TW201502148A - 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 20 DEG C 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 [mu]m or less.

Description

Thermoplastic resin composition and method of producing the same

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

Acrylonitrile/butadiene/styrene copolymer (ABS) is excellent in processability and appearance, and has higher strength or rigidity than polystyrene, and is excellent in heat resistance and chemical resistance. Automated (OA, Office Automation) equipment, and is used for a wider range of applications such as automotive parts and building materials. Further, an acrylonitrile/ethylene rubber/styrene copolymer (AES) using a vinyl rubber as a rubber component is also widely used.

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

As a method for producing AES, for example, it is known that an ethylene-based colloidal polymer is emulsified in a large-volume solvent, and a vinyl monomer such as acrylonitrile and an aromatic vinyl such as styrene are present in the presence of the ethylene-based colloidal polymer latex. A method in which a monomer is subjected to emulsion graft polymerization or the like (for example, refer to Patent Document 1). However, AES obtained by the complicated manufacturing process tends to easily mix impurities such as an emulsifier to reduce impact resistance or rigidity.

In addition, as a method of producing a thermoplastic resin composition such as AES by a melt-kneading method, for example, a monomer unit having (I) an aromatic vinyl monomer unit and a vinyl monomer unit having an epoxy group is proposed. Copolymers and (II) unsaturated dicarboxylic acids A method of melt-mixing a modified polyolefin-based polymer modified with an acid anhydride monomer unit and/or an unsaturated carboxylic acid monomer unit as a raw material (for example, refer to Patent Documents 2 to 3). However, the above method has a problem that it is difficult to efficiently carry out the reaction of (I) and (II), and the balance between impact resistance, rigidity, and appearance is insufficient.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Publication No. Sho 49-14549 (British Patent Application Publication No. 1323506)

Patent Document 2: Japanese Patent Laid-Open No. Hei 6-9840

Patent Document 3: Japanese Patent Laid-Open No. Hei 11-228769

An object of the present invention is to provide a thermoplastic resin composition which is excellent in a balance between impact resistance and rigidity and which is excellent in appearance and a method for producing the same.

In order to solve the above problems, the inventors of the present invention have found that the above problem can be solved by setting the rising temperature and the average particle diameter of the storage elastic modulus of the rubber component in the thermoplastic resin composition to a specific range. The present invention has been completed.

The thermoplastic resin composition of the present invention has the following constitution. The thermoplastic resin composition is obtained by blending the following components: (A) (a1) a vinyl monomer having a reactive functional group (i) and (a2) an aromatic vinyl monomer and (a3) vinyl cyanide a monomer copolymer of 0.1 to 95 parts by mass, (B) (b1) a copolymer of an aromatic vinyl monomer and (b2) a vinyl cyanide monomer: 0 to 94.9 parts by mass, and (C) a vinyl colloidal polymer having a reactive functional group (ii) 5~ 40 parts by mass, and (D) ethylene-based colloidal polymer 0 to 35 parts by mass

(wherein the total of (A), (B), (C) and (D) is 100 parts by mass), and the rising temperature of the storage elastic modulus in the dynamic viscoelasticity measurement is (C) having a reactive functional group ( Ii) The ethylene-based colloidal polymer has a glass transition temperature of +20 ° C or lower, and (C) the vinyl-based colloidal polymer having a reactive functional group (ii) is dispersed at an average particle diameter of 0.6 μm or less.

Further, the present invention has the following constitution as a method for producing the thermoplastic resin composition. The above thermoplastic resin composition is produced by melt-kneading the following components by chaotic mixing using a twin-screw extruder: (A) (a1) a vinyl having a reactive functional group (i) 0.1 to 95 parts by mass of the copolymer of the monomer and the (a2) aromatic vinyl monomer and the (a3) vinyl cyanide monomer, (B) (b1) aromatic vinyl monomer and (b2) vinyl cyanide 0 to 94.9 parts by mass of the monomer copolymer, (C) 5 to 40 parts by mass of the ethylene-based colloidal polymer having a reactive functional group (ii), and (D) 0 to 35 parts by mass of the ethylene-based colloidal polymer.

(Where the total of (A), (B), (C), and (D) is 100 parts by mass).

According to the thermoplastic resin composition of the present invention, it is possible to provide a molded article excellent in impact resistance, rigidity and appearance.

The thermoplastic resin composition of the present invention will be specifically described below.

<copolymer (A)>

The thermoplastic resin composition of the present invention may be formulated with (A) (a1) a vinyl monomer having a reactive functional group (i) and (a2) an aromatic vinyl monomer and (a3) a vinyl cyanide monomer. The copolymer (hereinafter sometimes referred to as "copolymer (A)")) is obtained. Further, it may be further copolymerized with (a4) another vinyl monomer copolymerizable with the above. The copolymer (A) is reacted with the following ethylene-based colloidal polymer (C) having a reactive functional group (ii) (hereinafter sometimes referred to as "colloidal polymer (C)") to form a graft. The compatibility between the copolymer (A) and the colloidal polymer (C) can be improved, and the impact resistance and appearance of the molded article obtained by molding the thermoplastic resin composition can be improved.

(a1) The vinyl monomer having a reactive functional group (i) used in the copolymer (A) used in the present invention, as long as it has a reactive functional group with the following colloidal polymer (C) The functional vinyl group monomer is not particularly limited. Examples of the reactive functional group (i) in the component (a1) include an epoxy group, an amine group, and a hydroxyl group. In particular, in terms of further improving the impact strength, an epoxy group is preferred.

Examples of the (a1) vinyl monomer having a reactive functional group (i) include, for example, glycidyl acrylate, glycidyl methacrylate, and acrylic acid condensed. Glyceryl ester, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, and p-glycidyl styrene. These may also be used in two or more types.

The (a2) aromatic vinyl monomer used in the copolymer (A) of the present invention is not particularly limited as long as it is an aromatic vinyl monomer having no reactive functional group (i) and a cyano group. For example, styrene, α-methylstyrene, p-methylstyrene, M-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, t-butylstyrene, and the like. These may also be used in two or more types. It is especially preferred to use styrene.

Examples of the (a3) vinyl cyanide monomer used in the copolymer (A) of the present invention include acrylonitrile, methacrylonitrile, and ethacrylonitrile. These may also be used in two or more types. It is especially preferred to use acrylonitrile.

(a4) Other vinyl-based monomer which can be copolymerized with (a1) component, (a2) component, and (a3) component, if it is used, for example, may be a methyl group or an ethyl group of acryl or methacrylic acid. (meth)acrylate monomer such as propyl, n-butyl or isobutyl ester, or maleimide, N-methylbutyleneimine and N-phenyl cis A maleic acid imide monomer such as butylene diimine. These may also be used in two or more types. In the case of improving the toughness and color tone, a (meth) acrylate monomer is preferably used. On the other hand, in the case of improving heat resistance and flame retardancy, it is preferred to use a maleimide-based monomer.

