WO2014192673A1 - Thermoplastic resin composition and method for producing same - Google Patents

Abstract

The present invention addresses the problem of providing: a thermoplastic resin composition which enables the production of a molded article having an excellent balance between impact resistance and stiffness and also having excellent appearance; and a method for producing the thermoplastic resin composition. The present invention is a thermoplastic resin composition comprising 0.1 to 95 parts by mass of (A) a copolymer of (a1) a vinyl monomer having a reactive functional group, (a2) an aromatic vinyl monomer and (a3) a vinyl cyanide monomer, 0 to 94.9 parts by mass of (B) a copolymer of (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer, 5 to 40 parts by mass of (C) an ethylene rubbery polymer having a reactive functional group, and 0 to 35 parts by mass of (D) an ethylene rubbery polymer (wherein the sum total of the amounts of the components (A), (B), (C) and (D) is 100 parts by mass), said thermoplastic resin composition being characterized in that the rising start temperature of the storage elastic modulus of the composition in a dynamic viscoelasticity measurement is a temperature that is higher by 20ºC than the glass transition temperature of (C) the ethylene rubbery polymer having a reactive functional group or lower, and (C) the ethylene rubbery polymer having a reactive functional group is dispersed at an average particle diameter of 0.6 μm or less.

Description

Thermoplastic resin composition and method for producing the same

The present invention relates to a thermoplastic resin composition and a method for producing the same.

Acrylonitrile / butadiene / styrene copolymer (ABS) is excellent in processability and appearance, has higher strength and rigidity than polystyrene, and is also excellent in heat resistance and chemical resistance. It is used not only for automobile parts and building materials, but also for a wider range of applications. Also, acrylonitrile / ethylene rubber / styrene copolymer (AES) using ethylene rubber as a rubber component is widely used.

Since ABS has a double bond in the main chain, there is a problem in weather resistance, and butadiene as a raw material is derived from crude oil, and there is a concern that the cost will increase due to a rise in the price of crude oil. On the other hand, AES has excellent weather resistance because it does not have a double bond in the main chain, and the raw material can also be produced from natural gas, so it is not easily affected by the price of crude oil.

As a method for producing AES, for example, an ethylene rubber polymer is emulsified in a large-capacity solvent, and a vinyl monomer such as acrylonitrile and an aromatic such as styrene in the presence of the ethylene rubber polymer latex. A technique of emulsion graft polymerization of a vinyl monomer is known (for example, see Patent Document 1). However, AES obtained by such a complicated manufacturing process tends to be mixed with impurities such as an emulsifier, and tends to decrease impact resistance and rigidity.

Moreover, as a method for producing a thermoplastic resin composition such as AES by a melt-kneading technique, for example, (I) an aromatic vinyl monomer unit and a vinyl monomer unit having an epoxy group are essential monomer units. And (II) an unsaturated dicarboxylic acid anhydride monomer unit and / or a modified polyolefin polymer modified with an unsaturated carboxylic acid monomer unit as a raw material, and a melt-mixing method, etc. It has been proposed (see, for example, Patent Documents 2 to 3). However, in this method, it is difficult to efficiently proceed the reaction between (I) and (II), and there is a problem that the balance between impact resistance, rigidity, and appearance is insufficient.

Japanese Patent Publication No.49-14549 (UK Patent Application Publication No. 1323506) JP-A-6-9840 JP-A-11-228769

The present invention is to solve the above problems, to provide a thermoplastic resin composition that is excellent in the balance between impact resistance and rigidity, and that can obtain a molded product excellent in appearance, and a method for producing the same. To do.

As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by setting the rising temperature and the average particle diameter of the storage elastic modulus of the rubber component in the thermoplastic resin composition within a specific range. As a result, the present invention has been completed.

The thermoplastic resin composition of the present invention has the following constitution.
(A) Copolymer of (a1) vinyl monomer having reactive functional group (i), (a2) aromatic vinyl monomer and (a3) vinyl cyanide monomer 0.1 ~ 95 parts by mass,
(B) a copolymer of (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer, 0 to 94.9 parts by mass,
(C) 5 to 40 parts by mass of an ethylene rubbery polymer having a reactive functional group (ii) and (D) 0 to 35 parts by mass of an ethylene rubbery polymer (provided that (A), (B), ( C) and (D) is a thermoplastic resin composition obtained by blending 100 parts by mass), and the rising temperature of the storage elastic modulus in dynamic viscoelasticity measurement is the above-mentioned (C) reactive functional group ( The glass transition temperature of the ethylene rubber polymer having ii) is not higher than 20 ° C. and (C) the ethylene rubber polymer having a reactive functional group (ii) is dispersed with an average particle diameter of 0.6 μm or less. A thermoplastic resin composition.

And as a manufacturing method of the said thermoplastic resin composition, this invention has the following structures.
(A) Copolymer of (a1) vinyl monomer having reactive functional group (i), (a2) aromatic vinyl monomer and (a3) vinyl cyanide monomer 0.1 ~ 95 parts by mass,
(B) a copolymer of (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer, 0 to 94.9 parts by mass,
(C) 5 to 40 parts by mass of an ethylene rubbery polymer having a reactive functional group (ii) and (D) 0 to 35 parts by mass of an ethylene rubbery polymer (provided that (A), (B), ( C) and (D) are 100 parts by mass). The method for producing the thermoplastic resin composition, wherein the mixture is melt kneaded by chaos mixing using a twin screw extruder.

According to the thermoplastic resin composition of the present invention, a molded product excellent in impact resistance, rigidity and appearance can be provided.

Hereinafter, the thermoplastic resin composition of the present invention will be specifically described.

<Copolymer (A)>
The thermoplastic resin composition of the present invention comprises (A) (a1) a vinyl monomer having a reactive functional group (i), (a2) an aromatic vinyl monomer, and (a3) a vinyl cyanide monomer. It can be obtained by blending with a copolymer (hereinafter, this copolymer may be referred to as “copolymer (A)”). Further, (a4) other vinyl monomers copolymerizable with these may be further copolymerized. The copolymer (A) reacts with an ethylene-based rubbery polymer (C) having a reactive functional group (ii) to be described later (hereinafter sometimes referred to as “rubbery polymer (C)”), and then grafted. By forming the product, the compatibility between the copolymer (A) and the rubbery polymer (C) is improved, and the impact resistance and appearance of the molded product obtained by molding the thermoplastic resin composition are improved. Can be made.

As the vinyl monomer having a reactive functional group (i) used in the copolymer (A) used in the present invention, it reacts with a reactive functional group of a rubbery polymer (C) described later. If it is a vinyl-type monomer which has a functional group to do, it will not specifically limit. Examples of the reactive functional group (i) in the component (a1) include an epoxy group, an amino group, and a hydroxyl group. In particular, an epoxy group is preferable from the viewpoint of further improving the impact strength.

(A1) Examples of vinyl monomers having a reactive functional group (i) include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate as vinyl monomers having an epoxy group. Allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, and the like. Two or more of these may be used.

The (a2) aromatic vinyl monomer used in the copolymer (A) used in the present invention is particularly an aromatic vinyl monomer having no reactive functional group (i) and cyano group. It is not limited. Examples thereof include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, t-butylstyrene and the like. Two or more of these may be used. In particular, styrene is preferably used.

Examples of the (a3) vinyl cyanide monomer used in the copolymer (A) used in the present invention include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. Two or more of these may be used. In particular, acrylonitrile is preferably used.

