JP2014156548A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is good in flowability and which provides a molded article excellent in scratch resistance, glossiness, color developing property and shock resistance, and to provide a molded article excellent in scratch resistance, glossiness, color developing property and shock resistance.SOLUTION: There is provided the thermoplastic resin composition including a graft copolymer (D) and a methacrylate ester resin (E). The graft copolymer (D) is obtained by polymerizing a vinyl-based monomer mixture (m1) including an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene α-olefin copolymer (A) having a mass average molecular weight (Mw) of 17×10to 35×10and a molecular weight distribution (Mw/Mn) of 1 to 3, or in the presence of a crosslinked ethylene α-olefin copolymer (C) obtained by subjecting the ethylene α-olefin copolymer (A) to cross-linking treatment. The methacrylate ester resin (E) is obtained by polymerizing a vinyl-based monomer mixture (m2) including methacrylate ester.

Description

  The present invention relates to a thermoplastic resin composition and a molded article thereof.

  Improving the impact resistance of the molded product not only expands the applications of the molded product, but also makes it extremely useful for industrial applications, such as enabling the molded product to be made thinner and larger. . Therefore, various techniques have been proposed so far for improving the impact resistance of the molded product. Among these methods, a method for increasing the impact resistance of a molded product by using a resin material in which a rubbery polymer and a hard resin are combined has already been industrialized. Examples of such resin materials include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylic ester (ASA) resin, acrylonitrile-ethylene / propylene / non-conjugated diene copolymer-styrene (AES) resin, and the like. Can be mentioned.

  Moreover, when high designability is calculated | required by a molded article, the coating process is performed to the molded article obtained from these resin materials, and high appearance quality is obtained. However, the painting process has problems such as a large environmental load, complicated processes, and a high defect rate. For this reason, a coloring agent may be blended in advance with the resin material, and the coating treatment of the molded product may be omitted. When coating treatment is omitted, high weather resistance is required for the molded product. Therefore, resin materials that can obtain molded products with good weather resistance, such as ethylene / propylene / non-conjugated diene as a rubbery polymer. AES resin, ASA resin, or the like using a polymer, acrylic ester rubber, hydrogenated rubber (hydrogenated butadiene rubber or the like), silicone rubber or the like is used.

  However, a molded product that uses a resin material that can obtain a molded product with good weather resistance and that does not require a coating process is used during manufacturing of the molded product, during processing of the molded product, while the molded product is used for a long time, etc. When the surface of the molded product is damaged, the designability is remarkably lowered. Therefore, improvement of scratch resistance is desired depending on the application of the molded product. Then, in order to improve the scratch resistance of a molded article, it has been proposed to use the following thermoplastic resin composition.

(1) A rubbery material containing a graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer, and a hard resin. The surface of the molded product is hardened using a thermoplastic resin composition having a low polymer ratio (see Patent Document 1).
(2) A lubricant (polyolefin wax, silicone oil) is added to the graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer. Etc.) is used to improve the slipperiness of the surface of the molded product (see Patent Document 2).
(3) A layered clay obtained by intercalating an organic compound with a graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. A thermoplastic resin composition containing a mineral is used (see Patent Document 3).
(4) A graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, and an aromatic vinyl compound and a vinyl cyanide compound A thermoplastic resin composition comprising a copolymer obtained by polymerizing a vinyl-based monomer mixture containing styrene and a copolymer obtained by copolymerizing methyl methacrylate and methyl acrylate in a specific ratio (See Patent Document 4).

When the thermoplastic resin composition (1) is used, the hardness of the surface of the molded product is increased, so that the scratch resistance against scratches is improved, but the ratio of the rubbery polymer is decreased, so that Impact strength decreases. Therefore, there is a limit to satisfy both the impact resistance and the scratch resistance of the molded product.
When the thermoplastic resin composition (2) is used, although the slipperiness of the surface of the molded product is improved, the improvement of scratch resistance is insufficient. Further, since the lubricant bleeds out on the surface of the molded product, the glossiness and color developability may be impaired.
In the thermoplastic resin composition of (3), the compatibility between the graft copolymer and the layered clay mineral intercalated with an organic compound is often insufficient. As a result, the appearance of the molded product may be poor (such as a decrease in glossiness or color developability) or impact resistance may be reduced.
(4) When the thermoplastic resin composition is used, the scratch resistance of the molded product against scratches is improved, but the scratch resistance of the molded product against scratches is insufficient.
Moreover, although it is calculated | required that the thermoplastic resin composition is excellent in the fluidity | liquidity at the time of shaping | molding, the fluidity | liquidity of the thermoplastic resin composition of (1)-(4) is not necessarily satisfactory.

JP-A-11-001600 JP 2000-119477 A JP 2003-277570 A JP 2008-291158 A

  The present invention is a thermoplastic resin composition having good flowability and excellent scratch resistance, gloss, color development, and impact resistance of the obtained molded article, and scratch resistance, gloss, color development, impact resistance. Provide molded products with excellent properties.

The thermoplastic resin composition of the present invention is an ethylene / α-olefin copolymer having a mass average molecular weight (Mw) of 17 × 10 ^{4 to} 35 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1 to 3. (A) or a vinyl system containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A) A graft copolymer (D) obtained by polymerizing the monomer mixture (m1) and a methacrylate ester resin (E) obtained by polymerizing a vinyl monomer mixture (m2) containing a methacrylate ester ).

  The molded article of the present invention uses the thermoplastic resin composition of the present invention.

The thermoplastic resin composition of the present invention has good fluidity. Moreover, according to the thermoplastic resin composition of the present invention, a molded product having excellent scratch resistance, gloss, color development and impact resistance can be obtained.
The molded article of the present invention is excellent in scratch resistance, gloss, color development and impact resistance.

It is the schematic explaining the abrasion-resistance test by gauze wear.

The following definitions of terms apply throughout this specification and the claims.
“Molded product” means a product formed by molding a thermoplastic resin composition.
“Scratch resistance” refers to the resistance to scratches (scratch resistance) caused by scratching the surface of a molded article with a hard, pointed object such as a nail, and work gloves, gauze, cloth, etc. It means both scratch resistance (scratch resistance) against scratches (scratches) that occur when the surface of a molded product is rubbed with a soft material.
“Lightness (L ^* )” means a lightness value (L ^* ) among color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729.
The “SCE method” means a method of measuring a color by using a spectrocolorimeter in accordance with JIS Z 8722 and removing specularly reflected light with an optical trap.

"Thermoplastic resin composition"
The thermoplastic resin composition of the present invention contains a graft copolymer (D) and a methacrylic ester resin (E). The thermoplastic resin composition of the present invention may contain a styrene-based copolymer (F), other thermoplastic resins, and various additives as necessary within the range not impairing the effects of the present invention. .