In the total of 100% by mass of each of the monomers (a1) to (a4) constituting the copolymer (A) used in the present invention, (a1) the amount of the vinyl monomer having a reactive functional group (i) is preferably a compounding amount. It is 0.01 to 20% by mass. By setting the amount of the component (a1) to 0.01% by mass or more, the reaction between the copolymer (A) and the following colloidal polymer (C) can be more effectively carried out, and the impact resistance of the obtained molded article can be further improved. Sex and appearance. The amount is more preferably 0.1% by mass or more. On the other hand, when the amount of the component (a1) is 20% by mass or less, the fluidity can be improved and the moldability can be improved. Further, the amount is more preferably 15% by mass or less. The amount of the aromatic vinyl monomer (a2) is preferably from 5 to 98.99% by mass. By setting the amount of the component (a2) to 5% by mass or more, the moldability and the rigidity of the molded article can be further improved. The amount is more preferably 20% by mass or more. On the other hand, by setting the amount of the component (a2) to 98.99 mass% Hereinafter, the heat resistance of the molded article can be improved. The amount is more preferably 90% by mass or less. The amount of the (a3) vinyl cyanide monomer is preferably from 1 to 60% by mass. By setting the amount of the component (a3) to 1% by mass or more, the rigidity and heat resistance of the molded article can be further improved. On the other hand, when the amount of the component (a3) is 60% by mass or less, the moldability and the rigidity of the molded article can be further improved. Moreover, the compatibility between the copolymer (A) and the colloidal polymer (C) can be improved, and the impact resistance and appearance of the molded article obtained by molding the thermoplastic resin composition can be further improved. The amount is more preferably 45% by mass or less. Further, when it is copolymerized with (a4) another vinyl monomer, the amount of the component (a4) is preferably 90% by mass or less. By setting the amount of the component (a4) to 90% by mass or less, the moldability and the rigidity of the molded article can be further improved. 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 setting the weight average molecular weight of the copolymer (A) to 10,000 or more, the impact resistance and rigidity of the molded article 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, the moldability can be improved and the gloss unevenness can be reduced. The molecular weight is more preferably 250,000 or less, and most preferably 200,000 or less. In the meantime, the lower the weight average molecular weight of (A), the shorter the graft chain becomes, whereby the molecules of (C) become less likely to be stretched at the time of molding, and gloss unevenness can be reduced. In addition, the weight average molecular weight of the copolymer (A) refers to a polystyrene-converted value obtained by a gel permeation chromatography using a hexafluoroisopropanol (HFIP) solution. In the case where a plurality of kinds of the copolymer (A) are blended, it is preferred that the weight average molecular weight of the entire plurality of copolymers (A) is within the above range.

The method for producing the copolymer (A) used in the present invention is not particularly limited, and for example, the above-mentioned (a1) component, (a2) component, (a3) component, and optionally (a4) component are used as raw materials, and a block is used. Polymerization, suspension polymerization, emulsion polymerization, solution polymerization, block- The copolymerization method is carried out by a known polymerization method such as a suspension polymerization method or a solution-block polymerization method, whereby a copolymer (A) can be obtained.

<copolymer (B)>

The thermoplastic resin composition of the present invention can be obtained by blending a copolymer of (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer (hereinafter sometimes referred to as "copolymer (B)") as needed. . By blending the copolymer (B), the moldability and the rigidity of the molded article can be improved. The copolymer (B) may be a polymer obtained by copolymerizing (b1) an aromatic vinyl monomer and (b2) a vinyl cyanide monomer, or may be copolymerized with the above ( B3) Other vinyl monomers are copolymerized.

The (b1) aromatic vinyl monomer is not particularly limited as long as it is an aromatic vinyl monomer having no reactive functional group. For example, a monomer or the like exemplified as (a2) above may be mentioned. These may also be used in two or more types. It is especially preferred to use styrene.

The (b2) vinyl cyanide monomer may, for example, be a monomer exemplified as (a3). These may also be used in two or more types. It is especially preferred to use acrylonitrile.

In addition, as the (b3) other vinyl monomer which can be copolymerized with the component (b1) and the component (b2), if necessary, the monomer exemplified as (a4) is mentioned, for example. These may also be used in two or more types. In the case of improving the toughness and color tone, it is preferred to use a (meth) acrylate monomer. On the other hand, in the case of improving heat resistance and flame retardancy, a maleimide-based monomer is preferably used.

In the total of 100% by mass of each of the monomers (b1) to (b3) constituting the copolymer (B) used in the present invention, the amount of the (b1) aromatic vinyl monomer is preferably from 5 to 99% by mass. By setting the blending amount of the component (b1) to 5% by mass or more, the moldability and the rigidity of the molded article can be further improved. The amount is more preferably 20% by mass or more. On the other hand, by When the amount of the component (b1) is set to 99% by mass or less, the heat resistance of the molded article can be improved, and the amount is more preferably 90% by mass or less. The blending amount of the (b2) vinyl cyanide monomer is preferably from 1 to 60% by mass. By setting the amount of the component (b2) to 1% by mass or more, the heat resistance of the molded article can be improved. On the other hand, when the blending amount of the component (b2) is 60% by mass or less, the moldability can be improved. The amount is more preferably 45% by mass or less. In the case of further copolymerizing with (b3) another vinyl monomer, the amount of the component (b3) is preferably 90% by mass or less. By setting the amount of the component (b3) to 90% by mass or less, the moldability and the rigidity and heat resistance of the molded article can be improved, and the amount is more preferably 79% by mass or less.

The weight average molecular weight of the copolymer (B) used in the present invention is preferably 100,000 or more and 300,000 or less. By setting the weight average molecular weight of the copolymer (B) to 100,000 or more, the impact resistance and rigidity of the molded article can be further improved. On the other hand, by setting the weight average molecular weight of the copolymer (B) to 300,000 or less, the moldability can be improved. 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 the copolymer (B) is a polystyrene equivalent value obtained by a gel permeation chromatography using a hexafluoroisopropanol (HFIP) solution. In the case of formulating a plurality of copolymers (B), it is preferred that the weight average molecular weight of the entire plurality of copolymers (B) is within the above range.

The production method of the copolymer (B) used in the present invention is not particularly limited, and a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk-suspension polymerization method, and a solution-block form can be used. A known polymerization method such as a polymerization method is obtained by polymerizing the component (b1), the component (b2), and the component (b3) as necessary.

<Colloidal polymer (C)>

The thermoplastic resin composition of the present invention can be obtained by blending a colloidal polymer (C). By By blending the colloidal polymer (C), the impact resistance of the molded article can be improved.

The rubber component constituting the colloidal polymer (C) used in the present invention may be a polymer having ethylene as a polymerization component, and may be a copolymer with other unsaturated monomers as necessary. For example, an ethylene polymer and an ethylene/α-olefin copolymer are mentioned. Here, "/" means a copolymer. The ethylene/α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and examples thereof include an ethylene/propylene copolymer, an ethylene/butene copolymer, and an ethylene/hexene copolymer. , ethylene/octene copolymer, and the like. These may also be formulated in two or more types. The reactive functional group (ii) as the colloidal polymer (C) is preferably one which reacts with the reactive functional group (i) described above. For example, a carboxyl group, an acid anhydride group, etc. are mentioned. It is also possible to have two or more reactive functional groups. In the present invention, an acid anhydride group is more preferred.