(A4) Other vinyl monomers copolymerizable with the components (a1), (a2), and (a3) used as necessary include, for example, methyl or ethyl of acrylic acid or methacrylic acid (Meth) acrylic acid ester monomers such as propyl, n-butyl and isobutyl esterified compounds, and maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide. Two or more of these may be used. A (meth) acrylic acid ester monomer is preferably used for the purpose of improving toughness and color tone. On the other hand, maleimide monomers are preferably used for the purpose of improving heat resistance and flame retardancy.

Blending of (a1) a vinyl monomer having a reactive functional group (i) in a total of 100% by mass of the monomers (a1) to (a4) constituting the copolymer (A) used in the present invention The amount is preferably 0.01 to 20% by mass. (A1) By making the compounding quantity of a component 0.01 mass% or more, reaction of a copolymer (A) and the rubbery polymer (C) mentioned later can be advanced more effectively, and the molded article obtained Impact resistance and appearance can be further improved. This amount is more preferably 0.1% by mass or more. On the other hand, when the blending amount of the component (a1) is 20% by mass or less, the fluidity can be improved and the molding processability can be improved. Further, the amount is more preferably 15% by mass or less. The blending amount of the (a2) aromatic vinyl monomer is preferably 5 to 99.99% by mass. By setting the blending amount of the component (a2) to 5% by mass or more, the moldability and the rigidity of the molded product can be further improved. The amount is more preferably 20% by mass or more. On the other hand, the heat resistance of a molded article can be improved by making the compounding quantity of (a2) component into 99.99 mass% or less. The amount is more preferably 90% by mass or less. The blending amount of the (a3) vinyl cyanide monomer is preferably 1 to 60% by mass. By setting the blending amount of the component (a3) to 1% by mass or more, the rigidity and heat resistance of the molded product can be further improved. On the other hand, when the blending amount of the component (a3) is 60% by mass or less, the moldability and the rigidity of the molded product can be further improved. In addition, the compatibility between the copolymer (A) and the rubbery polymer (C) is improved, and the impact resistance and appearance of a molded product obtained by molding the thermoplastic resin composition can be further improved. . The amount is more preferably 45% by mass or less. Further, when (a4) another vinyl monomer is copolymerized, the amount of the component (a4) is preferably 90% by mass or less. (A4) By making the compounding quantity of a component into 90 mass% or less, moldability and the rigidity of a molded product can be improved more. The amount is more preferably 79% by mass or less.

The weight average molecular weight of the copolymer (A) used in the present invention is preferably 10,000 or more and 300,000 or less. By making the weight average molecular weight of the copolymer (A) 10,000 or more, the impact resistance and rigidity of the molded product can be further improved. The molecular weight is more preferably 30,000 or more, and most preferably 50,000 or more. On the other hand, when the weight average molecular weight of the copolymer (A) is 300,000 or less, molding processability can be improved and gloss unevenness can be reduced. The molecular weight is more preferably 250,000 or less, and most preferably 200,000 or less. It is considered that the lower the weight average molecular weight of (A), the shorter the graft chain, the more difficult it is for the molecules of (C) to be stretched during molding, and the reduction in gloss unevenness. In addition, the weight average molecular weight of a copolymer (A) means the polystyrene conversion value obtained by a gel permeation chromatograph measurement using a hexafluoro isopropanol (HFIP) solution. When multiple types of copolymer (A) are mix | blended, it is preferable that the weight average molecular weight of the whole some copolymer (A) exists in the said range.

There are no particular restrictions on the method for producing the copolymer (A) used in the present invention. For example, the above-mentioned component (a1), component (a2), component (a3), and if necessary, using the component (a4) as a raw material, It can be obtained by polymerization using a known polymerization method such as a combination method, suspension polymerization method, emulsion polymerization method, solution polymerization method, bulk-suspension polymerization method and solution-bulk polymerization method.

<Copolymer (B)>
If necessary, the thermoplastic resin composition of the present invention comprises a copolymer of (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer (hereinafter referred to as “copolymer (B)”). In some cases). By blending the copolymer (B), the moldability and the rigidity of the molded product can be improved. The copolymer (B) may be a polymer obtained by copolymerizing (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer, and (b3) other copolymerizable with these. Further, a vinyl monomer may be copolymerized.

(B1) The aromatic vinyl monomer is not particularly limited as long as it is an aromatic vinyl monomer having no reactive functional group. For example, the monomer etc. which were illustrated previously as (a2) are mentioned. Two or more of them may be used. In particular, styrene is preferably used.

(B2) Examples of the vinyl cyanide monomer include the monomers exemplified above as (a3). Two or more of them may be used. In particular, acrylonitrile is preferably used.

In addition, as the other vinyl-based monomer (b3) copolymerizable with the component (b1) and the component (b2) used as necessary, for example, the monomer previously exemplified as (a4), etc. Is mentioned. Two or more of them may be used. A (meth) acrylic acid ester monomer is preferably used for the purpose of improving toughness and color tone. On the other hand, maleimide monomers are preferably used for the purpose of improving heat resistance and flame retardancy.

Of the total 100% by mass of each of the monomers (b1) to (b3) constituting the copolymer (B) used in the present invention, the blending amount of the (b1) aromatic vinyl monomer is 5 to 99% by mass. Is preferred. By setting the blending amount of the component (b1) to 5% by mass or more, the moldability and the rigidity of the molded product can be further improved. The amount is more preferably 20% by mass or more. On the other hand, the heat resistance of a molded product can be improved by making the compounding quantity of (b1) component into 99 mass% or less, and also 90 mass% or less is more preferable. (B2) The amount of the vinyl cyanide monomer is preferably 1 to 60% by mass. By setting the blending amount of the component (b2) to 1% by mass or more, the heat resistance of the molded product can be improved. On the other hand, when the blending amount of the component (b2) is 60% by mass or less, molding processability can be improved. The amount is more preferably 45% by mass or less. Further, when (b3) another vinyl monomer is copolymerized, the blending amount of the component (b3) is preferably 90% by mass or less. By adjusting the blending amount of the component (b3) to 90% by mass or less, molding processability, rigidity of the molded product and heat resistance can be improved, and 79% by mass or less is more preferable.

The weight average molecular weight of the copolymer (B) used in the present invention is preferably from 100,000 to 300,000. By setting the weight average molecular weight of the copolymer (B) to 100,000 or more, the impact resistance and rigidity of the molded product can be further improved. On the other hand, moldability can be improved by making the weight average molecular weight of a copolymer (B) into 300,000 or less. The molecular weight is more preferably 250,000 or less, and most preferably 200,000 or less. In addition, the weight average molecular weight of a copolymer (B) means the polystyrene conversion value obtained by a gel permeation chromatograph measurement using a hexafluoroisopropanol (HFIP) solution. When blending a plurality of types of copolymers (B), it is preferable that the weight average molecular weight of the whole of the plurality of copolymers (B) is within the above range.

The method for producing the copolymer (B) used in the present invention is not particularly limited, and the component (b1), the component (b2) and, if necessary, the component (b3) are mixed into a bulk polymerization method, a suspension polymerization method, an emulsion weight. It can be obtained by polymerization using a known polymerization method such as a combination method, a solution polymerization method, a bulk-suspension polymerization method and a solution-bulk polymerization method.

<Rubber polymer (C)>
The thermoplastic resin composition of the present invention can be obtained by blending the rubber polymer (C). By blending the rubber polymer (C), the impact resistance of the molded product can be improved.