The graft copolymer (D) is the following (α) or (β).
(Α) A product obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the ethylene / α-olefin copolymer (A).
(Β) A product obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the crosslinked ethylene / α-olefin copolymer (C).

Specific examples of (α) include the following.
(Α1) A product obtained by polymerizing the vinyl monomer mixture (m1) in a solution containing the ethylene / α-olefin copolymer (A).
(Α2) A product obtained by polymerizing a vinyl monomer mixture (m1) in an aqueous olefin resin dispersion (B) containing an ethylene / α-olefin copolymer (A).

Specific examples of (β) include the following.
(Β1) A product obtained by polymerizing a vinyl monomer mixture (m1) in a solution containing a crosslinked ethylene / α-olefin copolymer (C).
(Β2) A product obtained by polymerizing the vinyl monomer mixture (m1) in an aqueous dispersion containing the crosslinked ethylene / α-olefin copolymer (C).

The methacrylic ester resin (E) is (γ) below.
(Γ) A product obtained by polymerizing a vinyl monomer mixture (m2).

The styrene copolymer (F) is the following (δ).
(Δ) A product obtained by polymerizing the vinyl monomer mixture (m3).
Hereinafter, each component ((A)-(F), (m1)-(m3) etc.) is demonstrated.

<Ethylene / α-olefin copolymer (A)>
In the present invention, it is important to use the ethylene / α-olefin copolymer (A) so that the molded article exhibits excellent impact resistance.
The ethylene / α-olefin copolymer (A) comprises 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.

  Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-icosene, 1-docosene, etc. From the viewpoint of impact resistance, an α-olefin having 3 to 20 carbon atoms is preferable, and propylene is particularly preferable.

  The ethylene unit content of the ethylene / α-olefin copolymer (A) is 45 to 45% when the total of all the structural units constituting the ethylene / α-olefin copolymer (A) is 100% by mass. 65 mass% is preferable and 50-60 mass% is more preferable. When the ethylene unit content is within the above range, the balance of the scratch resistance and impact resistance of the molded product is further improved. In particular, when the ethylene unit content is 50 to 60% by mass, the scratch resistance and impact resistance of the molded product are further improved.

  In the present invention, the fluidity of the thermoplastic resin composition is improved, and the molded article exhibits excellent scratch resistance, gloss, color development and impact resistance, so that the mass average molecular weight (Mw) and the mass are increased. It is important to use an ethylene / α-olefin copolymer (A) in which the molecular weight distribution (Mw / Mn) represented by the ratio between the average molecular weight (Mw) and the number average molecular weight (Mn) is in a specific range. .

The mass average molecular weight (Mw) of the ethylene / α-olefin copolymer (A) is 17 × 10 ^{4 to} 35 × 10 ⁴ , and preferably 26 × 10 ^{4 to} 32 × 10 ⁴ . When the mass average molecular weight (Mw) is smaller than 17 × 10 ⁴ , the scratch resistance and impact resistance of the molded product are inferior. On the other hand, when the mass average molecular weight (Mw) is larger than 35 × 10 ⁴ , the fluidity of the thermoplastic resin composition, the glossiness of the molded product, and the color developability are poor. When the mass average molecular weight (Mw) is 26 × 10 ^{4 to} 32 × 10 ⁴ , the fluidity of the thermoplastic resin composition and the scratch resistance, impact resistance, and gloss of the molded product are further improved.

  The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (A) is 1 to 3, and preferably 1.9 to 2.5. When the molecular weight distribution (Mw / Mn) is larger than 3, the molded article has poor scratch resistance and impact resistance. When the molecular weight distribution (Mw / Mn) is 1.9 to 2.5, the fluidity of the thermoplastic resin composition, the scratch resistance and the impact resistance of the molded product are further improved.

  The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer (A) are values measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

  The method for producing the ethylene / α-olefin copolymer (A) is not limited. The ethylene / α-olefin copolymer (A) is usually produced by polymerizing ethylene and an α-olefin using a metallocene catalyst or a Ziegler-Natta catalyst.

As a metallocene catalyst, a catalyst obtained by combining an organic compound having a cyclopentadienyl skeleton with a transition metal (zirconium, titanium, hafnium, etc.), a metallocene complex in which a halogen atom or the like is coordinated, an organic aluminum compound, an organic boron compound, or the like Is mentioned.
Examples of the Ziegler-Natta catalyst include a catalyst in which a halide of a transition metal (titanium, vanadium, zirconium, hafnium, etc.) is combined with an organic aluminum compound, an organic boron compound, or the like.

  Examples of the polymerization method include a method in which ethylene and an α-olefin are copolymerized in a solvent in the presence of the catalyst. Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may use the raw material alpha olefin as a solvent.

  By changing the reaction conditions such as the supply amount of ethylene, α-olefin, the type and amount of molecular weight regulators such as hydrogen, the type and amount of catalyst, the reaction temperature, and the pressure, an ethylene / α-olefin copolymer (A ) Ethylene unit content, mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be adjusted.

<Olefin resin aqueous dispersion (B)>
The aqueous olefin resin dispersion (B) is obtained by dispersing the ethylene / α-olefin copolymer (A) in an aqueous medium.

  The preparation method of the olefin resin aqueous dispersion (B) is not limited. As a preparation method, for example, the ethylene / α-olefin copolymer (A) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.) and dispersed by applying mechanical shearing force. The ethylene / α-olefin copolymer (A) is dissolved in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) together with the emulsifier, and added to the aqueous medium. After adding and emulsifying, there may be mentioned a method of sufficiently stirring and distilling off the hydrocarbon solvent. In preparing the aqueous olefin resin dispersion (B), an emulsifier, an acid-modified olefin polymer, and the like may be added as other components.

Examples of the emulsifier include known ones, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
The amount of the emulsifier added can suppress thermal coloring of the resulting thermoplastic resin composition, and the particle size of the aqueous olefin resin dispersion (B) can be easily controlled. When potassium oleate is used as the emulsifier, 1-8 mass parts is preferable with respect to 100 mass parts of alpha olefin copolymer (A).

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 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 (A). 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 molded product is further improved.

The method for adding the acid-modified olefin polymer is not limited. Crosslinking may be performed after mixing the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer, or the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer. You may mix, after each crosslinking process.
The mixing method of the ethylene / α-olefin copolymer (A) and the acid-modified olefin polymer is not limited. Examples of the mixing method include a melt kneading method using a kneader, a Banbury mixer, a multi-screw extruder and the like.