For example, in the case of obtaining an ethylene-based colloidal polymer (C) having an acid anhydride group as the reactive functional group (ii), the above rubber component such as an acid anhydride, a peroxide, and an ethylene/α-olefin copolymer may be used. Manufactured by reaction. Further, for example, when a vinyl-based colloidal polymer (C) having a carboxyl group as a reactive functional group is to be obtained, it can be produced by copolymerizing the above-mentioned rubber component with an unsaturated carboxylic acid. Examples of the acid anhydride include maleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic anhydride, itaconic anhydride, phenyl maleic anhydride, and citraconic anhydride. Etc. It is especially preferred to use maleic anhydride. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, and the like.

Further, a commercially available product can be used as the vinyl-based colloidal polymer having an acid anhydride group. The commercially available product is, for example, a maleic anhydride-modified ethylene-butene copolymer ("Tafmer" (registered trademark) MH7020, MH5040) manufactured by Mitsui Chemicals, Inc., and the like.

In terms of the improvement in color tone and the balance of various physical properties, the quality of the colloidal polymer (C) used in the present invention by the reactive functional group (ii) is preferably 0.1 to 0.1% of the entire colloidal polymer (C). 10% by mass. For example, having an acid anhydride group as a reactive functional group In the case of the colloidal polymer (C) of the group (ii), the acid-modified mass of the colloidal polymer (C) can be a solution obtained by dissolving the colloidal polymer (C) at 130 ° C with xylene, using potassium hydroxide. A 0.02 mol/L ethanol solution (manufactured by Aldrich) was used as a titration solution, and a 1% ethanol solution of phenolphthalein was used as an indicator.

The glass transition temperature of the colloidal polymer (C) used in the present invention is preferably -10 ° C or lower, more preferably -30 ° C or lower, further preferably -45 ° C or lower. When the glass transition temperature of the colloidal polymer (C) is -10 ° C or lower, the impact resistance of the molded article can be further improved. Further, in the present invention, the glass transition temperature of the colloidal polymer (C) can be determined by DSC measurement (differential scanning calorimetry). The DSC measurement can be carried out using a differential scanning calorimeter (DSCQ200 (manufactured by TA Instruments)). The measurement conditions were as follows: a sample of 10 mg, a nitrogen gas atmosphere, a temperature increase rate of 5 ° C/min, a temperature modulation range of ±1 ° C, and a temperature modulation cycle of 60 seconds were heated from -80 ° C to 150 ° C.

<Colloidal polymer (D)>

The thermoplastic resin composition of the present invention can be obtained by blending (D) a vinyl-based colloidal polymer (hereinafter sometimes referred to as "colloidal polymer (D)") as needed. By blending the colloidal polymer (D), the impact resistance of the molded article can be further improved.

The colloidal polymer (D) used in the present invention is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and examples thereof include an ethylene/α-olefin copolymer, an ethylene/propylene copolymer, and ethylene. /butene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer, and the like. These may also be formulated in two or more types.

The glass transition temperature of the colloidal polymer (D) used in the present invention is preferably -10 ° C or lower, more preferably -30 ° C or lower, further preferably -45 ° C or lower. When the glass transition temperature of the colloidal polymer (D) is -10 ° C or lower, the impact resistance of the molded article can be further improved. Further, in the present invention, the glass transition temperature of the colloidal polymer (D) can be determined by DSC measurement (differential scanning calorimetry). The DSC measurement can be carried out using a differential scanning calorimeter (DSCQ200 (manufactured by TA Instruments)). The measurement conditions were as follows: a sample of 10 mg, a nitrogen gas atmosphere, a temperature increase rate of 5 ° C/min, a temperature modulation range of ±1 ° C, and a temperature modulation cycle of 60 seconds were heated from -80 ° C to 150 ° C.

The blending amount of each component in the thermoplastic resin composition of the present invention is 0.1 to 95 parts by mass based on 100 parts by mass of the total of (A) to (D), and the copolymer (B) is 0 to 94.9 parts by mass, the colloidal polymer (C) is 5 to 40 parts by mass, and the colloidal polymer (D) is 0 to 35 parts by mass. When the amount of the copolymer (A) is less than 0.1 part by mass, it is difficult to form a graft of the copolymer (A) and the colloidal polymer (C), and the copolymer (A) and the colloidal polymer (C) cannot be obtained. Since the compatibility of the compatibility is improved, the impact resistance and the appearance of the molded article tend to decrease. 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 colloidal polymer (C) is relatively low, and thus the impact resistance of the molded article tends to decrease. The blending amount of the copolymer (A) is preferably 90 parts by mass or less. In addition, when the blending amount of the copolymer (B) exceeds 94.9 parts by mass, the blending amount of the copolymer (A) and the colloidal polymer (C) is relatively low, and thus the impact resistance of the molded article tends to decrease. In addition, when the amount of the colloidal polymer (C) is less than 5 parts by mass, it is difficult to form a graft of the copolymer (A) and the colloidal polymer (C), and the impact resistance of the molded article is lowered. The blending amount of the colloidal polymer (C) is preferably 10 parts by mass or more. On the other hand, when the blending amount of the colloidal polymer (C) exceeds 40 parts by mass, the formability and the rigidity of the molded article tend to decrease. The blending amount of the colloidal polymer (C) is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. In addition, when the blending amount of the copolymer (D) exceeds 35 parts by mass, the blending amount of the copolymer (A) and the colloidal polymer (C) is relatively low, and thus the impact resistance of the molded article tends to decrease. Copolymer (D) The blending amount is preferably 20 parts by mass or less.

<Peroxide (E)>

The thermoplastic resin composition of the present invention can be obtained by blending (E) a peroxide (hereinafter sometimes referred to as "peroxide (E)") as needed. The peroxide (E) promotes the reaction between the copolymer (A) and the colloidal polymer (C) to further improve the impact resistance of the molded article. Examples of the peroxide include benzammonium peroxide, dicumyl peroxide, di-tert-butyl peroxide, t-butyl cumene peroxide, cumene hydroperoxide, and 2 , 5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne-3, and the like. Further, a commercially available product can be used as the peroxide (E). As a commercial item, the "made by the Nippon Oil Co., Ltd. ("Perhexa" (trademark) 25B), etc. are mentioned, for example. These may also be formulated in two or more types.

The amount of the peroxide (E) to be added to the thermoplastic resin composition of the present invention is preferably 0.1 to 1 part by mass based on 100 parts by mass of the total of (A) to (D). By setting the amount of the peroxide (E) to 0.1 part by mass or more, the impact resistance of the molded article can be further improved. On the other hand, by setting the 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-based polymer (hereinafter sometimes referred to as "ethylene-based polymer (F)") as needed. By blending the ethylene-based polymer (F), the impact resistance and gloss of the molded article can be further improved.