The rubber component constituting the rubbery polymer (C) used in the present invention may be a polymer containing ethylene as a polymerization component, and may be a copolymer with another unsaturated monomer as necessary. May be. Examples thereof include an ethylene polymer and an ethylene / α-olefin copolymer. Here, “/” indicates a copolymer. The ethylene / α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, such as an ethylene / propylene copolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer. Examples thereof include a polymer and an ethylene / octene copolymer. Two or more of these may be blended. As the reactive functional group (ii) of the rubber polymer (C), those reactive with the reactive functional group (i) described above are preferable. Examples thereof include a carboxyl group and an acid anhydride group. You may have 2 or more types of reactive functional groups. In the present invention, an acid anhydride group is more preferable.

For example, when it is desired to obtain an ethylene-based rubbery polymer (C) having an acid anhydride group as the reactive functional group (ii), an acid anhydride and an acid anhydride are added to the rubber component such as an ethylene / α-olefin copolymer. It can be produced by reacting a peroxide. For example, when it is desired to obtain an ethylene-based rubbery polymer (C) having a carboxyl group as a reactive functional group, it can be produced by copolymerizing the aforementioned rubber component and an unsaturated carboxylic acid. Examples of the acid anhydride include maleic anhydride, 1,2-dimethylmaleic anhydride, ethylmaleic anhydride, itaconic anhydride, phenylmaleic anhydride, citraconic anhydride, and maleic anhydride is preferably used. Is done. Examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid.

Moreover, a commercially available product can be used as the ethylene-based rubbery polymer having an acid anhydride group. Examples of commercially available products include maleic anhydride-modified ethylene-butene copolymers (“Tuffmer” (registered trademark) MH7020, MH5040) manufactured by Mitsui Chemicals, Inc.

The amount of modification by the reactive functional group (ii) of the rubbery polymer (C) used in the present invention is 0.1 to 10% by mass of the whole rubbery polymer (C) from the viewpoint of improving the color tone and balancing various physical properties. Is preferred. For example, in the case of the rubbery polymer (C) having an acid anhydride group as the reactive functional group (ii), the amount of acid modification of the rubbery polymer (C) is 130 with the xylene of the rubbery polymer (C). It can be measured from a solution dissolved at 0 ° C. using a 0.02 mol / L ethanol solution (manufactured by Aldrich) of potassium hydroxide as a titrant and a 1% ethanol solution of phenolphthalein as an indicator.

The glass transition temperature of the rubbery polymer (C) used in the present invention is preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and further preferably −45 ° C. or lower. If the glass transition temperature of the rubber polymer (C) is −10 ° C. or lower, the impact resistance of the molded product can be further improved. In the present invention, the glass transition temperature of the rubbery polymer (C) can be determined by DSC measurement (differential scanning calorimetry). The DSC measurement can be performed using a differential scanning calorimeter (DSCQ200 (manufactured by TA Instruments)). The measurement conditions are as follows: 10 mg of sample, under a nitrogen atmosphere, the temperature is increased from −80 ° C. to 150 ° C. at a temperature increase rate of 5 ° C./min with a temperature modulation amplitude of ± 1 ° C. and a temperature modulation period of 60 seconds.

<Rubber polymer (D)>
The thermoplastic resin composition of the present invention can be obtained by blending (D) an ethylene rubber polymer (hereinafter sometimes referred to as “rubber polymer (D)”), if necessary. . By blending the rubber polymer (D), the impact resistance of the molded product can be further improved.

The rubbery polymer (D) used in the present invention is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, such as an ethylene / α-olefin copolymer or an ethylene / propylene copolymer. Ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer, and the like. Two or more of these may be blended.

The glass transition temperature of the rubbery polymer (D) used in the present invention is preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and further preferably −45 ° C. or lower. If the glass transition temperature of the rubbery polymer (D) is −10 ° C. or less, the impact resistance of the molded product can be further improved. In the present invention, the glass transition temperature of the rubber polymer (D) can be determined by DSC measurement (differential scanning calorimetry). The DSC measurement can be performed using a differential scanning calorimeter (DSCQ200 (manufactured by TA Instruments)). The measurement conditions are as follows: 10 mg of sample, under a nitrogen atmosphere, the temperature is increased from −80 ° C. to 150 ° C. at a temperature increase rate of 5 ° C./min with a temperature modulation amplitude of ± 1 ° C. and a temperature modulation period of 60 seconds.

The amount of each component in the thermoplastic resin composition of the present invention is 0.1 to 95 parts by weight of the copolymer (A) to 100 parts by weight of the total of (A) to (D). B) 0 to 94.9 parts by mass, rubbery polymer (C) 5 to 40 parts by mass, and rubbery polymer (D) 0 to 35 parts by mass. When the blending amount of the copolymer (A) is less than 0.1 parts by mass, a graft product of the copolymer (A) and the rubbery polymer (C) is hardly formed, and the copolymer (A) and Since the effect of improving the compatibility with the rubber polymer (C) cannot be obtained, the impact resistance and appearance of the molded product tend to be lowered. The blending amount of the copolymer (A) is preferably 1 part by mass or more. On the other hand, when the blending amount of the copolymer (A) exceeds 95 parts by mass, the blending amount of the rubbery polymer (C) becomes relatively low, and the impact resistance of the molded product tends to be lowered. The blending amount of the copolymer (A) is preferably 90 parts by mass or less. Further, when the blending amount of the copolymer (B) exceeds 94.9 parts by mass, the blending amounts of the copolymer (A) and the rubber-like polymer (C) are relatively low, so There is a tendency for impact properties to decrease. Further, when the blending amount of the rubbery polymer (C) is less than 5 parts by mass, a graft product of the copolymer (A) and the rubbery polymer (C) is difficult to be generated, and the impact resistance of the molded product. Decreases. The amount of the rubber polymer (C) is preferably 10 parts by mass or more. On the other hand, when the blending amount of the rubber polymer (C) exceeds 40 parts by mass, the moldability and the rigidity of the molded product tend to decrease. The amount of the rubber polymer (C) is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. Further, if the blending amount of the copolymer (D) exceeds 35 parts by mass, the blending amount of the copolymer (A) and the rubbery polymer (C) becomes relatively low, so that the impact resistance of the molded product. Tends to decrease. The blending amount of the copolymer (D) is preferably 20 parts by mass or less.

<Peroxide (E)>
The thermoplastic resin composition of the present invention can be obtained by blending (E) peroxide (hereinafter sometimes referred to as “peroxide (E)”) as necessary. The peroxide (E) can promote the reaction between the copolymer (A) and the rubbery polymer (C), and can further improve the impact resistance of the molded product. Examples of the peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di-t. -Butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, and the like. A commercially available product can be used as the peroxide (E). As a commercial item, the NOF Corporation make ("Perhexa" (trademark) 25B) etc. are mentioned, for example. Two or more of these may be blended.

The blending amount of the peroxide (E) in the thermoplastic resin composition of the present invention is preferably 0.1 to 1 part by mass with respect to 100 parts by mass in total of (A) to (D). By setting the blending amount of the copolymer (E) to 0.1 parts by mass or more, the impact resistance of the molded product can be further improved. On the other hand, by setting the blending amount of the peroxide (E) to 1 part by mass or less, side reactions such as gelation can be suppressed.
<Ethylene polymer (F)>
The thermoplastic resin composition of the present invention can be obtained by blending (F) an ethylene polymer (hereinafter sometimes referred to as “ethylene polymer (F)”) as necessary. By blending the ethylene polymer (F), the impact resistance and gloss of the molded product can be further improved.