The volume average diameter of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B) is preferably 0.2 to 0.6 μm from the viewpoint of excellent physical property balance of the molded product. When the volume average diameter is within the above range, the impact resistance of the molded product is further improved.
As a method of controlling the volume average diameter of the ethylene / α-olefin copolymer (A) in the olefin resin aqueous dispersion (B), the type or amount of the emulsifier, the type or content of the acid-modified olefin polymer, The method of adjusting the shear force, temperature conditions, etc. which are applied at the time of kneading is mentioned.
The volume average diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion is the same as the ethylene / α-olefin of the thermoplastic resin composition. The volume average diameter of the copolymer (A) and the crosslinked ethylene / α-olefin copolymer (C) is confirmed by image processing of an electron micrograph.

<Crosslinked ethylene / α-olefin copolymer (C)>
The crosslinked ethylene / α-olefin copolymer (C) is obtained by crosslinking the ethylene / α-olefin copolymer (A).

In the present invention, the gel content of the crosslinked ethylene / α-olefin copolymer (C) may be within a specific range in order that the molded product exhibits excellent scratch resistance, impact resistance, and color developability. preferable.
The gel content of the cross-linked ethylene / α-olefin copolymer (C) is preferably 35 to 75% by mass, and preferably 40 to 70% by mass from the viewpoint of balance between scratch resistance, impact resistance, and color developability of the molded product. % Is more preferable, and 45 to 65% by mass is particularly preferable.

  The crosslinking treatment of the ethylene / α-olefin copolymer (A) is performed by a known method. As a method for the crosslinking treatment, (a) a method for carrying out the crosslinking treatment by adding an organic peroxide and, if necessary, a polyfunctional compound to the ethylene / α-olefin copolymer (A); ) A method of performing a crosslinking treatment with ionizing radiation, and the like, and the method (a) is preferable from the viewpoint of impact resistance and color developability of the molded product.

Specifically, as the method of (a), an ethylene / α-olefin copolymer (A) or an aqueous olefin resin dispersion (B) is mixed with an organic peroxide and, if necessary, a multifunctional compound. The method of adding and heating is mentioned.
The gel content of the crosslinked ethylene / α-olefin copolymer (C) 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. The heating temperature is preferably −5 ° C. to + 30 ° C., which is the 10-hour half-life temperature of the organic peroxide.
The heating time is preferably 3 to 15 hours.

  The organic peroxide is for forming a crosslinked structure in the ethylene / α-olefin copolymer (A). Examples of the organic peroxide include a peroxy ester compound, a peroxy ketal compound, a dialkyl peroxide compound, and the like. An organic peroxide may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the peroxyester compound include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 -Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexyl peroxy 2-hexyl Hexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexano Ate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl Peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoe , Bis (t-butylperoxy) isophthalate.

  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) Examples include 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-butyl peroxide) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butyl. Examples include cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

  As the organic peroxide, dialkyl such as dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, etc., because it is easy to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C). Peroxide compounds are particularly preferred.

  The addition amount of the organic peroxide is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted to a range of 35 to 75% by mass, so that the ethylene / α-olefin copolymer (A ) 0.1-5 parts by mass is preferable with respect to 100 parts by mass.

  The polyfunctional compound is used in combination with an organic peroxide as necessary in order to adjust the gel content of the crosslinked ethylene / α-olefin copolymer (C). Examples of polyfunctional compounds include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate, and the like. From the viewpoint of easily adjusting the gel content, divinylbenzene is preferred. A polyfunctional compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the polyfunctional compound is such that the gel content of the crosslinked ethylene / α-olefin copolymer (C) can be easily adjusted to 35 to 75% by mass, and thus the ethylene / α-olefin copolymer (A) 100 is used. 10 parts by mass or less is preferable with respect to parts by mass.

  Volume average of crosslinked ethylene / α-olefin copolymer (C) in an aqueous dispersion of crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking olefin resin aqueous dispersion (B) with an organic peroxide. The diameter does not change with respect to the volume average diameter of the ethylene / α-olefin copolymer (A) in the aqueous olefin resin dispersion (B).

<Vinyl monomer mixture (m1)>
The vinyl monomer mixture (m1) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.

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. Styrene and α-methylstyrene are preferable from the viewpoints of fluidity, color developability of molded products, and impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 65 to 82% by mass, more preferably 73 to 80% by mass, and further preferably 75 to 80% by mass in 100% by mass of the vinyl monomer mixture (m1). When the content of the aromatic vinyl compound is within the above range, the color developability and impact resistance of the molded product are further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and still more preferably 20 to 25% by mass in 100% by mass of the vinyl monomer mixture (m1). When the content of the vinyl cyanide compound is within the above range, the color developability and impact resistance of the molded product are further improved.

The vinyl monomer mixture (m1) may contain, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith within a range not impairing the effects of the present invention.
Other monomers include acrylic acid esters (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc.) ), Maleimide compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like. Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.

<Graft copolymer (D)>
The graft copolymer (D) is obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C). Obtained by.

  Since the graft copolymer (D) can sufficiently secure a molecular chain (graft component) contributing to elastic deformation, the ethylene / α-olefin copolymer contained in the graft copolymer (D) under shear stress (A) Deformation of the particles or the crosslinked ethylene / α-olefin copolymer (C) particles is suppressed. Therefore, by blending the graft copolymer (D), the molded product can exhibit excellent impact resistance and scratch resistance.

  The graft copolymer (D) is a vinyl monomer mixture (in the presence of 50 to 80% by mass of an ethylene / α-olefin copolymer (A) or a crosslinked ethylene / α-olefin copolymer (C)). m1) 20 to 50% by mass (however, the total of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) and the vinyl monomer mixture (m1) is 100%) %) Is preferred. When the ethylene / α-olefin copolymer (A) or the cross-linked ethylene / α-olefin copolymer (C) is 50 to 80% by mass, the fluidity of the thermoplastic resin composition and the impact resistance of the molded product are obtained. Further, the balance of physical properties of glossiness and color development is further improved.

  The graft ratio of the graft copolymer (D) is preferably 20 to 100% by mass from the viewpoint of the balance between the fluidity of the thermoplastic resin composition and the impact resistance, color development and gloss of the molded product.

  Examples of the polymerization method include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.), and emulsion polymerization method from the point that the scratch resistance and gloss of the molded product are further improved. Is particularly preferred.

  As a method for producing the graft copolymer (D) by emulsion polymerization, for example, an organic peroxide is mixed into the vinyl monomer mixture (m1), and then the vinyl monomer mixture (m1) is converted into an olefin. Examples thereof include a method of continuously adding the aqueous resin dispersion (B) or the aqueous dispersion of the crosslinked ethylene / α-olefin copolymer (C). The organic peroxide is preferably used as a redox initiator that combines an organic peroxide, a transition metal, and a reducing agent. In the polymerization, a chain transfer agent, an emulsifier or the like may be used depending on the situation.