The component constituting the ethylene-based polymer (F) used in the present invention may be a polymer having a functional group based on ethylene and having a reaction with the reactive functional group (i). a copolymer with other unsaturated monomers. For example, an ethylene polymer and an ethylene/α-olefin copolymer are mentioned. Here, "/" means a copolymer. As The ethylene/α-olefin copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and examples thereof include an ethylene/propylene copolymer, an ethylene/butene copolymer, and an ethylene/hexene copolymer. Ethylene/octene copolymer or the like. These may also be formulated in two or more types. The reactive functional group of the ethylene-based polymer (F) is preferably a one which reacts with the reactive functional group (i) described above. For example, a carboxyl group, an acid anhydride group, etc. are mentioned. It is also possible to have two or more reactive functional groups. In the present invention, an acid anhydride group is preferred.

Further, a commercially available product can be used as the ethylene-based polymer having an acid anhydride group. The commercially available product is, for example, an acid-modified ethylene-based polymer ("Hi-Wax" (registered trademark) 1105A, 2203A) manufactured by Mitsui Chemicals, Inc., and the like.

The weight average molecular weight of the ethylene-based polymer (F) used in the present invention is preferably 500 or more and 30,000 or less. When the weight average molecular weight of the ethylene-based polymer (F) is 500 or more, the impact resistance and rigidity of the molded article can be further improved. The molecular weight is more preferably 700 or more, and most preferably 1,000 or more. On the other hand, when the weight average molecular weight of the ethylene-based polymer (F) is 30,000 or less, the compatibility with the colloidal polymer (C) can be improved, and gloss unevenness can be reduced. The molecular weight is preferably 20,000 or less, and most preferably 10,000 or less.

The blending amount of the ethylene-based polymer (F) in the thermoplastic resin composition of the present invention is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total of (A) to (D) and (F). By setting the amount of the ethylene-based polymer (F) to 0.1 part by mass or more, the impact resistance of the molded article can be further improved. On the other hand, when the amount of the ethylene-based polymer (F) is 10 parts by mass or less, the impact resistance of the molded article can be suppressed from being lowered.

The thermoplastic resin composition of the present invention may further be formulated with a flame retardant, a filler, other thermoplastic resin, a thermosetting resin, a soft thermoplastic resin, various additives or modifiers, within a range not impairing the effects of the present invention. And get.

By formulating a flame retardant in the thermoplastic resin composition of the present invention, Improve flame retardancy. The flame retardant is not particularly limited, and a so-called general flame retardant can be adjusted. For example, a phosphorus-based compound, a halogen-based organic compound, an organic compound containing nitrogen such as melamine, an inorganic compound such as magnesium hydroxide or aluminum hydroxide, a polyorganosiloxane compound, arsenic oxide, cerium oxide, or cerium oxide can be given. Metal oxides such as iron oxide, zinc oxide, and tin oxide, ruthenium oxide, and the like. These may also be formulated in two or more types. A phosphorus compound or a halogen organic compound is preferred, and a phosphorus compound is preferred.

The phosphorus-based 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, phosphonite, and phosphine oxide. Among them, an aromatic phosphate ester can be preferably used.

Examples of the halogen-based organic compound include hexachloropentadiene, hexabromobiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromobiphenyl, and decabromodiphenyl oxide. OctaBDE, tetrabromobisphenol A, tetrabromophthalimide, hexabromobutene, tris(chlorotetrabromophenyl)triphosphate, hexabromocyclododecane or various A compound or the like which has been modified by a substituent. These may also be formulated in two or more types.

In the case of the blending of the flame retardant, it is generally used in the range of 0.1 to 30 parts by mass based on 100 parts by mass of the total of the component (A), the component (B), the component (C), and the component (D), and more preferably A range of 1 to 20 parts by mass. When the amount of the flame retardant is 0.1 parts by mass or more, 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 article can be improved.

By blending the filler in the thermoplastic resin composition of the present invention, the strength and dimensional stability of the molded article can be improved. The shape of the filler may be fibrous, and may be non-fibrous, or a fibrous filler and a non-fibrous filler may be used in combination. Examples of the fibrous filler include glass fibers, glass milled fibers, carbon fibers, potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, and aromatic polyamide fibers. Alumina fiber, strontium carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, and the like. Examples of the non-fibrous filler include ceric acid such as limestone, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, and alumina silicate, and alumina. Metal oxides such as cerium oxide, magnesium oxide, zirconium oxide, 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 and calcium hydroxide; A metal hydroxide such as aluminum hydroxide, glass beads, ceramic beads, boron nitride, and tantalum carbide. These may be hollow, and the fillers may be formulated in two or more types. In addition, the filler may be pretreated with a coupling agent such as an isocyanate compound, an organic decane compound, an organic titanate compound, an organoborane compound or an epoxy compound, and the molded article may be further improved. Mechanical strength.

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

In the thermoplastic resin composition of the present invention, a thermoplastic resin, a thermosetting resin, or a soft thermoplastic resin other than the above components (A) to (D) may be blended in a range that does not impair the effects of the present invention. Examples of the thermoplastic resin include polyethylene resin, polypropylene resin, acrylic resin, polyamide resin, polyphenylene sulfide resin, polyether ether ketone resin, polyester resin, polyfluorene resin, and polyether oxime. Resin, aromatic or aliphatic polycarbonate resin, polyarylate resin, polyphenylene ether resin, polyacetal resin, polyimide resin, polyether phthalimide resin, chlorinated polyethylene resin, chlorinated polypropylene Resin, aromatic or aliphatic polyketone resin, fluororesin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, polyurethane resin, cellulose acetate resin, polyvinyl alcohol resin, etc. . Examples of the thermosetting resin include a phenol resin, a melamine resin, a polyester resin, a polyoxyxylene resin, and an epoxy resin. Examples of the soft thermoplastic resin include: Ethylene/glycidyl methacrylate copolymer, polyester elastomer, polyamine elastomer, ethylene/propylene terpolymer, ethylene/1-butene copolymer, and the like.

When a thermoplastic resin, a thermosetting resin, or a soft thermoplastic resin is blended, the total amount of the components is 100% of the total amount of the component (A), the component (B), the component (C), and the component (D). The parts by mass are preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

In the thermoplastic resin composition of the present invention, various additives may be formulated within a range not impairing the effects of the present invention. Examples of the additive include a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, and an organic phosphorus compound; and crystal nucleation such as talc, kaolin, organophosphorus compound, or polyether ether ketone; Agent; release agent such as polyolefin compound, polyoxymethylene compound, long-chain aliphatic ester compound, long-chain aliphatic amide compound, anti-corrosion agent, anti-coloring agent, antioxidant, heat stabilizer, stearin Lubricants such as lithium acid or aluminum stearate, ultraviolet ray preventive agents, colorants, foaming agents, and the like.

<Thermoplastic resin composition>

The thermoplastic resin composition of the present invention is characterized in that the rising temperature of the storage elastic modulus in the dynamic viscoelasticity measurement is at least 20 ° C below the glass transition temperature of the above colloidal polymer (C), and the colloidal polymer (C) is The average particle diameter of 0.6 μm or less is dispersed. Further, the dispersed particles of the colloidal polymer (C) as referred to herein may be a graft of the colloidal polymer (C) and the above polymer (A).