The component constituting the ethylene polymer (F) used in the present invention may be any polymer having a functional group that reacts with the reactive functional group (i) using ethylene as a monomer component. It may be a copolymer with other unsaturated monomers. Examples thereof include an ethylene polymer and an ethylene / α-olefin copolymer. Here, “/” indicates a copolymer. The ethylene / α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, such as an ethylene / propylene copolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer. Examples thereof include a polymer and an ethylene / octene copolymer. Two or more of these may be blended. As the reactive functional group of the ethylene polymer (F), those reactive with the reactive functional group (i) described above are preferable. Examples thereof include a carboxyl group and an acid anhydride group. You may have 2 or more types of reactive functional groups. In the present invention, an acid anhydride group is preferred.

Also, commercially available products can be used as the ethylene polymer having an acid anhydride group. Examples of commercially available products include acid-modified ethylene polymers (“High Wax” (registered trademark) 1105A, 2203A) manufactured by Mitsui Chemicals, Inc.

The weight average molecular weight of the ethylene polymer (F) used in the present invention is preferably 500 or more and 30,000 or less. By setting the weight average molecular weight of the copolymer (A) to 500 or more, the impact resistance and rigidity of the molded product can be further improved. The molecular weight is more preferably 700 or more, and most preferably 1000 or more. On the other hand, by setting the weight average molecular weight of the ethylene polymer (F) to 30,000 or less, compatibility with the rubber polymer (C) is improved, and uneven gloss can be reduced. The molecular weight is more preferably 20,000 or less, and most preferably 10,000 or less.

The blending amount of the ethylene polymer (F) in the thermoplastic resin composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of (A) to (D) and (F). . By setting the blending amount of the ethylene polymer (F) to 0.1 parts by mass or more, the impact resistance of the molded product can be further improved. On the other hand, the impact resistance fall of a molded article can be suppressed by making the compounding quantity of an ethylene-type polymer (F) into 10 mass parts or less.

The thermoplastic resin composition of the present invention is within the range that does not impair the effects of the present invention, and further, flame retardant, filler, other thermoplastic resin, thermosetting resin, soft thermoplastic resin, various additives or modifications You may obtain by mix | blending an agent.

Flame retardancy can be improved by blending a flame retardant with the thermoplastic resin composition of the present invention. There is no restriction | limiting in particular in a flame retardant, So-called general flame retardant can be mix | blended. For example, phosphorus compounds, halogen organic compounds, nitrogen-containing organic compounds such as melamine, inorganic compounds such as magnesium hydroxide and aluminum hydroxide, polyorganosiloxane compounds, arsenic oxide, antimony oxide, bismuth oxide, iron oxide, oxidation Examples thereof include metal oxides such as zinc and tin oxide, and silica. Two or more of these may be blended. A phosphorus compound and a halogen organic compound are preferable, and a phosphorus compound is particularly preferable.

The phosphorus compound is not particularly limited as long as it is an organic or inorganic compound containing phosphorus, and examples thereof include ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate, and phosphine oxide. Of these, aromatic phosphates can be particularly preferably used.

Examples of the halogen-based organic compound include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromophthalimide, Examples include sabromobutene, trichlorotetrabromophenyl-triphosphate, hexabromocyclododecane, and compounds obtained by modifying these with various substituents. Two or more of these may be blended.

When a flame retardant is blended, it is generally used in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the components (A), (B), (C) and (D). A range of ˜20 parts by mass is more preferred. By blending 0.1 part by mass or more of the flame retardant, the flame retardant effect can be exhibited, and by blending 30 parts by mass or less, the mechanical strength and heat resistance of the molded product can be improved.

By blending a filler with the thermoplastic resin composition of the present invention, the strength and dimensional stability of the molded product can be improved. The shape of the filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used. Examples of the fibrous filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, and stone powder. Examples thereof include fibers and metal fibers. Non-fibrous fillers include, for example, silicates such as wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate, alumina, silicon oxide, magnesium oxide, oxidation Metal oxides such as zirconium, titanium oxide and iron oxide, metal carbonates such as calcium carbonate, magnesium carbonate and dolomite, metal sulfates such as calcium sulfate and barium sulfate, magnesium hydroxide, calcium hydroxide and aluminum hydroxide Examples thereof include metal hydroxide, glass beads, ceramic beads, boron nitride and silicon carbide. These may be hollow, and two or more of these fillers may be blended. In addition, these fillers may be pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound to further improve the mechanical strength of the molded product. Can be made.

When the filler is blended, the blending amount is not particularly limited, but usually 0.1 to 0.1 parts by mass with respect to a total of 100 parts by mass of the components (A), (B), (C) and (D). 200 parts by mass is blended.

The thermoplastic resin composition of the present invention may be blended with a thermoplastic resin other than the components (A) to (D), a thermosetting resin, or a soft thermoplastic resin within a range not impairing the effects of the present invention. It doesn't matter. Examples of the thermoplastic resin include polyethylene resin, polypropylene resin, acrylic resin, polyamide resin, polyphenylene sulfide resin, polyether ether ketone resin, polyester resin, polysulfone resin, polyether sulfone resin, aromatic or aliphatic polycarbonate resin, poly Arylate resin, polyphenylene oxide resin, polyacetal resin, polyimide resin, polyetherimide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, aromatic or aliphatic polyketone resin, fluorine resin, polyvinyl chloride resin, polyvinylidene chloride resin, Examples thereof include vinyl ester resins, polyurethane resins, cellulose acetate resins, and polyvinyl alcohol resins. Examples of the thermosetting resin include phenol resin, melamine resin, polyester resin, silicone resin, and epoxy resin. Examples of the soft thermoplastic resin include an ethylene / glycidyl methacrylate copolymer, a polyester elastomer, a polyamide elastomer, an ethylene / propylene terpolymer, and an ethylene / butene-1 copolymer.

When other thermoplastic resins, thermosetting resins or soft thermoplastic resins are blended, the total blending amount is 100 masses of the total of (A) component, (B) component, (C) component and (D) component. 30 parts by mass or less is preferable with respect to parts, and 10 parts by mass or less is more preferable.

In the thermoplastic resin composition of the present invention, various additives may be blended as long as the effects of the present invention are not impaired. Examples of the additives include plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds, crystal nucleating agents such as talc, kaolin, organic phosphorus compounds, polyether ether ketone, and polyolefins. Release agents such as compounds, silicone compounds, long chain aliphatic ester compounds, long chain aliphatic amide compounds, anticorrosives, anti-coloring agents, antioxidants, thermal stabilizers, lithium stearate, aluminum stearate, etc. And lubricants, UV inhibitors, colorants, foaming agents, and the like.

<Thermoplastic resin composition>
In the thermoplastic resin composition of the present invention, the rising temperature of the storage elastic modulus in dynamic viscoelasticity measurement is the glass transition temperature of the rubbery polymer (C) + 20 ° C. or less, and the rubbery polymer (C) is Dispersed with an average particle diameter of 0.6 μm or less. The dispersed particles of the rubbery polymer (C) mentioned here may be a graft product of the rubbery polymer (C) and the polymer (A) described above.

The rising temperature of the storage elastic modulus in the dynamic viscoelasticity measurement is an index representing the flexibility of the rubber polymer (C) in the thermoplastic resin composition. The rubbery polymer (C) tends to lose its inherent properties of the rubbery polymer (C) with changes such as the formation of a graft product by reaction with the polymer (A) described above. In the present invention, in the thermoplastic resin composition, attention is paid to the rising temperature of the storage elastic modulus as an index indicating the original characteristics of the rubber polymer (C), and this is the glass transition temperature of the rubber polymer (C) +20. It is characterized by being below ℃. As the rise temperature of the storage elastic modulus is closer to the glass transition temperature of the rubber polymer (C), the inherent property (flexibility) of the rubber polymer (C) is maintained in the thermoplastic resin composition. It shows that. When the rising temperature of the storage elastic modulus is higher than the glass transition temperature of the rubbery polymer (C) + 20 ° C., the flexibility of the rubbery polymer (C) is impaired, and the impact resistance of the molded product is lowered. The rising temperature of the storage elastic modulus is preferably the glass transition temperature of the rubbery polymer (C) + 15 ° C. or less.