The redox initiator does not require the polymerization reaction conditions to be at a high temperature, avoids deterioration of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C), and is molded. A combination of an organic peroxide and a ferrous sulfate-chelating agent-reducing agent is preferable from the viewpoint of avoiding a decrease in impact resistance of the product.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, and t-butyl hydroperoxide.
The redox initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of chain transfer agents include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allylsulfonic acid, methallylsulfonic acid, these Sodium salts, etc.), α-methylstyrene dimers, and the like, and mercaptans are preferred from the viewpoint of easy adjustment of the molecular weight. A chain transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
The addition amount of the chain transfer agent is preferably 2.0 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m1).

Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, and amino acid derivative salts.
Examples of nonionic surfactants include ordinary polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types.
Examples of the amphoteric surfactant include those having a carboxylate salt, sulfate ester salt, sulfonate salt, phosphate ester salt and the like in the anion portion and amine salts and quaternary ammonium salts in the cation portion.
The addition amount of the emulsifier is preferably 10 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m1).

The graft copolymer (D) obtained by the emulsion polymerization method is in a state of being dispersed in water. As a method for recovering the graft copolymer (D) from the aqueous dispersion containing the graft copolymer (D), for example, a precipitation agent is added to the aqueous dispersion, and after heating and stirring, the precipitation agent is separated. And a precipitation method in which the precipitated graft copolymer (D) is washed with water, dehydrated and dried.
Examples of the precipitating agent include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. A precipitation agent may be used individually by 1 type, and may be used in combination of 2 or more type.
An antioxidant may be added to the aqueous dispersion containing the graft copolymer (D) as necessary.

<Vinyl monomer mixture (m2)>
The vinyl monomer mixture (m2) contains at least a methacrylic acid ester as an essential component, and is a maleimide compound, an aromatic vinyl compound, an acrylic acid ester, and another vinyl monomer copolymerizable with the methacrylic acid ester. Is a monomer mixture containing as an optional component.

The content of the methacrylic acid ester is preferably 50 to 100% by mass in 100% by mass of the vinyl monomer mixture (m2) from the viewpoint of scratch resistance and color developability of the molded product.
If the content of the methacrylic acid ester is 50 to 94% by mass, the content of the maleimide compound is 5 to 49% by mass, and the content of the aromatic vinyl compound is 1 to 45% by mass, the resistance of the molded product Scratch resistance, color development, impact resistance, and heat resistance are even better.

  Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, Examples include isoamyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, penzyl methacrylate, phenyl methacrylate, and the like. From the viewpoint of superiority, at least one of methyl methacrylate and ethyl methacrylate is preferable. A methacrylic acid ester may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of maleimide compounds include N-alkylmaleimide (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide). , N-t-butylmaleimide, etc.), N-cycloalkylmaleimide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.) and the like. From the viewpoint of further improving the heat resistance and impact resistance of the molded product, N-arylmaleimide is preferred, and N-phenylmaleimide is particularly preferred. A maleimide type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  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. Styrene and α-methylstyrene are preferable from the viewpoint of further excellent impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and the like, and methyl acrylate is preferred from the viewpoint that the heat resistance and impact resistance of the molded product are further improved. One kind of acrylic acid ester may be used alone, or two or more kinds may be used in combination.

  Examples of other vinyl monomers include vinyl cyanide compounds (acrylonitrile, methacrylonitrile, etc.). Another vinyl-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

<Methacrylate resin (E)>
The methacrylic ester resin (E) is obtained by polymerizing the vinyl monomer mixture (m2).
The polymerization method is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, etc.).

As a method for producing a methacrylic ester resin (E) by an emulsion polymerization method, for example, a vinyl monomer mixture (m2), an emulsifier, a polymerization initiator, and a chain transfer agent are charged in a reactor and polymerized by heating. And the method of collect | recovering methacrylic ester resin (E) by the precipitation method from the aqueous dispersion containing methacrylic ester resin (E) is mentioned.
Examples of the emulsifier include usual emulsion polymerization emulsifiers (potassium rosinate, sodium alkylbenzenesulfonate, etc.).
Examples of the polymerization initiator include organic and inorganic peroxide initiators.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.
As the precipitation method, a method similar to that used when recovering the graft copolymer (D) from the aqueous dispersion can be employed.

Examples of the method for producing a methacrylate ester resin (E) by suspension polymerization include, for example, a vinyl monomer mixture (m2), a suspending agent, a suspending aid, a polymerization initiator, and a chain transfer agent in a reactor. And heating to polymerize, and the slurry is dehydrated and dried to recover the methacrylic ester resin (E).
Examples of the suspending agent include tricalcium phosphite and polyvinyl alcohol.
Examples of the suspension aid include sodium alkylbenzene sulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.

  A methacrylic ester resin (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

<Vinyl monomer mixture (m3)>
The vinyl monomer mixture (m3) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.

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. Styrene and α-methylstyrene are preferable from the viewpoints of fluidity, color developability of molded products, and impact resistance. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 15 to 95% by mass in 100% by mass of the vinyl monomer mixture (m3). When the content of the aromatic vinyl compound is within the above range, the impact resistance of the molded product is further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 5 to 85% by mass in 100% by mass of the vinyl monomer mixture (m3). When the content of the vinyl cyanide compound is within the above range, the impact resistance of the molded product is further improved.

The vinyl monomer mixture (m3) may contain a methacrylic acid ester and a maleimide compound as necessary.
Examples of the methacrylic acid ester and the maleimide compound include those exemplified in the vinyl monomer mixture (m2).

<Styrene copolymer (F)>
The styrene copolymer (F) is obtained by polymerizing a vinyl monomer mixture (m3) containing an aromatic vinyl compound and a vinyl cyanide compound.

  The polymerization method is not limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, etc.). From the viewpoint of heat resistance of the molded product, suspension polymerization method and bulk polymerization method are available. preferable.

<Other thermoplastic resins>
Other thermoplastic resins include, for example, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, poly Examples include arylate, liquid crystal polyester, polyethylene, polypropylene, fluororesin, and polyamide (nylon).

<Various additives>
Examples of various additives include antioxidants, lubricants, processing aids, pigments, fillers, silicone oils, paraffin oils, and the like.

<Content of each component>
The content of the graft copolymer (D) is preferably 10 to 30% by mass in a total of 100% by mass of the graft copolymer (D), the methacrylic ester resin (E) and the styrene copolymer (F). 15-25 mass% is more preferable. When the content of the graft copolymer (D) is within the above range, the balance of physical properties such as fluidity of the thermoplastic resin composition, scratch resistance, impact resistance, color development, and heat resistance of the molded product is excellent. .