The rising temperature of the storage elastic modulus in the dynamic viscoelasticity measurement is an index indicating the softness of the colloidal polymer (C) in the thermoplastic resin composition. The colloidal polymer (C) tends to lose the original properties of the colloidal polymer (C) as it undergoes a change in a graft or the like by reaction with the above polymer (A). The invention is characterized in that it is hot In the plastic resin composition, as an index indicating the original properties of the colloidal polymer (C), attention is paid to the rising temperature of the storage elastic modulus, which is a glass transition temperature of the colloidal polymer (C) + 20 ° C or lower. The closer the rising temperature of the storage elastic modulus is to the glass transition temperature of the colloidal polymer (C), the more the characteristic (softness) originally possessed by the colloidal polymer (C) is maintained in the thermoplastic resin composition. When the rising temperature of the storage elastic modulus is higher than the glass transition temperature of the colloidal polymer (C) by +20 ° C, the flexibility of the colloidal polymer (C) is impaired and the impact resistance of the molded article is lowered. The rising temperature of the storage elastic modulus is preferably a glass transition temperature of the colloidal polymer (C) of +15 ° C or less.

Further, the average particle diameter of the colloidal polymer (C) is 0.6 μm or less, which means that the colloidal polymer (C) is dispersed by finer particles. Therefore, the dispersion structure of the thermoplastic resin composition becomes more uniform, and the flexibility of the colloidal polymer (C) can be sufficiently exhibited, and the impact resistance and gloss of the molded article can be improved. The average particle diameter is preferably 0.5 μm or less, more preferably 0.4 μm or less. When the average particle diameter of the colloidal polymer (C) exceeds 0.6 μm, the impact resistance and gloss of the molded article are lowered.

Previously, in order to improve the dispersibility of the colloidal polymer, a large amount of graft chains were required in the colloidal polymer, but as the graft chain increased, the flexibility of the thermoplastic resin composition was lowered to impair the impact resistance of the molded article. Reduce the situation. On the other hand, if the flexibility of the colloidal polymer is to be maintained in the thermoplastic resin composition, the average particle diameter of the colloidal polymer becomes large, and the impact resistance of the molded article may be lowered. In the present invention, for example, a thermoplastic resin composition obtained by blending a copolymer (A) or a copolymer (B) having a weight average molecular weight in the above preferred range; the quality of using the reactive functional group is as described above. a thermoplastic resin composition obtained by a preferred range of the colloidal polymer (C); a thermoplastic resin composition obtained by using the above (E) peroxide; or a thermoplastic resin composition obtained by using the following production method or the like Maintaining colloid on one side of the resin composition The flexibility of the polymer (C) is finely dispersed, and the impact resistance of the molded article can be greatly improved.

In the present invention, the temperature at which the storage elastic modulus is increased in the dynamic viscoelasticity measurement of the thermoplastic resin composition and the average particle diameter of the colloidal polymer (C) can be measured by preparing a test piece from a molded article. In the case of the general molding conditions, the rising temperature of the storage elastic modulus and the average particle diameter of the colloidal polymer (C) are not changed. In the present invention, a test piece is produced from a molded article obtained by injection molding under the following conditions. , ie, temperature: 220 ° C, mold temperature: 60 ° C, injection speed: 100 mm / sec, injection time: 10 seconds, cooling time: 20 seconds, forming pressure: pressure of the resin filled in the mold (forming lower limit pressure) + 2 MPa .

With respect to the 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 article having a thickness of 3 mm formed by the above-described conditions, and was measured by a bending mode using DMS6100 manufactured by Seiko Instruments. The measurement conditions were as follows: a frequency of 0.5 Hz, a distance between clamps of 20 mm, a temperature increase rate of 2 ° C/min, and a temperature increase from -100 ° C to 0 ° C. The vertical axis represents the storage elastic modulus, and the horizontal axis represents the temperature, and the temperature corresponding to the point at which the tangent line of the plateau region in which the elastic modulus is stored intersects with the tangent line at which the slope after the rise becomes a straight line portion is taken as the rising temperature of the storage elastic modulus.

Further, regarding the average particle diameter of the colloidal polymer (C), a sample obtained by cutting an ultrathin section from the molded article formed under the above conditions was observed by a transmission electron microscope to a magnification of 1,000 times, and was observed. Take photos at the observation site. From the electron micrograph, 100 colloidal polymers (C) which form a dispersed phase were randomly selected, and the long diameter of each was measured, and the average value of these values was made into the average particle diameter.

The thermoplastic resin composition of the present invention can be used, for example, by chaotic mixing in the twin-screw extruder, the copolymer (A), the copolymer (B), the colloidal polymer (C) as needed, and optionally And the gelatinous polymer (D) and other components as needed Obtained by melt kneading. By performing melt-kneading by chaotic mixing, the copolymer (A) and the colloidal polymer (C) can be uniformly and efficiently reacted. In the present invention, for example, a copolymer (A) having a weight average molecular weight of 10,000 or more and 300,000 or less and a colloidal polymer (C) having an acid-modified mass of 0.1 to 10% by mass are used, and melt-kneading by chaotic mixing is performed. Thereby, the thermoplastic resin composition having the above characteristics can be easily obtained. In the case of a thermoplastic resin composition prepared by blending a copolymer (B) and/or a colloidal polymer (D), it is preferred to use at least the above (A) and (by chaotic mixing using a twin screw extruder). C) After melt-kneading, the above (B) and/or (D) are further blended and melt-kneaded. As a condition for melt-kneading the above (B) and/or (D) by melt-kneading the above (A) and (C) by chaotic mixing using a twin-screw extruder, chaotic mixing may be performed. It can also be a usual melt kneading. By performing the melt-kneading of the above (A) and (C) by chaotic mixing using a twin-screw extruder, the reaction of the above (A) and (C) can be carried out more efficiently, and the surface gloss of the molded article can be improved. The above additives and the like can be formulated at any stage. For example, it may be blended with the above-mentioned copolymer (A), the copolymer (B), the colloidal polymer (C), and the colloidal polymer (D) as needed, and the above (A)~ may be used in advance. (D) After the melt-kneading, it may be blended, and at least one of the above (A) to (D) may be blended in advance to perform melt-kneading, and then the remaining components may be blended.

Explain the chaotic mixture. When considering the mixing of the two kinds of fluids, the equations can be obtained by using the position as the initial value and solving the equation for controlling the motion of the fluid particles with respect to all the points on the boundary surfaces of the initial two kinds of fluids. The time of the boundary surface develops. In order to quickly mix the two fluids, the boundary surface must be folded at a small interval, so the area of the boundary surface has to be increased sharply. First, the distance between the two points on the boundary surface must be extremely close. Increased eagerly. Thus, in the solution of the equation governing the motion of the fluid, the mixture of chaotic solutions with a distance between two points increasing exponentially with time is called chaotic mixing. Chaotic mixing is documented in, for example, Chaos, Solitons & Fractals Vol.6 p425-438.

