method) and the like.

  Examples of the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and metal salts such as calcium chloride, calcium acetate and aluminum sulfate. The coagulant is selected according to the emulsifier used in the polymerization. That is, when only a carboxylic acid soap such as fatty acid soap or rosin acid soap is used as an emulsifier, any coagulant may be used. When the emulsifier contains an emulsifier exhibiting stable emulsifying ability even in an acidic region such as sodium dodecylbenzenesulfonate, a metal salt must be used.

  As a method for obtaining a dry graft copolymer (C) from the slurry graft copolymer (C), (i) the emulsifier residue remaining in the slurry is eluted in water by washing, and then the slurry is Examples include a method of dehydrating with a centrifugal dehydrator or a press dehydrator and further drying with an airflow dryer or the like, and (ii) a method of simultaneously performing dehydration and drying with a press dehydrator or an extruder. After drying, the graft copolymer (C) is obtained in the form of powder or particles. Moreover, the graft copolymer (C) discharged | emitted from the press dehydrator or the extruder can also be sent directly to the extruder or molding machine which manufactures a thermoplastic resin composition.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention comprises a copolymer (A) and a methacrylate ester resin (B) of the present invention, or a copolymer (A) of the present invention and a methacrylate ester resin (B) and a graft. The copolymer (C) is included as at least an essential component.
According to the thermoplastic resin composition containing at least the copolymer (A) and the methacrylic ester resin (B) as essential components, a thermoplastic resin composition having excellent transparency and fluidity is provided.
According to the thermoplastic resin composition further containing the graft copolymer (C) in this thermoplastic resin composition, a thermoplastic resin composition excellent in transparency, fluidity, and impact resistance is provided.

<Content ratio of each component>
When the thermoplastic resin composition of the present invention includes a copolymer (A) and a methacrylic ester resin (B), the content of the copolymer (A) is determined by the copolymer (A) and methacrylic acid. When the total amount of the ester resin (B) is 100% by mass, it is preferably 5 to 80% by mass, and more preferably 10 to 70% by mass. When the content of the copolymer (A) is within the above range, the resulting thermoplastic resin composition and its molded article have excellent transparency.

  When the thermoplastic resin composition of the present invention comprises a copolymer (A), a graft copolymer (C), a methacrylic ester resin (B), and a graft copolymer (C), The content of the copolymer (A) in the thermoplastic resin composition is determined when the total of the copolymer (A), the methacrylic ester resin (B), and the graft copolymer (C) is 100% by mass. 5 to 40% by mass, more preferably 10 to 30% by mass. When the content of the copolymer (A) is within the above range, the resulting thermoplastic resin composition and the molded article thereof have excellent impact resistance and transparency.

  The content of the graft polymer (C) in the thermoplastic resin composition of the present invention is 100 masses of the total of the copolymer (A), the methacrylic ester resin (B), and the graft copolymer (C). %, It is preferably 10 to 40% by mass, and preferably 15 to 35% by mass. Moreover, it is preferable that it is 20-85 mass%, and it is preferable that the content rate of a methacrylic ester resin (B) is 35-75 mass%. When the content of the graft polymer (C) or the methacrylic ester resin (B) is in the above range, the resulting thermoplastic resin composition and the molded article have excellent impact resistance and transparency.

<Other thermoplastic resins>
The thermoplastic resin composition of the present invention contains a thermoplastic resin other than the copolymer (A), the methacrylic ester resin (B), and the graft copolymer (C) as necessary. Also good. Other thermoplastic resins are not particularly limited. For example, polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, polyacetal resin, modified polyphenylene ether (modified PPE resin), Examples include ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester resin, polyethylene resin, polypropylene resin, fluororesin, and polyamide resin (nylon).
However, when the thermoplastic resin composition of the present invention contains these other thermoplastic resins, the copolymer (A) of the present invention, the methacrylic ester resin (B), and further the graft copolymer ( In order to effectively obtain the effects of impact resistance and transparency due to the inclusion of C), the proportion of other thermoplastic resins in 100% by mass of the total resin components in the thermoplastic resin composition is 30% by mass or less. It is preferable that

<Additives>
In the thermoplastic resin composition of the present invention, the thermoplastic resin composition to be obtained and other properties conventionally used at the time of molding (molding) and molding, as long as the physical properties of the resulting thermoplastic resin composition and molded product thereof are not impaired. Additives such as lubricants, pigments, dyes, fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, oxidative degradation inhibitors, weathering agents, release agents, plasticizers, antistatic agents, flame retardants, etc. Can be blended.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention can be produced by mixing the above-described components by a known method using a known device. For example, there is a melt mixing method as a general method, and examples of an apparatus used in this method include an extruder, a Banbury mixer, a roller, and a kneader. Either a batch type or a continuous type may be employed for mixing. Moreover, there is no restriction | limiting in particular in the mixing order of each component, etc., All the components should just be mixed uniformly.