  The content of the methacrylic ester resin (E) is preferably 30 to 90% by mass in a total of 100% by mass of the graft copolymer (D), methacrylic ester resin (E) and styrene copolymer (F). 35-85 mass% is more preferable. When the content of the methacrylic ester resin (E) is within the above range, the balance of physical properties such as fluidity of the thermoplastic resin composition, scratch resistance, impact resistance, color development, and heat resistance of the molded product is excellent. .

  The content of the styrene copolymer (F) is 0 to 40% by mass in 100% by mass in total of the graft copolymer (D), the methacrylic ester resin (E), and the styrene copolymer (F). Preferably, 1-40 mass% is more preferable from the point of the fluidity | liquidity of a thermoplastic resin composition, the impact resistance of a molded article, and heat resistance.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition is a mixture of a graft copolymer (D) and a methacrylic ester resin (E) and, if necessary, a styrene copolymer (F), other thermoplastic resins, and various additives. It is obtained by doing. You may pelletize with an extruder, a Banbury mixer, a kneading roll, etc.

<Effect>
In the thermoplastic resin composition of the present invention described above, the ethylene / α-olefin copolymer (A) having the mass average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) within a specific range or the Graft copolymer obtained by polymerizing the vinyl monomer mixture (m1) in the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the ethylene / α-olefin copolymer (A). Since the coalescence (D) and the methacrylic ester resin (E) are contained, a molded product having good fluidity and excellent scratch resistance, gloss, color development and impact resistance can be obtained. Moreover, even if heat resistance is imparted to the molded article, impact resistance is not impaired.

"Molding"
The molded article of the present invention can be obtained by molding the thermoplastic resin composition of the present invention by a known molding method.
Examples of the molding method include injection molding, press molding, extrusion molding, vacuum molding, and blow molding.
Applications of the molded article include vehicle exterior parts, office equipment, home appliances, building materials, etc., and vehicle exterior parts are preferred.

  In the molded article of the present invention described above, since the thermoplastic resin composition of the present invention is used, it is excellent in scratch resistance, gloss, color developability and impact resistance. Moreover, if the thing of a specific copolymer composition is used as methacrylic ester resin (E), or a styrene-type copolymer (F) is used, it will be excellent also in heat resistance.

Hereinafter, an example is shown concretely. However, the present invention is not limited to these examples.
In the following, “%” means “mass%” and “part” means “part by mass”.
Various measurements and evaluation methods in the following examples and comparative examples are as follows.

<Measurement Method of Mass Average Molecular Weight (Mw), Molecular Weight Distribution (Mw / Mn)>
Mass average molecular weight in terms of polystyrene using GPC (GPC: “GPC / V2000” manufactured by Waters, column: “Shodex AT-G + AT-806MS” manufactured by Showa Denko KK) and o-dichlorobenzene (145 ° C.) as a solvent. (Mw), number average molecular weight (Mn) were measured, and molecular weight distribution (Mw / Mn) was calculated.

<Method for measuring acid value>
The acid value was measured according to JIS K 2501.

<Measurement method of volume average diameter>
The volume average diameter (MV) was measured using a micro track (“Nano Track 150” manufactured by Nikkiso Co., Ltd.) using pure water as a measurement solvent.
The volume of the ethylene / α-olefin copolymer (A) dispersed in the olefin resin aqueous dispersion (B) and the volume of the crosslinked ethylene / α-olefin copolymer (C) dispersed in the aqueous dispersion. Image analysis of an electron microscope that the average diameter indicates the volume average diameter of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C) in the thermoplastic resin composition as it is. Confirmed by.

<Measurement method of gel content>
Coagulated powder sample [D1] 0.5 g obtained by coagulating an aqueous or solvent dispersion of the crosslinked ethylene / α-olefin copolymer (C) with dilute sulfuric acid, washing with water, and drying is 200 mL, 110 ° C. toluene. 5 hours, and then filtered through a 200 mesh wire mesh, the residue is dried, the mass of the dried product [D2] is measured, and from the following formula (1), a crosslinked ethylene / α-olefin copolymer The gel content of (C) was determined.
Gel content rate (%) = dry substance amount [D2] (g) / coagulated powder sample mass [D1] (g) × 100 (1)

<Measurement method of graft ratio>
1 g of the graft copolymer (D) is added to 80 mL of acetone, heated to reflux at 65 to 70 ° C. for 3 hours, and the resulting suspended 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 from following formula (2). In Formula (2), Y is the mass (g) of the acetone-insoluble component of the graft copolymer (D), and X is the total mass (g) of the graft copolymer (D) used to determine Y. The rubber fraction is the solid content of the graft copolymer (D) of the ethylene / α-olefin copolymer (A) or the crosslinked ethylene / α-olefin copolymer (C).
Graft rate (%) = {(Y-X × rubber fraction) / X × rubber fraction} × 100 (2)

<Melting and kneading>
Graft copolymer (D), methacrylic ester resin (E), and other components as necessary are mixed in the formulations shown in Tables 22 to 31, and a twin screw extruder with a 30 mmφ vacuum vent ("PCM30" manufactured by Ikegai Co., Ltd.). )) Was melt kneaded at a cylinder temperature of 200 to 260 ° C. and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition. Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.).

<Measurement of melt volume rate (MVR)>
About the thermoplastic resin composition, MVR was measured according to the ISO 1133 standard. In addition, MVR becomes a standard of the fluidity | liquidity of a thermoplastic resin composition.

<Injection molding>
The pellets of the thermoplastic resin composition obtained by melt-kneading are subjected to bending elasticity with an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. Test pieces for rate and Charpy impact tests were obtained, 2 mm thick flat plates (10 cm × 10 cm).

<Measurement of flexural modulus>
The specimen was measured for flexural modulus according to ISO 178 standard.

<Evaluation of impact resistance: Charpy impact test>
The test piece 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 heat resistance>
Based on the ISO test method 75 standard, the deflection temperature (° C.) under load was measured by 1.83 MPa, 4 mm, and the flatwise method.

<Evaluation of glossiness>
The gloss of the 2 mm thick flat plate was measured with a digital variable gloss meter (“UGV-5D” manufactured by Suga Test Instruments Co., Ltd.) under conditions of an incident angle of 60 ° and a reflection angle of 60 °.

<Evaluation of color development>
100 parts of the thermoplastic resin composition was mixed with 0.8 parts of carbon black and colored, and a black colored plate (molded product (Ma)) of 100 × 100 mm (thickness 2 mm) was obtained by injection molding. . For the molded product (Ma), the lightness L ^* was measured by a SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). The L ^* measured in this way is referred to as “L ^* (ma)”. The lower L ^* , the more black and the better the color developability.