In the present invention, chaotic mixing is preferably in the particle tracking method, when the line length is set to L and the initial line length is set to L ₀ , the logarithm of the elongation of the imaginary line (InL/L ₀ ) becomes 2 or more. In the case where the logarithm of the elongation of the imaginary line (InL/L ₀ ) is large, it means that in the solution of the equation governing the motion of the fluid, the distance between the two points tends to increase exponentially with time. The particle tracking method is as follows: at time t=0, the initial positions of 1000 particles are randomly determined in the cross section of the upstream surface of the evaluated screw, and the screw evaluated by the analysis is traced by simulation. The movement of the velocity field. When the screw is rotated only at time t=T, the time at which the probability of existence of the particle is the highest is t=tp according to the history of the coordinates of each particle, and the line length at this time is set to L. The logarithm of the elongation of the imaginary line (InL/L ₀ ). The particle tracking method is described, for example, in Journal of Non-Newtonian Fluid Mechanics Vol. 91, Issues 2-3, 1 July 2000, p273-295. As the kneading temperature of the chaotic mixing, it is preferred to set a region higher than the glass transition temperature by 1 to 150 ° C based on the polymer having the highest glass transition temperature among the polymers to be used. Here, the kneading temperature means the set temperature of the cylinder of the twin-screw extruder. It suffices to provide at least a portion of the region set to the above temperature between the molten portions of the polymer and the die. By making the kneading temperature 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 appropriately lowered, and the kneading can be more sufficiently performed. Further, by setting the glass transition temperature to +150 ° C or lower, it is easy to sufficiently stretch and the chaotic mixed state can be formed more easily.

In the particle tracking method, the screw having an InL/L ₀ of 2 or more is more preferably a screw of 3 or more, and more preferably a screw of 4 or more.

As the above-mentioned screw for the twin-screw extruder which is effective for generating chaotic mixing state The rod may, for example, be a twist kneading disk including a kneading disk, and the angle between the top of the front end side of the disk and the top of the rear side thereof, that is, the spiral angle θ, is in the half rotation direction of the screw 0° < θ < 90 °. Further, chaotic mixing can be more effectively produced by alternately combining a back mixing screw and a torsion kneading disc, the counter-mixing screw including a flight screw, and the screw portion is oriented from the front end side of the screw A resin passage is formed on the rear end side.

In the present invention, the total length ratio of the region in which the melt-kneading is carried out by chaotic mixing (chaotic mixing zone) is in the range of 5 to 80% with respect to the entire length of the screw of the twin-screw extruder. By setting the ratio of the chaotic mixing zone to 5% or more, it is possible to perform stretching with high efficiency and folding. The ratio is more preferably 10% or more, and still more preferably 15% or more. On the other hand, by setting the ratio of the chaotic mixing zone to 80% or less, the extrusion processability can be improved. The ratio is more preferably 70% or less, and still more preferably 60% or less. Further, in the present invention, the chaotic mixing zone of the twin-screw extruder is preferably not distributed at a specific position in the screw but disposed in the entire region.

The thermoplastic resin composition of the present invention can be usually molded by any of known methods such as injection molding, extrusion molding, vacuum pressure molding, expansion molding, and blow molding. The shape of the molded article is not particularly limited, and examples thereof include a film, a sheet, a fiber, a non-woven fabric, and various injection molding shapes. Further, it may be made into a composite with other materials, and may be applied by coating, plating, or the like.

The molded article of the present invention can be used as a structural material in order to exhibit excellent impact resistance and appearance. For example, the following items. Various gears, various boxes. Sensor, LED (Light-Emitting Diode) lamp, connector, socket, resistor, relay box, switch, coil bobbin, capacitor, variable capacitor case, optical pickup , oscillator, terminal block, converter, plug, printed wiring board, tuner, Yang Sounder, microphone, headphone, small motor, head base, power module, housing, semiconductor, liquid crystal, fixed disk drive (FDD, Fixed Disk Drive) bracket, FDD chassis, motor brush Stands, parabolic antennas, computer-related parts, etc. are representative of electrical and electronic parts. Generators, motors, transformers, converters, voltage regulators, rectifiers, inverters, relays, power contacts, switches, interrupters, knife switches, multipoles, motor parts cabinets , VTR (Video Tape Recorder) parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, CD, DVD and other sound machine parts. Household and business electrical parts represented by lighting parts, refrigerator parts, air conditioning parts, air conditioner outdoor units, typewriter parts, and word processor parts. Office computer related parts, telephone related parts, mobile phone related parts, fax machine related parts, photocopying machine related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, etc., various bearings, motor parts, igniters, typewriters Wait for the mechanical related parts. Optical machines and precision machinery related parts represented by microscopes, binoculars, cameras, clocks, etc. Alternator terminal, alternator connector, IC regulator, potentiometer base for dimmer, intake nozzle vent pipe, intake manifold, air flow meter, air pump, fuel pump, engine cooling water connector, constant temperature Housing, carburetor body, carburetor spacer, engine frame, ignition coil holder, ignition box body, clutch coil holder, sensor housing, idle speed control valve, vacuum switching valve, electronic control unit (ECU, Electronic Control Unit a housing, a vacuum pump case, a suppression switch, a rotation sensor, an acceleration sensor, a distributor cover, a coil base, an anti-lock brake system (ABS), an actuator case, Top and bottom of radiator box, cooling fan, fan cover, hood, cylinder head cover, oil cover, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, steam canister housing, air cleaning Housing, timing belt cover, brake booster parts, various boxes, fuel related, exhaust system, suction system, etc. Various tanks, fuel-related, exhaust systems, suction systems, various hoses, various clamps, exhaust valves, and other valves, various tubes, exhaust sensors, cooling water sensors, oil temperature sensors , brake car product sensor, brake pad wear sensor, throttle position sensor, crank position sensor, air conditioner thermostat base, air conditioning panel switch substrate, heating heater flow control valve, radiator motor Brush holder, pump impeller, turbine blade, scraper motor related parts, stepper motor rotor, brake piston, solenoid coil former, engine oil filter, ignition box, torque lever, starter switch, start Relays, seat belt parts, air deflector blades, wash rods, window glass switch handles, window glass switch handle knobs, light control levers, distributors, sun visor brackets, various motor housings, roof luggage Shelf, fender, trim, bumper, door mirror mount, horn terminal, window washer nozzle, wiper arm, trim, mirror housing, spoiler, hood vent, wheel cover, wheel cover, Radiator grille, Curtain wall cover frame, lamp mirror, lamp socket, lamp housing, lamp cover, door handle and other automotive exterior materials, center console, instrument panel, instrument panel core, instrument panel pad, glove box, handle column , armrests, handcart handlebars, front pillar trim, door trim, column trim, control box, etc., automotive wiring, harness connector, super multi-way (SMJ) connector, printed circuit board (PCB, Printed Circuit Board) ) Automotive parts such as connectors, metal eyelet connectors, and connectors for fuses. Personal computers, printers, monitors, cathode ray tubes (CRT, Cathode Ray Tube) displays, fax machines, photocopiers, word processors, notebook computers, mobile phones, personal portable telephone systems (PHS, Personal Handyphone System), DVD drive, PD (Phase Change Rewritable Optical Disk) driver, floppy disk drive and other memory device housings, chassis, relays, switches, box components, transformer components, coil holders, etc. Electronic machine parts; mechanical parts, agricultural materials, horticultural materials, fishery materials, civil engineering, construction materials, and other various uses.