[Molding]
The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention. Examples of the molding method include an injection molding method, an injection compression molding machine method, an extrusion method, a blow molding method, a vacuum molding method, a pressure forming method, a calendar molding method, and an inflation molding method. Among these, the injection molding method and the injection compression molding method are preferable because they are excellent in mass productivity and a molded product with high dimensional accuracy can be obtained.

[Usage]
The thermoplastic resin composition of the present invention and the molded product thereof are excellent in impact resistance, transparency, and fluidity. Therefore, the molded product formed by molding the thermoplastic resin composition of the present invention is a vehicle interior / exterior. It is suitable for applications such as parts and exterior parts of home appliances.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Measurement method of physical properties]
The measuring method of the physical property of each component used in the following examples and comparative examples is as follows.

<Measurement method of volume average particle diameter>
An ethylene / α-olefin copolymer (D) dispersed in an aqueous olefin resin dispersion (F) using Microtrac (“Nanotrack 150” manufactured by Nikkiso Co., Ltd.) and ion-exchanged water as a measurement solvent The volume average particle diameter of the crosslinked ethylene / α-olefin copolymer (E) dispersed in the aqueous dispersion was measured.

<Measurement method of gel content>
5 g of a coagulated powder sample [Z1] obtained by coagulating an aqueous dispersion of a crosslinked ethylene / α-olefin copolymer (E) with dilute sulfuric acid, washing with water and drying in 200 mL of 110 ° C. toluene. Soaking for a period of time, then filtering through a 200 mesh wire mesh, drying the residue, measuring the mass [Z2] of the dried product, and from the following formula (1), the crosslinked ethylene / α-olefin copolymer (E) The gel content of was determined.
Gel content rate (mass%) = dry substance amount [Z2] (g) / coagulated powder sample mass [Z1] (g) × 100
... (1)

<Measurement method of graft ratio>
1 g of the graft copolymer (C) is added to 80 mL of acetone and heated to reflux at 65 to 70 ° C. for 3 hours. The resulting suspension acetone solution is added to a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.). The mixture was centrifuged at 14,000 rpm for 30 minutes to separate a precipitation component (acetone insoluble component) and an acetone solution (acetone soluble component). And the precipitation component (acetone insoluble component) was dried, the mass (Y (g)) was measured, and the graft ratio was computed by following formula (2). In Formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (C), X is the total mass (g) of the graft copolymer (C) used to determine Y, The rubber fraction is a solid content concentration in the aqueous dispersion of the ethylene / α-olefin copolymer (D) or the crosslinked ethylene / α-olefin copolymer (E) used for the production of the graft copolymer (C). .
Graft rate (mass%) = {(Y-X × rubber fraction) / X × rubber fraction} × 100
... (2)

<Method for Measuring Molecular Weight of Copolymer (A)>
The weight average molecular weight of the copolymer (A) was measured by dissolving it in tetrahydrofuran (THF) using gel permeation chromatography (GPC), and expressed in terms of standard polystyrene.

[Preparation of copolymer (A)]
<Preparation of copolymer (A-1)>
150 parts by mass of ion-exchanged water in a pressure-resistant reaction vessel and 10 parts by mass of a macromonomer (“AA-6” manufactured by Toa Gosei Chemical Co., Ltd., number average molecular weight 6,000) as a vinyl monomer mixture (m1), A mixture of 68 parts by mass of styrene and 22 parts by mass of acrylonitrile, 0.2 parts by mass of 2,2′-azobis (isobutyronitrile), 0.25 parts by mass of n-octyl mercaptan, 0.47 parts by mass of calcium hydroxyapatite Then, 0.003 part by mass of potassium alkenyl succinate was charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. Then, it heated up to 90 degreeC and reaction was completed by hold | maintaining for 60 minutes. The contents were washed with a centrifugal dehydrator, dehydrated repeatedly, and dried to obtain a copolymer (A-1).