<Evaluation of scratch resistance>
Using a pencil hardness tester, a pencil with a hardness of 3H was pressed against the surface of the molded product (Ma) with a load of 750 g, and the molded product (Ma) was moved by about 5 cm in this state, whereby the molded product (Ma) The surface was scratched with a pencil to scratch the molded product (Ma). The brightness L ^* of the surface of the scratched molded article (Mb) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mb)”.

(Scratch resistance determination 1)
A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded product (Mb) was calculated from the following formula (3). As the absolute value of ΔL ^* (mb−ma) is larger, the scratches are more conspicuous.
ΔL ^* (mb−ma) = L ^* (mb) −L ^* (ma) (3)

When the absolute value of ΔL ^* (mb−ma) is 3.0 or less, the scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 3.0 to 7.0 or less, scratches are hardly noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mb−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

(Scratch resistance determination 2)
Using a shape measurement laser microscope ("VK-9700" manufactured by Keyence Corporation) as an index for determining the ease of scratches on the molded product (Ma), the 10-point average roughness (Rz jis) of the molded product (Mb) is used. It was measured. The larger the value of Rz jis, the easier it is to scratch.

<Evaluation of scratch resistance>
As shown in FIG. 1, a rod-like jig 10 having a tip portion 11 formed in a hemispherical shape was prepared, and the tip portion 11 was covered with a laminated sheet 12 in which eight sheets of gauze were stacked. The tip part 11 covered with the laminated sheet 12 is brought into contact with the surface of the molded product (Ma) 13 so that the rod-shaped jig 10 is at a right angle, and the tip part 11 is brought into contact with the surface of the molded product (Ma) 13. Were slid in the horizontal direction (arrow direction in the figure) and reciprocated 100 times. At that time, the applied load was 1 kg. After reciprocating 100 times, the lightness L ^* of the surface of the scratched molded article (Mc) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mc)”.

(Abrasion resistance judgment 1)
A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded article (Mc) was calculated from the following formula (4). As the absolute value of ΔL ^* (mc−ma) is larger, scratches are more conspicuous.
ΔL ^* (mc−ma) = L * (mc) −L * (ma) (4)

When the absolute value of ΔL ^* (mc−ma) is 3.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc-ma) is more than 3.0 to 7.0 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is more than 7.0, scratches are conspicuous and the design of the molded product is impaired.

(Scratch resistance determination 2)
Measure the 10-point average roughness (Rz jis) of a molded product (Mc) with a shape measurement laser microscope (VK-9700, manufactured by Keyence Corporation) as an index for determining the ease of scratching of the molded product (Ma). did. The larger the value of Rz jis, the easier it is to scratch.

<Each component>
In the following examples, the following ethylene / α-olefin copolymer (A), olefin resin aqueous dispersion component (B), crosslinked ethylene / α-olefin copolymer (C), graft copolymer (D), Methacrylate resin (E) and styrene copolymer (F) were used.

<Ethylene / α-olefin copolymer (A)>
(Preparation of ethylene / propylene copolymer (A-1))
After fully substituting the stainless polymerization tank equipped with a 20 L stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ prepared to 8.0 mmol / L was added. ₅ ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 0.8 mmol / L as a catalyst was further added to 5 L / h. Hexane was continuously fed in an amount of 5 L / h. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. Using a bubbling tube, ethylene was supplied in an amount of 2000 L / h, propylene was supplied in an amount of 1000 L / h, hydrogen was supplied in an amount of 8 L / h, 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 (A-1). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-1). Table 1 shows the properties of the ethylene / propylene copolymer (A-1).

(Preparation of ethylene / propylene copolymers (A-2) to (A-8))
As shown in Tables 1 and 2, the ethylene / propylene copolymers (A-2) to (A-) were the same as the ethylene / propylene copolymers (A-1) except that the supply amount of hydrogen was changed. 8) was obtained. Tables 1 and 2 show the properties of the ethylene / propylene copolymers (A-2) to (A-8).

(Preparation of ethylene / propylene copolymer (A-9))
After sufficiently substituting a 20 L stainless steel tank with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added, and 110 L of propylene (standard state) and 800 mL of hydrogen were added. After heating to 40 ° C., it was pressurized with ethylene so that the total pressure was 0.6 MPa [gage]. When the internal pressure reached 0.6 MPa [gage], 10 mL of a 1.0 mM / mL hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance is 0.16 mM in terms of boron, and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium chloride is 0. Polymerization was initiated by injecting 30 mL of a toluene solution containing 0004 mM with nitrogen. Thereafter, the temperature was adjusted to 40 ° C. for 5 minutes, and ethylene was supplied so that the pressure became 0.6 MPa [gage]. Five minutes after the start of the polymerization, 50 mL of methanol was inserted to stop the polymerization, and the pressure was released to atmospheric pressure to obtain a polymerization solution containing an ethylene / propylene copolymer (A-9). The obtained polymerization solution was deashed with hydrochloric acid, poured into methanol for precipitation, and then dried to obtain an ethylene / propylene copolymer (A-9). Table 4 shows the polymer properties of the ethylene / propylene copolymer (A-9).

(Preparation of ethylene / propylene copolymer (A-10))
20 parts of ethylene / propylene copolymer (A-1) and 80 parts of ethylene / propylene copolymer (A-9) are mixed, and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) Were melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-10). Table 4 shows the properties of the ethylene / propylene copolymer (A-10).

(Preparation of ethylene / propylene copolymer (A-11))
An ethylene / propylene copolymer (A-11) is obtained in the same manner as the ethylene / propylene copolymer (A-1) except that VCl ₄ is used instead of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst. It was. Table 2 shows the properties of the ethylene / propylene copolymer (A-11).

(Preparation of ethylene / propylene copolymer (A-12))
75 parts of ethylene / propylene copolymer (A-1) and 25 parts of ethylene / propylene copolymer (A-11) are mixed, and a twin screw extruder with a 30 mmφ vacuum vent (“Ikegai Co., Ltd.,“ PCM30 ”) Were melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-12). Table 4 shows the properties of the ethylene / propylene copolymer (A-12) polymer.

(Preparation of ethylene / propylene copolymer (A-13))
Mixing 50 parts of ethylene / propylene copolymer (A-1) and 50 parts of ethylene / propylene copolymer (A-11), a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) Was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-13). Table 4 shows the properties of the ethylene / propylene copolymer (A-13).