Example

In order to explain the present invention more specifically, the following examples and comparative examples are described, but the present invention is not limited to the examples. First, the components used in the examples and comparative examples will be described.

[Reference Example 1] (A-1) Copolymer

The monomer mixture containing 75.7 parts by mass of styrene, 24 parts by mass of acrylonitrile, and 0.3 parts by mass of glycidyl methacrylate was subjected to suspension polymerization to prepare a beaded copolymer (A-1). The content ratio of each monomer unit was 75.7 mass% of styrene unit, 24 mass% of acrylonitrile unit, and 0.3 mass% of glycidyl methacrylate unit. Using the obtained hexafluoroisopropanol (HFIP) solution of the copolymer (A-1), the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography, and it was 170,000. The glass transition temperature determined by DSC measurement (differential scanning calorimetry) was 115 °C. The DSC measurement conditions were as follows: a sample of 10 mg, a nitrogen gas atmosphere, a temperature increase rate of 5 ° C / min, a temperature modulation range of ± 1 ° C, and a temperature modulation cycle of 60 seconds were raised from -80 ° C to 150 ° C.

[Reference Example 2] (A-2) Copolymer

A monomer mixture containing 74.5 parts by mass of styrene, 22.5 parts by mass of acrylonitrile, and 3 parts by mass of glycidyl methacrylate was subjected to suspension polymerization to prepare a beaded copolymer (A-2). The content of each monomer unit is 74.5 mass% of styrene unit, 22.5% by mass of acrylonitrile unit, and 3 mass% of glycidyl methacrylate unit. Using the HFIP solution of the obtained copolymer (A-2), the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography, and it was 110,000. The glass transition temperature determined by DSC measurement was 110 °C. In addition, the DSC measurement conditions were set to be the same as in Reference Example 1.

[Reference Example 3] (A-3) Copolymer

The monomer mixture containing 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 prepare a beaded copolymer (A-3). The content ratio of each monomer unit is 72% by mass of styrene unit, 22% by mass of acrylonitrile unit, and 6% by mass of glycidyl methacrylate unit. 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), and it was 70,000. The glass transition temperature determined by DSC measurement was 109 °C. In addition, the DSC measurement conditions were set to be the same as in Reference Example 1.

[Reference Example 4] (B-1) Copolymer

The monomer mixture containing 70 parts by mass of styrene and 30 parts by mass of acrylonitrile was subjected to suspension polymerization to prepare a beaded copolymer (B-1). The content ratio of each monomer unit is 70% by mass of styrene unit and 30% by mass of acrylonitrile unit. Using the HFIP solution of the obtained copolymer (B-1), the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography, and it was 150,000. The glass transition temperature determined by DSC measurement was 110 °C. In addition, the DSC measurement conditions were set to be the same as in Reference Example 1.

[Reference Example 5] Graft Copolymer 1

Ethylene/propylene/5-ethylene-2-derived by Mitsui Chemicals Co., Ltd. 57 parts by mass of an olefin copolymer (EPDM) (Mitsui EPT X-3012P) was dissolved in 400 parts by mass of n-hexane to which 200 parts by mass of dichloroethylene was added. Then, 10 parts by mass of acrylonitrile, 33 parts by mass of styrene, and 17 parts by mass of benzamidine peroxide were added, and polymerization was carried out at 65 ° C for 10 hours in a nitrogen atmosphere. After the polymerization, the polymerization reaction solution was poured into an excessive amount of methanol, and the precipitated precipitate was separated and vacuum-dried to obtain a graft polymer 1.

[Reference Example 6] Resin Composition 1

A twin-screw extruder (TEX30XSSST manufactured by JSW Co., Ltd.) (L/D = 45.5) having a screw rotation number of 200 rpm was supplied, and 43 parts by mass of the (A-2) copolymer was supplied, and the following (C-1) colloidal polymer was supplied. 57 parts by mass was 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 melting section was adjusted to 230 °C. Further, the screw structure of the extruder is set to include a kneading disk and a screw screw. As the kneading disc, a twist kneading disc is used, and the angle between the top of the tip end side of the twisted kneading disc and the top of the rear side thereof, that is, the helix angle θ is in the range of 0° < θ < 90° in the half rotation direction of the screw. As the kneading disc, a back-mixing screw having a resin passage formed from the tip end side toward the rear end side is used. The total length of the region (chaotic mixing zone) in which the kneading disk and the screw screw are alternately combined and the mixture is melt-kneaded while performing chaotic mixing is 50% with respect to the entire length of the screw of the extruder. Hereinafter, the screw configuration is referred to as A type. Furthermore, for the purpose of this condition, the software SCREWFLOW-MULTI is analyzed by Computer Aided Engineering (CAE) manufactured by JSW, and is randomly determined in the profile of the upstream surface of the screw at time t=0. The initial position of each particle is used to simulate the movement of the velocity field of the screw evaluated by the analysis by simulation, and the imaginary line when the line length is (L) and the initial line length is (L ₀ ) is obtained. The logarithm of the elongation (InL/L ₀ ), and the result InL/L ₀ was 4.3. The gut spouted from the mold was immediately quenched in ice water to fix the structure, and then granulated by a strand cutter to obtain granules.

(C-1) colloidal polymer

The maleic anhydride-modified ethylene-butene copolymer ("Tafmer" (registered trademark) MH5040, manufactured by Mitsui Chemicals, Inc., and the glass transition temperature determined by DSC measurement was -65 ° C) was used. In addition, the DSC measurement conditions were set to be the same as in Reference Example 1.

(D-1) colloidal polymer

Using Mitsui Chemicals Co., Ltd. to produce ethylene/propylene/5-ethylene-2-nor Alkene copolymer (EPDM) (Mitsui EPT X-3012P, glass transition temperature determined by DSC measurement was -51 ° C). In addition, the DSC measurement conditions were set to be the same as in Reference Example 1.

(E-1) peroxide

2,5-Dimethyl-2,5-di-t-butylperoxy hexane ("Perhexa" (registered trademark) 25B) manufactured by Nippon Oil Co., Ltd. was used.

(F-1) ethylene polymer

An acid-modified polyolefin ("Hi-Wax" (registered trademark) 1105A, molecular weight 1500) manufactured by Mitsui Chemicals, Inc. was used.

Next, the evaluation methods in the respective examples and comparative examples will be described. Injection molding machine (SE75DUZ) manufactured by Sumitomo Heavy Industries Co., Ltd. at forming temperature: 220 ° C, mold temperature: 60 ° C, injection speed: 100 mm / sec, injection time: 10 seconds, cooling time: 20 seconds, forming Pressure: The pellets obtained by the respective examples and comparative examples were injection-molded into the test pieces described in the following items under the conditions that the resin was filled in the pressure of the mold (minimum lower molding pressure) + 2 MPa.

(1) Average particle size

A sample obtained by cutting an ultrathin section from a molded article of 3 mm thick formed by the above conditions was observed by a transmission electron microscope (HITACHI, ELECTRON MICROSCOPE H-700) to a magnification of 1000 times, and the observation portion was taken. photo. From the electron micrograph, 100 colloidal polymers (C) which form a dispersed phase were randomly selected, and the long diameter of each was measured, and the average value of these values was made into the average particle diameter.