Further, the average particle size of the rubber polymer (C) being 0.6 μm or less indicates that the rubber polymer (C) is dispersed with finer particles. Therefore, the dispersion structure of the thermoplastic resin composition becomes more uniform, the rubber polymer (C) can fully exhibit the inherent flexibility, and the impact resistance and gloss of the molded product can be improved. . 0.5 μm or less is preferable, and 0.4 μm or less is more preferable. When the average particle diameter of the rubber polymer (C) exceeds 0.6 μm, the impact resistance and gloss of the molded product are lowered.

Conventionally, in order to increase the dispersibility of the rubber polymer, a large amount of the graft chain was required for the rubber polymer. However, as the graft chain increased, the flexibility of the thermoplastic resin composition decreased, and the molded product In some cases, the impact resistance of the resin deteriorated. On the other hand, if it is attempted to maintain the flexibility of the rubbery polymer in the thermoplastic resin composition, the average particle diameter of the rubbery polymer becomes large, and the impact resistance of the molded product may also decrease. In the present invention, for example, the use of a thermoplastic resin composition obtained by blending the copolymer (A) or the copolymer (B) having a weight average molecular weight within the above-mentioned preferred range, Use of a thermoplastic resin composition obtained by blending the rubbery polymer (C) having a modified amount in the above-mentioned preferred range, and a thermoplastic resin composition obtained by blending the above-mentioned (E) peroxide. Can be finely dispersed while maintaining the flexibility of the rubbery polymer (C) in the thermoplastic resin composition by means such as using a manufacturing method described later, and the impact resistance of the molded product. Can be greatly improved.

In the present invention, the rising temperature of the storage elastic modulus and the average particle diameter of the rubbery polymer (C) in the dynamic viscoelasticity measurement of the thermoplastic resin composition can be measured by preparing a test piece from the molded product. . Under general molding conditions, the rise temperature of the storage elastic modulus and the average particle diameter of the rubbery polymer (C) are not changed. In the present invention, the molding temperature is 220 ° C., the mold temperature is 60 ° C., Injection speed: 100 mm / second, injection time: 10 seconds, cooling time: 20 seconds, molding pressure: pressure from which all resin is filled in the mold (molding lower limit pressure) + 2MPa Make it.

The storage elastic modulus is measured in a bending mode using a DMS6100 manufactured by Seiko Instruments Inc. after cutting a test piece having a length of 45 mm and a width of 12.8 mm from a molded product having a thickness of 3 mm molded according to the above conditions. The measurement conditions are a frequency of 0.5 Hz, a distance between chucks of 20 mm, a heating rate of 2 ° C./min, and −100 ° C. to 0 ° C. The storage elastic modulus is plotted on the vertical axis, the temperature is plotted on the horizontal axis, and the temperature corresponding to the point at which the tangent of the plateau region of the storage modulus intersects with the tangent of the portion where the slope becomes a straight line after rising is expressed as the rising temperature of the storage elastic modulus. And

Further, the average particle diameter of the rubber polymer (C) is observed by magnifying the sample obtained by cutting an ultrathin section from the molded article molded under the above conditions by 1000 times using a transmission electron microscope. Take a picture of the area. From this electron micrograph, 100 rubbery polymers (C) forming a dispersed phase are randomly selected, the major axis of each is measured, and the number average value is taken as the average particle size.

The thermoplastic resin composition of the present invention includes, for example, the copolymer (A), if necessary, a copolymer (B), a rubbery polymer (C), if necessary, a rubbery polymer (D), and other if necessary The components can be obtained by melt kneading by chaotic mixing in a twin screw extruder. By melt-kneading by chaos mixing, the copolymer (A) and the rubbery polymer (C) can be reacted uniformly and efficiently. In the present invention, for example, a copolymer (A) having a weight average molecular weight of 10,000 to 300,000 and a rubbery polymer (C) having an acid modification amount of 0.1 to 10% by mass are used. By performing melt kneading by chaos mixing, a thermoplastic resin composition having the above characteristics can be easily obtained. In the case of a thermoplastic resin composition obtained by blending the copolymer (B) and / or the rubbery polymer (D), at least the above (A) and (C) are mixed by chaos mixing using a twin screw extruder. After melt-kneading, it is preferable to further blend (B) and / or (D) and melt-knead. The conditions for further blending (B) and / or (D) above after melt-kneading (A) and (C) by chaos mixing using a twin-screw extruder and then melt-kneading are chaotic mixing. Or it may be ordinary melt-kneading. By melting and kneading (A) and (C) by chaos mixing using a twin screw extruder, the reaction of (A) and (C) proceeds more efficiently, and the surface gloss of the molded product is increased. Can be improved. Components such as the aforementioned additives can be blended at any stage. For example, the copolymer (A), if necessary, the copolymer (B), the rubbery polymer (C), if necessary, may be blended together with the rubbery polymer (D). (D) may be blended after melt-kneading, or may be blended in advance with at least one of the above-mentioned (A) to (D) and melt-kneaded, and then the remaining components may be blended.

Explain chaotic mixing. Considering the mixing of two fluids, solving the equation governing the motion of fluid particles with their positions as initial values for all points on the boundary surface of the initial two fluids, the time evolution of the boundary surface is Can be sought. In order for the two fluids to mix quickly, this boundary surface must be folded at small intervals, so the area of the boundary surface must increase rapidly, and at first the boundary that was very close The distance between two points on the surface needs to increase rapidly. In this way, a mixture having a chaotic solution in which the distance between two points exponentially increases with time in a solution of an equation governing fluid motion is called chaotic mixing. Chaos mixing is described, for example, in Chaos, “Solitons” & “Fractals” Vol.6 “p425-438”.

In the present invention, the chaotic mixing is performed by the logarithm of the imaginary line elongation (lnL / L ₀ ) when the line length is L and the initial line length is L ₀ in the particle tracking method. 2 or more is preferable. When the logarithm of the imaginary line stretch (lnL / L ₀ ) is large, it means that the distance between the two points tends to increase exponentially with time in the solution of the equation governing the fluid motion. Yes. In this particle tracking method, the initial position of 1000 particles is randomly determined in the cross section of the upstream face of the screw to be evaluated at time t = 0, and the movement accompanying the velocity field of the evaluated screw obtained by analysis is tracked by simulation. It is a method to do. After the screw rotates for time t = T, from the record of the coordinate history of each particle, the time when the probability of existence of the particle is the highest is t = tp, and the line length at this time is L. The logarithm of elongation (lnL / L ₀ ) can be obtained. The particle tracking method is described in, for example, Journal of Non-Newtonian Fluid Mechanics Vol. 91, Issues 2-3, 1 July 2000, p273-295.
As a kneading temperature by chaos mixing, it is preferable to provide a zone 1 to 150 ° C. higher than the glass transition temperature based on the polymer having the highest glass transition temperature among the polymers to be used. Here, the kneading temperature refers to the set temperature of the cylinder of the twin screw extruder. What is necessary is just to provide at least one zone set to the said temperature between a polymer fusion | melting part and die head. By making the kneading temperature 1 ° C. or more higher than the glass transition temperature of the polymer having the highest glass transition temperature among the polymers to be used, the viscosity can be lowered moderately and the melt kneading can be carried out more sufficiently. Moreover, by setting it as glass transition temperature +150 degrees C or less, extending | stretching can fully advance easily and a chaos mixed state can be formed more easily.