(Preparation of ethylene / propylene copolymer (A-14))
20 parts of ethylene / propylene copolymer (A-1) and 80 parts of ethylene / propylene copolymer (A-11) are mixed, and a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) Was melt-kneaded at 200 ° C. and 93.325 kPa vacuum to prepare an ethylene / propylene copolymer (A-14). Table 4 shows the polymer properties of the ethylene / propylene copolymer (A-14).

(Preparation of ethylene / propylene copolymers (A-15) to (A-20))
As shown in Table 3, the ethylene / propylene copolymer (A-15 to (A−) was used in the same manner as the ethylene / propylene copolymer (A-1) except that the supply amounts of ethylene, propylene and hydrogen were changed. Table 3 shows the properties of the ethylene / propylene copolymer (A-15 to (A-20)).

<Olefin resin aqueous dispersion component (B)>
(Preparation of aqueous dispersion of olefin resin (B-1))
100 parts of ethylene / propylene copolymer (A-1) and maleic anhydride-modified polyethylene (manufactured by Mitsui Chemicals, "Mitsui High Wax 2203A") as the acid-modified olefin polymer, mass average molecular weight: 2,700, acid value: 30 mg / g) 20 parts and 4 parts of potassium oleate as an anionic emulsifier were mixed.
While supplying this mixture at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40) and continuously supplying a 14% potassium hydroxide aqueous solution at 240 g / h. The mixture was melt-kneaded by heating to 220 ° C., and the resulting melt-kneaded product was extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the extruder and cooled to 90 ° C. The taken-out solid was put into warm water at 80 ° C. and continuously dispersed to obtain an aqueous olefin resin dispersion (B-1) having a volume average diameter of 0.25 μm.

(Preparation of olefin resin aqueous dispersions (B-2) to (B-20))
As shown in Table 2, the olefin resin was the same as the aqueous olefin resin dispersion (B-1) except that (A-1) was changed to (A-2) to (A-20) as the A component. Aqueous dispersions (B-2) to (B-20) were obtained.
Tables 5 to 7 show the volume average diameters of the ethylene / α-olefin copolymers (A) dispersed in each of the aqueous olefin resin dispersions (B-1) to (B-20).

<Crosslinked ethylene / α-olefin copolymer (C)>
(Preparation of crosslinked ethylene / α-olefin copolymer (C-1))
Ion exchange water was added to the olefin resin aqueous dispersion (B-1) (100 parts as a solid content) so that the solid concentration was 35%, and 0.5 parts of t-butylcumyl peroxide as an organic peroxide, As a polyfunctional compound, 1 part of divinylbenzene was added and reacted at 130 ° C. for 5 hours to prepare a crosslinked ethylene / α-olefin copolymer (C-1). The gel content of the crosslinked ethylene / α-olefin copolymer (C-1) was measured and found to be 51%. The results are shown in Table 8.

(Preparation of crosslinked ethylene / α-olefin copolymers (C-2) to (C-15))
As shown in Table 8, except that the type of olefin resin aqueous dispersion (B) and the amount of t-butylcumyl peroxide added were changed, the same procedure as for the crosslinked ethylene / α-olefin copolymer (C-1) was performed. Then, crosslinked ethylene / α-olefin copolymers (C-2) to (C-15) were obtained. Table 8 shows the gel contents of the crosslinked ethylene / α-olefin copolymers (C-2) to (C-15).

(Adjustment of crosslinked ethylene / α-olefin copolymer (C-16) to (C-24))
As shown in Table 9 and Table 10, except that the addition amount of t-butylcumyl peroxide was changed, the crosslinked ethylene / α-olefin copolymer was treated in the same manner as the crosslinked ethylene / α-olefin copolymer (C-1). Polymers (C-16) to (C-24) were obtained. Tables 9 and 10 show the gel contents of the crosslinked ethylene / α-olefin copolymers (C-16) to (C-24).

<Graft copolymer (D)>
(Preparation of graft copolymer (D-1))
An aqueous olefin resin dispersion (B-1) (70 parts as a solid content of the ethylene / propylene copolymer (A-1)) is placed in a stainless polymerization tank equipped with a stirrer, and an aqueous olefin resin dispersion (B-1). Ion-exchanged water was added to the solution so that the solid concentration was 30%, and 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were added, and the temperature was set to 80 ° C. Styrene (23.4 parts), acrylonitrile (6.6 parts) and cumene hydroperoxide (0.6 parts) were continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. After the polymerization, an antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1), solids are precipitated with sulfuric acid, and after washing, dehydration and drying, A polymer (D-1) was obtained. When the graft ratio of the graft copolymer (D-1) was measured, it was 30%. The results are shown in Table 11.

(Preparation of graft copolymers (D-2) to (D-14))
As shown in Tables 11 to 14, except that the type of the olefin resin aqueous dispersion (B) was changed, the graft copolymers (D-2) to ( D-14) was obtained. The graft ratios of the graft copolymers (D-2) to (D-14) are shown in Tables 11 to 14.

(Preparation of graft copolymer (D-15))
In a stainless polymerization tank equipped with a stirrer, 70 parts of ethylene / propylene copolymer (A-1) and 300 parts of toluene were charged, and the contents were stirred at 70 ° C. for 1 hour to uniformly dissolve. After sufficiently purging with nitrogen, 23.4 parts of styrene, 6.6 parts of acrylonitrile, 0.24 parts of t-dodecyl mercaptan and 0.22 parts of t-butylperoxyisopropyl monocarbonate were added, and the internal temperature was 110 ° C. The mixture was heated up to react for 4 hours. The internal temperature was raised to 120 ° C. and reacted for 2 hours. After the polymerization, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. The reaction mixture was extracted, and unreacted substances and the solvent were distilled off by steam distillation. The volatile matter was substantially devolatilized at 220 ° C. and 93.325 kPa vacuum in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.), pelletized, and graft copolymer (D-15 ) When the graft ratio of the graft copolymer (D-15) was measured, it was 26%. The results are shown in Table 14.

(Preparation of graft copolymers (D-16) to (D-39))
As shown in Table 15 to Table 18, the graft copolymer (D) except that the aqueous olefin resin dispersion (B-1) was changed to an aqueous dispersion containing a crosslinked ethylene / α-olefin copolymer (C). In the same manner as in -1), graft copolymers (D-16) to (D-39) were obtained. The graft ratios of the graft copolymers (D-16) to (D-39) are shown in Tables 15 to 18.

<Methacrylate resin (E)>
(Preparation of methacrylate ester resin (E-1))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 99 parts of methyl methacrylate, 1 part of methyl acrylate, 0.2 part of 2,2′-azobis (isobutyronitrile), 0.25 part of n-octyl mercaptan , 0.47 part of calcium hydroxyapatite and 0.003 part of potassium alkenyl succinate were charged. The internal temperature of the polymerization tank was set to 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered methacrylate resin (E-1). The monomers are shown in Table 19.