<Preparation of copolymer (A-2)>
The copolymer (A-1) was produced in the same manner as the copolymer (A-1) except that the vinyl monomer mixture (m1) was changed to 20 parts by mass of macromonomer, 60 parts by mass of styrene and 20 parts by mass of acrylonitrile. -2) was obtained.

<Preparation of copolymer (A-3)>
The copolymer (A1) was produced in the same manner as the copolymer (A-1) except that the vinyl monomer mixture (m1) was changed to 30 parts by mass of macromonomer, 52 parts by mass of styrene and 18 parts by mass of acrylonitrile. -3) was obtained.

<Preparation of copolymer (A-4)>
A copolymer (M-1) was produced by the same production method as that for the copolymer (A-1) except that 60 parts by mass of methyl methacrylate, 30 parts by mass of styrene, and 10 parts by mass of acrylonitrile were used. A-4) was obtained.

<Preparation of copolymer (A-5)>
A copolymer (M-1) was produced by the same production method as that for the copolymer (A-1) except that 20 parts by mass of methyl methacrylate, 60 parts by mass of styrene, and 20 parts by mass of acrylonitrile were used. A-5) was obtained.

<Preparation of copolymer (A-6)>
A copolymer (A-6) was obtained by the same production method as the copolymer (A-1), except that the vinyl monomer mixture (m1) was changed to 75 parts by mass of styrene and 25 parts by mass of acrylonitrile. .

  Table 1 shows the monomer compositions and mass average molecular weights of the copolymers (A-1) to (A-6).

[Preparation of Methacrylate-Based Resin (B)]
In a pressure-resistant reaction vessel, 150 parts by mass of ion-exchanged water, a mixture of 99 parts by mass of methyl methacrylate and 1 part by mass of methyl acrylate as a vinyl monomer mixture (m2), and 2,2′-azobis (isobutyronitrile) ) 0.2 parts by mass, n-octyl mercaptan 0.25 parts by mass, calcium hydroxyapatite 0.47 parts by mass, potassium alkenyl succinate 0.003 parts by mass, the internal temperature was raised to 75 ° C., 3 Time reaction was performed. Then, it heated up to 90 degreeC and reaction was completed by hold | maintaining for 60 minutes. The contents were washed with a centrifugal dehydrator, dehydrated repeatedly, and dried to obtain a methacrylic ester resin (B).

[Preparation of graft copolymer (C)]
<Preparation of ethylene / propylene copolymer (D)>
The stainless steel polymerization tank equipped with a 20 L stirrer was sufficiently purged with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _1.5 prepared to 8.0 mmol / L was added. ) Is continuously supplied at a rate of 5 L / h for 1 hour, and a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L is further added as a catalyst in an amount of 5 L / h. Then, hexane was continuously supplied in an amount of 5 L / h. On the other hand, the polymerization solution was continuously extracted from the upper part of the polymerization tank so that the polymerization solution in the polymerization vessel was always 10 L. Next, ethylene was supplied in an amount of 2000 L / h, propylene in an amount of 1000 L / h, and hydrogen in an amount of 8 L / h using a bubbling tube, and a polymerization reaction was performed at 35 ° C.
A polymerization reaction was performed under the above conditions to obtain a polymerization solution containing an ethylene / propylene copolymer (D). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol, precipitated, and dried to obtain an ethylene / propylene copolymer (D).

<Preparation of aqueous olefin resin dispersion (F)>
100 parts by mass of an ethylene / propylene copolymer (D), 20 parts by mass of maleic anhydride-modified polyethylene (“Mitsui High Wax 2203A” manufactured by Mitsui Chemicals, Inc., mass average molecular weight 2700, acid value 30 mg-KOH / g) , 5 parts by mass of a surfactant (“KS soap” manufactured by Kao Corporation) was supplied to the twin screw extruder (screw diameter: 30 mm, L / D; 40, barrel temperature: 200 ° C.) from its inlet. Melt kneaded. Further, 0.5 parts by mass of potassium hydroxide and 2.4 parts by mass of ion-exchanged water were supplied from a supply port provided in the vent part of the twin-screw extruder, and melt-kneaded in the twin-screw extruder. The solid dispersion discharged from the tip of the twin-screw extruder was dispersed in warm water and diluted to a solid content concentration of around 40% by mass to obtain an aqueous olefin resin dispersion (F). The volume average particle size of the ethylene / propylene copolymer (D) dispersed in the olefin resin aqueous dispersion (F) was measured to be 0.39 μm.