As an effective screw for generating chaotic mixing state, the particle tracking method is preferably screw lnL / L ₀ is 2 or more, more preferably screw is 3 or more, still more preferably a screw to be 4 or more.

As a screw of a twin-screw extruder effective for generating such a chaotic mixed state, for example, a screw made of a kneading disk, the helical angle θ which is the angle between the top of the disk front side and the top of the rear side is a screw. And twist kneading discs in the range of 0 ° <θ <90 ° in the half rotation direction. Furthermore, chaos mixing is made more effective by combining back mixing screws with twist kneading discs, which are composed of flight screws, and in which resin passages are formed in the flight section from the screw front side to the rear end side. Can be generated.

In the present invention, it is preferable that the ratio of the total length of the melt-kneading zone (chaos mixing zone) by chaotic mixing to the total length of the screw of the twin screw extruder is in the range of 5 to 80%. By setting the ratio of the chaos mixing zone to 5% or more, it can be efficiently stretched and folded. 10% or more is more preferable, and 15% or more is more preferable. On the other hand, when the ratio of the chaos mixing zone is 80% or less, the extrusion processability can be improved. 70% or less is more preferable, and 60% or less is more preferable. Moreover, in this invention, it is preferable that the chaos mixing zone of a twin-screw extruder is arrange | positioned over the whole region, without uneven distribution in the specific position in a screw.

The thermoplastic resin composition of the present invention can be molded by any method such as generally known injection molding, extrusion molding, vacuum / pressure molding, inflation molding, blow molding and the like. The shape of the molded product is not particularly limited, and examples thereof include films, sheets, fibers / clothes, nonwoven fabrics, and various injection molded shapes. Moreover, it can also be set as a composite with another material, and can also be used after painting, plating, etc.

The molded product of the present invention can be usefully used as a structural material by utilizing excellent impact resistance and appearance. For example, the following articles. Various gears and various cases. Sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, terminal board, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, Electrical and electronic parts such as small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts. Generator, Electric motor, Transformer, Current transformer, Voltage regulator, Rectifier, Inverter, Relay, Power contact, Switch, Circuit breaker, Knife switch, Other pole rod, Electric parts cabinet, VTR parts, TV parts, Iron Audio equipment parts such as hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio compact discs, DVDs. Household and office electrical product parts such as lighting parts, refrigerator parts, air conditioner parts, air conditioner outdoor units, typewriter parts, word processor parts, etc. Office computer related parts, telephone related parts, mobile phone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, submersible bearings, motor parts, lighters, typewriters, etc. Machine-related parts represented by Optical equipment such as microscopes, binoculars, cameras, and watches, and precision machine related parts. Alternator terminal, alternator connector, IC regulator, light meter potentiometer base, air intake nozzle snorkel, intake manifold, air flow meter, air pump, fuel pump, engine coolant joint, thermostat housing, carburetor main body, carburetor spacer, engine Mount, ignition hobbin, ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS , Radiator Top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing, timing belt cover, brake Booster parts, various cases, fuel / exhaust / intake system tubes, tanks, fuel / exhaust / intake system hoses, various clips, exhaust gas valves and other valves, pipes, exhaust gas Sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air Thermostat base, air conditioning panel switch board, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, step motor rotor, brake piston, solenoid bobbin, engine oil filter, ignition Equipment case, torque control lever, starter switch, starter relay, safety belt parts, register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, distributor, sun visor bracket, various motor housings, roof rail , Fender, garnish, bumper, door mirror stay, haunter Automobiles such as minal, window washer nozzle, wiper arm, molding, mirror housing, spoiler, hood louver, wheel cover, wheel cap, radiator grill, grill apron cover frame, lamp reflector, lamp socket, lamp housing, lamp bezel, door handle Exterior materials, center console, instrument panel, instrument panel core, instrument panel pad, glove box, handle column, armrest, lever parking, front pillar trim, door trim, pillar trim, console box and other automotive interior materials, wire harness connector, SMJ connector, PCB Automotive parts such as connectors, door grommet connectors, and various connectors such as fuse connectors. PC, printer, display, CRT display, fax, copy, word processor, notebook computer, mobile phone, PHS, DVD drive, PD drive, flexible disk drive and other storage device housing, chassis, relay, switch, case member, transformer member Electrical and electronic equipment parts such as coil bobbins; machine parts, agricultural materials, horticultural materials, fishery materials, civil engineering and construction materials, and other various uses.

In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples. First, components used in Examples and Comparative Examples will be described.

Reference Example 1 (A-1) Copolymer Suspension polymerization of a monomer mixture composed of 75.7 parts by mass of styrene, 24 parts by mass of acrylonitrile, and 0.3 parts by mass of glycidyl methacrylate resulted in a bead-shaped copolymer. (A-1) was prepared. The content of each monomer unit was 75.7% by mass of styrene units, 24% by mass of acrylonitrile units, and 0.3% by mass of glycidyl methacrylate units. Using a hexafluoroisopropanol (HFIP) solution of the obtained copolymer (A-1), the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography and found to be 170,000. The glass transition temperature determined by DSC measurement (differential scanning calorimetry) was 115 ° C. The DSC measurement conditions were as follows: sample 10 mg, in a nitrogen atmosphere, from −80 ° C. to 150 ° C. with a temperature modulation rate of ± 1 ° C. and a temperature modulation period of 60 seconds at a temperature increase rate of 5 ° C./min

Reference Example 2 (A-2) Copolymer Suspension polymerization of a monomer mixture comprising 74.5 parts by mass of styrene, 22.5 parts by mass of acrylonitrile, and 3 parts by mass of glycidyl methacrylate resulted in a bead-shaped copolymer. (A-2) was prepared. The content of each monomer unit was 74.5% by mass of styrene units, 22.5% by mass of acrylonitrile units, and 3% by mass of glycidyl methacrylate units. Using a HFIP solution of the obtained copolymer (A-2), the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography and found to be 110,000. The glass transition temperature determined by DSC measurement was 110 ° C. The DSC measurement conditions were the same as in Reference Example 1.

[Reference Example 3] (A-3) Copolymer A monomer mixture consisting of 72 parts by mass of styrene, 22 parts by mass of acrylonitrile, and 6 parts by mass of glycidyl methacrylate was subjected to suspension polymerization to produce a bead-like copolymer (A-3). ) Was prepared. The content of each monomer unit was 72% by mass of styrene units, 22% by mass of acrylonitrile units, and 6% by mass of glycidyl methacrylate units. When the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography using the HFIP solution of the obtained copolymer (A-3), it was 70,000. The glass transition temperature determined by DSC measurement was 109 ° C. The DSC measurement conditions were the same as in Reference Example 1.

[Reference Example 4] (B-1) Copolymer A monomer mixture comprising 70 parts by mass of styrene and 30 parts by mass of acrylonitrile was subjected to suspension polymerization to prepare a bead-shaped copolymer (B-1). The content of each monomer unit was 70% by mass of styrene units and 30% by mass of acrylonitrile units. The polystyrene equivalent weight average molecular weight was measured by gel permeation chromatography using the HFIP solution of the obtained copolymer (B-1) and found to be 150,000. The glass transition temperature determined by DSC measurement was 110 ° C. The DSC measurement conditions were the same as in Reference Example 1.