(Preparation of methacrylate ester resin (E-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 82 parts of methyl methacrylate, 12 parts of N-phenylmaleimide, 6 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl Mercaptan (0.25 part) and polyvinyl alcohol (0.7 part) were charged. The internal temperature of the polymerization tank was set at 75 ° C. for 3 hours, and the temperature was raised to 90 ° C. for 1 hour. The contents were extracted, washed with a centrifugal dehydrator, and dried to obtain a powdered methacrylate resin (E-2). The monomers are shown in Table 19.

(Preparation of methacrylate resin (E-3) to (E-11))
As shown in Table 19 and Table 20, except that the type of the vinyl monomer mixture (m2) was changed, the same as in the methacrylate ester resin (E-2), the methacrylate ester resin (E-3) to (E-11) was obtained.

<Styrene copolymer (F)>
(Preparation of styrene copolymer (F-1))
In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of 2,2′-azobis (isobutyronitrile), 25 parts of acrylonitrile, 75 parts of styrene, t -0.35 part of dodecyl mercaptan was charged and reacted at an initial temperature of 60 ° C for 5 hours. The temperature was raised to 120 ° C. and reacted for 4 hours. The contents were taken out to obtain a styrene copolymer (F-1).

(Preparation of styrene copolymer (F-2))
In a stainless polymerization tank equipped with a stirrer, 150 parts of ion exchange water, 7 parts of methyl methacrylate, 23 parts of acrylonitrile, 70 parts of styrene, 0.2 part of 2,2′-azobis (isobutyronitrile), n-octyl mercaptan 0 .25 parts, calcium hydroxyapatite 0.47 part, and potassium alkenyl succinate 0.003 part were charged, the internal temperature was raised to 75 ° C., and the reaction was performed for 3 hours. The reaction was completed by raising the temperature to 90 ° C. and holding for 60 minutes. The contents were taken out, repeatedly washed with a centrifugal dehydrator and dehydrated, and dried to obtain a styrene copolymer (F-2).

(Preparation of styrenic copolymers (F-3) to (F-6))
As shown in Table 21, except that the amount of the vinyl monomer mixture (m3) was changed, in the same manner as the styrene copolymer (F-2), the styrene copolymers (F-3) to ( F-6) was obtained.

[Example 1]
24 parts of graft copolymer (D-1) and 76 parts of methacrylic ester resin (E-1) were mixed, and 240 ° C., 93 ° C. in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.) A thermoplastic resin composition was prepared by melt kneading in a vacuum of 325 kPa. Table 22 shows the MVR of the thermoplastic resin composition.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Table 22.

[Examples 2-33]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the type of the graft copolymer (D) was changed as shown in Tables 22 to 27, and MVR was measured.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Table 22 to Table 27.

[Examples 34 to 56]
As shown in Table 28 to Table 31, the types and amounts of the graft copolymer (D), the methacrylic ester resin (E), and the styrene copolymer (F) were changed, and the melt kneading conditions were 250 ° C., 93 A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the pressure was changed to 325 kPa, and MVR was measured.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Table 28 to Table 31.

[Comparative Examples 1-6]
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the type of the graft copolymer (D) was changed as shown in Table 32, and MVR was measured.
The thermoplastic resin composition was pelletized, various molded products were molded, the flexural modulus was measured, and the impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance were evaluated. The results are shown in Table 32.

The thermoplastic resin compositions of Examples 1 to 56 were excellent in fluidity. In addition, the molded articles obtained in Examples 1 to 56 were excellent in impact resistance, heat resistance, glossiness, color development, scratch resistance, and scratch resistance.
Therefore, the thermoplastic resin composition of the present invention is excellent in fluidity, and when the thermoplastic resin composition of the present invention is used, impact resistance, glossiness, color development, scratch resistance, and scratch resistance are improved. It can be seen that an excellent molded product is obtained and can be applied to uses such as vehicle exterior parts, office equipment, home appliances, and building materials.

On the other hand, Comparative Example 1 using an ethylene / propylene copolymer (A-2) having a mass average molecular weight (Mw) of less than 17 × 10 ⁴ as the ethylene / α-olefin copolymer (A) is Impact and scratch resistance were low.
Comparative Example 2 using an ethylene / propylene copolymer (A-8) having a mass average molecular weight (Mw) exceeding 35 × 10 ⁴ as the ethylene / α-olefin copolymer (A) is a thermoplastic resin composition. The fluidity was significantly reduced and the gloss of the molded product was low.
Comparative Example 3 using an ethylene / propylene copolymer (A-11) having a molecular weight distribution (Mw / Mn) of more than 3 as the ethylene / α-olefin copolymer (A) is the impact resistance, Scratch resistance was low.
Comparative Example 4 using a crosslinked ethylene / α-olefin copolymer (C-2) obtained by crosslinking the ethylene / propylene copolymer (A-2) as a crosslinked ethylene / α-olefin copolymer (C) The impact resistance and scratch resistance of the molded product were low.
Comparative Example 5 using a crosslinked ethylene / α-olefin copolymer (C-5) obtained by crosslinking the ethylene / propylene copolymer (A-8) as the crosslinked ethylene / α-olefin copolymer (C) is as follows: The fluidity of the thermoplastic resin composition was remarkably lowered, and the gloss of the molded product was low.
Comparative Example 6 using a crosslinked ethylene / α-olefin copolymer (C-8) obtained by crosslinking the ethylene / propylene copolymer (A-11) as the crosslinked ethylene / α-olefin copolymer (C) is: The impact resistance and scratch resistance of the molded product were low.

  Molded articles using the thermoplastic resin composition of the present invention are useful as vehicle exterior parts, office equipment, home appliances, building materials and the like, and are particularly useful as vehicle exterior parts.

10 Jig 11 Tip 12 Laminated Sheet 13 Molded Product (Ma)

Claims (2)

The ethylene / α-olefin copolymer (A) or the ethylene / α-olefin having a mass average molecular weight (Mw) of 17 × 10 ^{4 to} 35 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 1 to 3 In the presence of the crosslinked ethylene / α-olefin copolymer (C) obtained by crosslinking the copolymer (A), a vinyl monomer mixture (m1) containing an aromatic vinyl compound and a vinyl cyanide compound is polymerized. A graft copolymer (D) obtained by
A thermoplastic resin composition comprising: a methacrylic ester resin (E) obtained by polymerizing a vinyl monomer mixture (m2) containing a methacrylic ester.   A molded article using the thermoplastic resin composition according to claim 1.

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