<Preparation of crosslinked ethylene / propylene copolymer (E)>
Ion exchange water is added to 100 parts by mass (as solid content) of the olefin resin aqueous dispersion (F) so that the solid content concentration becomes 35% by mass, and 0.5 mass of t-butylcumyl peroxide is used as the organic peroxide. 1 part by weight of divinylbenzene as a polyfunctional compound was added and reacted at 130 ° C. for 5 hours to crosslink the ethylene / propylene copolymer (D) dispersed in the aqueous olefin resin dispersion (F). An aqueous dispersion of a crosslinked ethylene / propylene copolymer (E) was obtained. When the gel content and the volume average particle diameter of the crosslinked ethylene / propylene copolymer (E) dispersed in the aqueous dispersion were measured, the gel content was 52 mass% and the volume average particle diameter was 0.39 μm. there were.

<Preparation of graft copolymer (C)>
Ion exchange water is added to 70 mass parts (as solid content) of the crosslinked ethylene / propylene copolymer (E) dispersed in the aqueous dispersion so that the solid content concentration becomes 30 mass%, and sodium pyrophosphate 0.3 Mass parts, 0.006 parts by mass of ferrous sulfate heptahydrate, and 0.35 parts by mass of fructose were charged, and the internal temperature was kept at 80 ° C. To this, a vinyl monomer mixture (m3) composed of 23.4 parts by mass of styrene and 6.6 parts by mass of acrylonitrile and 0.6 parts by mass of cumene hydroperoxide were respectively added for 140 minutes from different supply ports. At the same time, the polymerization was carried out by dropping. During this time, the internal temperature was controlled to be constant at 80 ° C. After completion of dropping, the mixture was kept at 80 ° C. for 100 minutes and then cooled to complete graft polymerization. The aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a graft copolymer (C). The graft ratio of the graft copolymer (C) was 29%.

[Examples 1-7, Comparative Examples 1-3, Reference Example 1]
Each component is mixed in the composition (parts by mass) shown in Table 2, and melt-kneaded at 240 ° C. using a 30 mmφ twin-screw extruder with a vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) to form a pellet-shaped thermoplastic resin composition I got a thing. The melt volume rate of the obtained thermoplastic resin composition was evaluated by the following method. Moreover, the transparency was evaluated by the following method for a molded product obtained by injection molding the obtained thermoplastic resin composition.
The evaluation results are shown in Table 2.

[Examples 8 to 14, Comparative Examples 4 to 6, Reference Example 2]
Each component is mixed in the composition (part by mass) shown in Table 3, and melt-kneaded at 240 ° C. using a 30 mmφ twin-screw extruder with a vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) to form a pellet-shaped thermoplastic resin composition I got a thing. The melt volume rate of the obtained thermoplastic resin composition was evaluated by the following method. Moreover, the impact resistance and transparency of the molded product obtained by injection molding of the obtained thermoplastic resin composition were evaluated by the following methods.
The evaluation results are shown in Table 3.

[Evaluation method]
<Measurement of melt volume rate (MVR)>
The thermoplastic resin composition was measured under the condition of 230 ° C. according to the ISO 1133 standard. In addition, MVR becomes a standard of the fluidity | liquidity of a thermoplastic resin composition, ie, a moldability.

<Evaluation of impact resistance: Charpy impact test>
The molded product was subjected to a Charpy impact test (notched) at 23 ° C. in accordance with ISO 179 standard, and the Charpy impact strength was measured.

<Evaluation of transparency>
The molded product was measured for HAZE according to the JIS K 7136 standard. The lower the HAZE of the molded product, the better the transparency and the better the color developability during coloring.

As shown in Examples 1 to 7 in Table 2, according to each example in which the copolymer (A) of the present invention was blended with a methacrylic ester resin (B), thermoplasticity excellent in fluidity and transparency. A resin composition and a molded product were obtained.
On the other hand, the thermoplastic resin compositions and molded articles obtained in Comparative Examples 1 to 3 were remarkably inferior in transparency.
From the comparison between Reference Example 1 containing only the methacrylate ester resin (B) and Examples 1 to 7 containing the copolymer (A) of the present invention, the copolymer (A) of the present invention was converted to a methacrylate ester. Even if it mix | blends with resin (B), there is almost no problem of a transparency fall, On the other hand, it turns out that fluidity | liquidity can be improved by mixing | blending the copolymer (A) of this invention.