[Reference Example 5] Graft copolymer 1
57 parts by mass of an ethylene / propylene / 5-ethylidene-2-norbornene copolymer (EPDM) (Mitsui EPT X-3012P) manufactured by Mitsui Chemicals, Ltd. was added to 400 parts by mass of n-hexane to which 200 parts by mass of ethylene dichloride was added. Dissolved. Next, 10 parts by mass of acrylonitrile, 33 parts by mass of styrene and 17 parts by mass of benzoyl peroxide were added, and polymerization was performed at 65 ° C. for 10 hours in a nitrogen atmosphere. After the polymerization, the polymerization reaction solution was poured into a large excess of methanol, the deposited precipitate was separated, and the graft polymer 1 was obtained through vacuum drying.

[Reference Example 6] Resin composition 1
(A-2) 43 parts by mass of a copolymer and 57 parts by mass of the following (C-1) rubbery polymer, a twin screw extruder (TEX30XSSST manufactured by JSW) with a screw rotation speed of 200 rpm (L / D = 45.5) and melt-kneaded. Here, L is the length from the raw material supply port to the discharge port, and D is the diameter of the screw (the same applies hereinafter). The cylinder set temperature after the polymer melt was adjusted to 230 ° C. The screw configuration of the extruder was composed of a kneading disk and a flight screw. As a kneading disk, a twist kneading disk in which the spiral angle θ, which is the angle between the top on the front end of the disk and the top on the rear side, is in the range of 0 ° <θ <90 ° in the half rotation direction of the screw. used. As the kneading disk, a back mixing screw in which a resin passage is formed from the screw front end side toward the rear end side was used. The kneading disk and the flight screw were alternately combined so that the total length of the melt kneading zone while mixing with chaos (chaos mixing zone) was 50% of the total length of the extruder screw. Hereinafter, this screw configuration is referred to as A type. For this condition, the initial position of 1000 particles in the cross section of the upstream surface of the screw was randomly determined at time t = 0 using the in-extruder CAE analysis software SCREWFLOW-MULTI from JSW, and obtained by analysis. the movement associated with the velocity field of the screw evaluating monitored by simulation, line length of the (L), the initial line length imaginary line of extension of the logarithm of the time to _{(L 0) (lnL / L} 0) the results obtained, lnL / _{L 0} was 4.3. The gut discharged from the die was immediately cooled in ice water to fix the structure, and then pelletized with a strand cutter to obtain pellets.

(C-1) Rubber polymer A maleic anhydride-modified ethylene-butene copolymer ("Toughmer" (registered trademark) MH5040, glass transition temperature -65 ° C determined by DSC measurement) manufactured by Mitsui Chemicals, Inc. was used. The DSC measurement conditions were the same as in Reference Example 1.

(D-1) Rubber polymer Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (EPDM) manufactured by Mitsui Chemicals, Inc. (Mitsui EPT X-3012P, glass transition temperature -51 ° C. determined by DSC measurement) It was used. The DSC measurement conditions were the same as in Reference Example 1.

(E-1) Peroxide 2,5-dimethyl-2,5-di-t-butylperoxyhexane (“Perhexa” (registered trademark) 25B) manufactured by NOF Corporation was used.

(F-1) Ethylene Polymer An acid-modified polyolefin (“High Wax” (registered trademark) 1105A, molecular weight 1500) manufactured by Mitsui Chemicals, Inc. was used.

Next, evaluation methods in each example and comparative example will be described. From the pellets obtained in each of the examples and comparative examples, using an injection molding machine (SE75DUZ) manufactured by Sumitomo Heavy Industries, Ltd., molding temperature: 220 ° C., mold temperature: 60 ° C., injection speed: 100 mm / second , Injection time: 10 seconds, cooling time: 20 seconds, molding pressure: test pieces described in the following items were injection molded under the conditions of pressure (molding lower limit pressure) at which the resin is completely filled in the mold + 2 MPa.

(1) Average particle diameter A sample obtained by cutting out an ultrathin section from a molded product having a thickness of 3 mm molded according to the above conditions was observed with a transmission electron microscope (HITACHI, ELECTRON MICROSCOPE H-700) at a magnification of 1000 times. The observation site was photographed. From this electron micrograph, 100 rubbery polymers (C) forming a dispersed phase were randomly selected, the major axis of each was measured, and the number average value was taken as the average particle size.

(2) Rise temperature of storage elastic modulus A test piece having a length of 45 mm and a width of 12.8 mm was cut out from a molded product having a thickness of 3 mm molded according to the above conditions, and storage elasticity was measured in a bending mode using a DMS6100 manufactured by Seiko Instruments Inc. The rate was measured. The measurement conditions were a frequency of 0.5 Hz, a distance between chucks of 20 mm, a heating rate of 2 ° C./min, and −100 ° C. to 0 ° C. The storage elastic modulus is plotted on the vertical axis, the temperature is plotted on the horizontal axis, and the temperature corresponding to the point at which the tangent of the plateau region of the storage modulus intersects with the tangent of the portion where the slope becomes a straight line after rising is expressed as the rising temperature of the storage elastic modulus. It was.

(3) Impact resistance Notched Izod impact strength was measured at 23 ° C. according to ASTM D-256 using a 1/4 inch thickness test piece molded according to the above conditions. The impact strength was measured for each of six test pieces, and the average value was defined as Izod impact strength. Further, the sample after the Izod impact test was visually observed to determine ductile fracture and brittle fracture.

(4) Flexural modulus The flexural modulus was evaluated according to ASTM D790 using a 1/4 inch thickness test piece molded according to the above conditions. The bending elastic modulus was measured for each of the three test pieces, and the average value was taken as the bending elastic modulus.

(5) Heat resistance (deflection temperature under load)
The deflection temperature under load was measured according to ASTM D648 (load: 1.82 MPa) using a test piece cut out from a molded product molded under the above conditions. The deflection temperature under load was measured for each of the two test pieces, and the average value was taken as the deflection temperature under load.

(6) Appearance The surface of a molded product having a thickness of 3 mm molded under the above conditions was visually observed, and gloss unevenness was evaluated according to the following criteria.

A: No gloss unevenness B: Partial gloss unevenness C: Overall gloss unevenness (7) Surface gloss Surface gloss at the center of a test piece of 80 mm × 80 mm × 3 mm thickness molded according to the above conditions Using a digital variable gloss meter (“UGV-5D” manufactured by Suga Test Instruments Co., Ltd.), the measurement was performed at an incident angle of 60 degrees. The average value measured three times was defined as the glossiness.

(8) Residual emulsifier 1 g of pellets obtained in each Example and Comparative Example were extracted with methanol, filtered with 0.5 μm filter paper, the filtrate was concentrated, and then dried with a vacuum dryer to extract components. The presence or absence of was determined by visual observation.

(Examples 1 to 5, 7, 8)
Each component shown in Table 1 was supplied to a twin screw extruder (TEX30XSSST, manufactured by JSW) (L / D = 45.5) (L / D = 45.5) at a blending ratio shown in Table 1 and a screw rotation speed of 200 rpm, and melt kneaded. The cylinder set temperature after the polymer melting part was adjusted to 150 ° C. Moreover, the screw structure of the extruder used the A type screw structure. For this condition, the initial position of 1000 virtual particles is randomly determined in the fluid at the upstream end of the screw at time t = 0, using the in-extruder CAE analysis software SCREWFLOW-MULTI, manufactured by Nippon Steel. Assuming that the screw rotation speed is 200 rpm, the resin temperature is 150 ° C., and the melt viscosity is 3000 Pa · s, the movement accompanying the velocity field of the screw to be evaluated obtained by analysis is traced by simulation, and the line length (L) and initial line length As a result of obtaining lnL / L ₀ when (L ₀ ), lnL / L ₀ was 4.2.

ガ The gut discharged from the die was immediately cooled in ice water to fix the structure, and then pelletized with a strand cutter to obtain pellets. Table 1 shows the results of evaluation of each property by the above method using the obtained pellets.

(Example 6)
(B-1) and the resin composition 1 obtained by the method described in Reference Example 6 were mixed at the mixing ratio shown in Table 1 so as to have the same composition as Example 3, and the screw rotation speed was 200 rpm. It supplied to the screw extruder (TEX30XSSST by JSW) (L / D = 45.5), and was melt-kneaded. The cylinder set temperature after the polymer melting part was adjusted to 150 ° C. Moreover, the screw structure of the extruder used the A type screw structure. For this condition, the initial position of 1000 virtual particles is randomly determined in the fluid at the upstream end of the screw at time t = 0 using the in-extruder CAE analysis software SCREWFLOW-MULTI from JSW. Assuming that the rotational speed is 200 rpm, the resin temperature is 150 ° C., and the melt viscosity is 2600 Pa · s, the movement accompanying the speed field of the screw to be evaluated obtained by analysis is traced by simulation, and the line length (L) and initial line length (L ₀₎ and the result of obtaining the lnL / _{L 0} when, lnL / _{L 0} was 4.1.

ガ The gut discharged from the die was immediately cooled in ice water to fix the structure, and then pelletized with a strand cutter to obtain pellets. Table 1 shows the results of evaluation of each property by the above method using the obtained pellets.

(Comparative Example 1)
Each component shown in Table 1 was supplied to a twin screw extruder (TEX30XSSST, manufactured by JSW) (L / D = 45.5) (L / D = 45.5) at a blending ratio shown in Table 1 and a screw rotation speed of 200 rpm, and melt kneaded. The cylinder set temperature after the polymer melt was adjusted to 230 ° C. Moreover, the screw structure shall have provided the general kneading disk (L / D = 3.8) from the position of L / D = 22,28. This screw configuration is called B type. When lnL / L ₀ was determined in the same manner as in Example 1 with a screw rotation speed of 200 rpm, a resin temperature of 230 ° C., and a melt viscosity of 500 Pa · s, lnL / L ₀ was 1.5.

ガ The gut discharged from the die was immediately cooled in ice water to fix the structure, and then pelletized with a strand cutter to obtain pellets. Table 2 shows the results of evaluation of each property by the above method using the obtained pellets.

(Comparative Example 2)
Pellets were obtained in the same manner as in Comparative Example 1 except that each component and the blending ratio were changed as shown in Table 1. When lnL / L ₀ was determined in the same manner as in Example 1 with screw rotation speed = 200 rpm, resin temperature = 230 ° C., melt viscosity = 500 Pa · s, lnL / L ₀ was 1.5. Table 1 shows the results of evaluation of each property by the above method using the obtained pellets.

(Comparative Examples 3 to 4)
Pellets were obtained in the same manner as in Example 1 except that each component and the blending ratio were changed as shown in Table 1. When lnL / L ₀ was determined in the same manner as in Example 1 with screw rotation speed = 200 rpm, resin temperature = 150 ° C., and melt viscosity = 3000 Pa · s, lnL / L ₀ was 4.2. Table 2 shows the results of evaluation of each property by the above method using the obtained pellets.

(Comparative Example 5)
The cylinder set temperature was changed to 230 ° C, and the screw configuration was changed from the position of L / D = 22, 28 to a screw configuration (B type) with a general kneading disk (L / D = 3.8). Except for the above, pellets were obtained in the same manner as in Example 1. When lnL / L ₀ was determined in the same manner as in Example 1 with screw rotation speed = 200 rpm, resin temperature = 230 ° C., melt viscosity = 500 Pa · s, lnL / L ₀ was 1.5. Table 2 shows the results of evaluation of each property by the above method using the obtained pellets.

The thermoplastic resin composition of the present invention can be used for various applications such as electric / electronic parts, home appliances, OA equipment, automobile parts, and mechanical mechanism parts.

Claims (9)

1. (A) Copolymer of (a1) vinyl monomer having reactive functional group (i), (a2) aromatic vinyl monomer and (a3) vinyl cyanide monomer 0.1 ~ 95 parts by mass,
   (B) a copolymer of (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer, 0 to 94.9 parts by mass,
   (C) 5 to 40 parts by mass of an ethylene rubbery polymer having a reactive functional group (ii) and (D) 0 to 35 parts by mass of an ethylene rubbery polymer (provided that (A), (B), ( C) and (D) is a thermoplastic resin composition obtained by blending 100 parts by mass), and the rising temperature of the storage elastic modulus in dynamic viscoelasticity measurement is the above-mentioned (C) reactive functional group ( The glass transition temperature of the ethylene rubber polymer having ii) is not higher than 20 ° C. and (C) the ethylene rubber polymer having a reactive functional group (ii) is dispersed with an average particle diameter of 0.6 μm or less. A thermoplastic resin composition.
2. Weight of copolymer of (A) (a1) vinyl monomer having reactive functional group (i), (a2) aromatic vinyl monomer and (a3) vinyl cyanide monomer The thermoplastic resin composition according to claim 1, wherein the average molecular weight is 10,000 or more and 300,000 or less.
3. 2. The composition obtained by further blending (E) 0.1 to 1 part by mass of peroxide with respect to a total of 100 parts by mass of (A), (B), (C) and (D). Or the thermoplastic resin composition of 2.
4. The weight average molecular weight of the copolymer of (B) (b1) aromatic vinyl monomer and (b2) vinyl cyanide monomer is 100,000 or more and 300,000 or less. The thermoplastic resin composition according to claim 1.
5. Reaction in the copolymer of (A) (a1) vinyl monomer having reactive functional group (i), (a2) aromatic vinyl monomer and (a3) vinyl cyanide monomer The thermoplastic resin composition according to any one of claims 1 to 4, wherein the functional functional group (i) is an epoxy group.
6. 6. The thermoplastic resin composition according to claim 1, wherein the reactive functional group (ii) in the ethylene-based rubbery polymer having the reactive functional group (ii) is an acid anhydride group. .
7. (A) Copolymer of (a1) vinyl monomer having reactive functional group (i), (a2) aromatic vinyl monomer and (a3) vinyl cyanide monomer 0.1 ~ 95 parts by mass,
   (B) a copolymer of (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer, 0 to 94.9 parts by mass,
   (C) 5 to 40 parts by mass of an ethylene rubbery polymer having a reactive functional group (ii) and (D) 0 to 35 parts by mass of an ethylene rubbery polymer (provided that (A), (B), ( The method for producing a thermoplastic resin composition according to any one of claims 1 to 6, wherein the total of C) and (D) is 100 parts by mass) by chaos mixing using a twin screw extruder.
8. Chaotic mixing is a chaotic mixing in which the logarithm of the imaginary line elongation (lnL / L ₀ ) is 2 or more when the line length (L) and the initial line length (L ₀ ) are used in the particle tracking method. A method for producing a thermoplastic resin composition according to claim 7.
9. 9. The method according to claim 7, further comprising the step of melt-kneading at least the (A) and (C) by further blending the (B) and / or (D) after being melt-kneaded by chaos mixing in a twin-screw extruder. The manufacturing method of the thermoplastic resin composition of description.