As shown in Examples 8 to 14 of Table 3, according to each Example in which the copolymer (A) of the present invention was blended with a methacrylic ester resin (B) and a graft copolymer (C), it was transparent. A thermoplastic resin composition and a molded article having excellent properties, impact resistance, and fluidity were obtained.
On the other hand, the thermoplastic resin compositions and molded articles obtained in Comparative Examples 4 to 6 were remarkably inferior in transparency and insufficient in impact resistance.
In Reference Example 2 in which only the methacrylate ester resin (B) is used, and in Examples 8 to 14 in which the copolymer (A) and the graft copolymer (C) of the present invention are blended with the methacrylate ester resin (B). From the comparison, it can be seen that the impact resistance can be greatly improved according to the present invention.

Claims (12)

  Comprising a copolymer (A) obtained by polymerizing a vinyl monomer mixture (m1) containing an aromatic vinyl compound, a vinyl cyanide compound and a macromonomer, the macromonomer comprising a polymethacrylate ester as a main skeleton And a copolymer (A) which is a macromonomer having a vinyl group at one end of the polymethacrylic acid ester.   The number average molecular weight of the macromonomer is 1,000 to 20,000, the content of the aromatic vinyl compound in 100% by mass of the vinyl monomer mixture (m1) is 45 to 72% by mass, and cyanation The vinyl compound content is 15 to 23% by mass, the macromonomer content is 5 to 40% by mass, and the weight average molecular weight of the copolymer (A) is 30,000 to 1,000,000. The copolymer (A) according to claim 1.   The copolymer (A) according to claim 1 or 2, which is an improver for a methacrylate ester resin (B) obtained by polymerizing a vinyl monomer mixture (m2) containing a methacrylate ester.   A copolymer (A) according to any one of claims 1 to 3 and a methacrylate ester resin (B) obtained by polymerizing a vinyl monomer mixture (m2) containing a methacrylate ester. A thermoplastic resin composition comprising:   The thermoplastic resin composition according to claim 4, wherein the content of methacrylic acid ester in 100% by mass of the vinyl monomer mixture (m2) is 80 to 100% by mass.   The heat according to claim 4 or 5, wherein the content of the copolymer (A) in a total of 100% by mass of the copolymer (A) and the methacrylic ester resin (B) is 5 to 80% by mass. Plastic resin composition.   Furthermore, the ethylene / α-olefin copolymer (D) includes a graft copolymer (C) obtained by graft polymerization of a vinyl monomer mixture (m3) containing an aromatic vinyl compound and a vinyl cyanide compound. The thermoplastic resin composition according to any one of 4 to 6.   The content of the aromatic vinyl compound in 100% by mass of the vinyl monomer mixture (m3) is 65 to 82% by mass, and the content of the vinyl cyanide compound is 18 to 35% by mass. The thermoplastic resin composition as described.   The ethylene / α-olefin copolymer (D) and the vinyl monomer mixture (m3) have a total content of 100% by mass of the ethylene / α-olefin copolymer (D) of 50 to 80% by mass. The content of the vinyl-based monomer mixture (m3) is 20 to 50% by mass, and the graft ratio of the graft copolymer (C) is 25 to 100%. Thermoplastic resin composition.   The ethylene / α-olefin copolymer (D) is a crosslinked ethylene / α-olefin copolymer (E) crosslinked, and the gel content of the crosslinked ethylene / α-olefin copolymer (E) is 35. The thermoplastic resin composition according to any one of claims 7 to 9, which is -75 mass%.   The content of the copolymer (A) in a total of 100% by mass of the copolymer (A), the methacrylic ester resin (B) and the graft copolymer (C) is 5 to 40% by mass, and methacrylic acid. The heat according to any one of claims 7 to 10, wherein the content of the ester resin (B) is 20 to 85% by mass and the content of the graft copolymer (C) is 10 to 40% by mass. Plastic resin composition.   A molded article formed by molding the thermoplastic resin composition according to any one of claims 3 to 11.