(2) The rising temperature of the 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 article of 3 mm thick formed under the above conditions, and a storage elastic modulus was measured by a bending mode using DMS6100 manufactured by Seiko Instruments. The measurement conditions were as follows: a frequency of 0.5 Hz, a distance between clamps of 20 mm, a temperature increase rate of 2 ° C/min, and a temperature increase from -100 ° C to 0 ° C. The vertical axis represents the storage elastic modulus, and the horizontal axis represents the temperature, and the temperature corresponding to the point at which the tangent line of the plateau region in which the elastic modulus is stored intersects with the tangent line at which the slope after the rise becomes a straight line portion is taken as the rising temperature of the storage elastic modulus.

(3) Impact resistance

The Izod notched impact strength was measured at 23 ° C according to ASTM D-256 using a 1/4 inch thick test piece formed by the above conditions. The impact strength was measured for each of the six test pieces, and the average value was set to the Izod impact strength. Further, the samples after the Ehrlich impact test were visually observed to judge ductile fracture and brittle fracture.

(4) Bending elastic modulus

The flexural modulus of elasticity was evaluated in accordance with ASTM D790 using a 1/4 inch thick test piece formed by the above conditions. Determine the flexural modulus of the three test pieces and flatten them The mean value is taken as the bending elastic modulus.

(5) Heat resistance (load bending temperature)

The test bending piece cut out from the molded article formed under the above conditions was used, and the load bending temperature was measured in accordance with ASTM D648 (load: 1.82 MPa). The load bending temperature was measured for each of the two test pieces, and the average value was taken as the load bending temperature.

(6) Appearance

The surface of the molded article of 3 mm thick formed by the above conditions was visually observed, and gloss unevenness was evaluated by the following criteria.

A: Matte unevenness

B: uneven gloss is observed in part

C: Overall uneven gloss is observed

(7) Surface gloss

The surface gloss of the center portion of the test piece of 80 mm × 80 mm × 3 mm thick formed by the above conditions was measured at a incident angle of 60 degrees using a digital variable angle gloss meter ("UGV-5D" manufactured by Suga Test Instruments Co., Ltd.). The average value of the three measurements was taken as the gloss.

(8) Residual emulsifier

1 g of the pellet obtained by each of the examples and the comparative examples was extracted with methanol, and then filtered through a 0.5 μm filter paper, and the filtrate was concentrated, dried by a vacuum dryer, and visually observed for the presence or absence of an extract component.

(Examples 1 to 5, 7, 8)

The components shown in Table 1 were supplied to a twin-screw extruder (TEX30XSSST manufactured by JSW Co., Ltd.) (L/D = 45.5) having a screw rotation number of 200 rpm in the mixing ratio shown in Table 1, and melt-kneaded. The cylinder set temperature after the polymer melting section was adjusted to 150 °C. Further, the screw structure of the extruder was constituted by a screw of type A. Furthermore, for the present conditions, the SCEWFLOW-MULTI in the extruder is manufactured by Nippon Steel Co., Ltd., and the initial position of 1000 imaginary particles is randomly determined at the foremost part of the upstream of the screw at time t=0. The number of screw revolutions was 200 rpm, the resin temperature was 150 ° C, and the melt viscosity was 3,000 Pa s. The movement of the velocity field of the screw evaluated by the analysis was traced by simulation, and the line length was determined to be (L). ), InL/L ₀ when the initial line length is set to (L ₀ ), and the result InL/L ₀ is 4.2.

The strip spouted from the mold was immediately quenched in ice water to fix the structure, and then granulated by a strand cutter to obtain granules. Using the obtained pellets, each characteristic was evaluated by the above method, and the results are shown in Table 1.

(Example 6)

The twin-screw extruder (TEX30XSSST manufactured by JSW Co., Ltd.) (L/D=45.5) supplied to the screw rotation number of 200 rpm in the same manner as in the third embodiment and having the same composition as shown in Table 1 was supplied. The above (B-1) and the resin composition 1 obtained by the method described in the above Reference Example 6 were melt-kneaded. The cylinder set temperature after the polymer melting section was adjusted to 150 °C. Further, the screw structure of the extruder was constituted by a screw of type A. Furthermore, for the present conditions, the CAE analysis software SCREWFLOW-MULTI of the extruder manufactured by JSW Corporation is used, and the initial position of 1000 imaginary particles is randomly determined at the fluid of the foremost part of the upstream of the screw at time t=0. The number of screw revolutions was 200 rpm, the resin temperature was 150 ° C, and the melt viscosity was 2600 Pa s. The movement of the velocity field of the screw evaluated by the analysis was traced by simulation, and the line length was determined to be (L). When the initial line length is set to (L ₀ ), InL/L ₀ , and the result InL/L ₀ is 4.1.

The strip spouted from the mold was immediately quenched in ice water to fix the structure, and then granulated by a strand cutter to obtain granules. Using the obtained pellets, each characteristic was evaluated by the above method, and the results are shown in Table 1.

(Comparative Example 1)

A twin-screw extruder (TEX30XSSST manufactured by JSW Co., Ltd.) (L/D = 45.5) having a screw rotation number of 200 rpm was used in the mixing ratio shown in Table 1, and each component shown in Table 1 was supplied and melt-kneaded. The cylinder set temperature after the polymer melting section was adjusted to 230 °C. Further, the screw configuration is such that a general kneading disc (L/D = 3.8) is provided at a position of L/D = 22, 28. This screw configuration is referred to as a B type. In the case of screw rotation number = 200 rpm, resin temperature = 230 ° C, and melt viscosity = 500 Pa s, InL / L _{0 was} obtained in the same manner as in Example 1, and as a result, InL / L ₀ was 1.5.

The strip spouted from the mold was immediately quenched in ice water to fix the structure, and then granulated by a strand cutter to obtain granules. Using the obtained pellets, each characteristic was evaluated by the above method, and the results are shown in Table 2.

(Comparative Example 2)

Granules were obtained in the same manner as in Comparative Example 1, except that the components and the blending ratio were changed as shown in Table 1. In the case of screw rotation number = 200 rpm, resin temperature = 230 ° C, and melt viscosity = 500 Pa s, InL / L _{0 was} obtained in the same manner as in Example 1, and as a result, InL / L ₀ was 1.5. Using the obtained pellets, each characteristic was evaluated by the above method, and the results are shown in Table 1.

(Comparative examples 3 to 4)

Granules were obtained in the same manner as in Example 1 except that the components and the blending ratio were changed as shown in Table 1. In the case of screw rotation number = 200 rpm, resin temperature = 150 ° C, and melt viscosity = 3000 Pa s, InL / L _{0 was} obtained in the same manner as in Example 1, and as a result, InL / L ₀ was 4.2. Using the obtained pellets, each characteristic was evaluated by the above method, and the results are shown in Table 2.

(Comparative Example 5)

In addition, the screw setting temperature is changed to 230 ° C, and the screw configuration is changed to a screw configuration (B type) in which a general kneading disc (L/D = 3.8) is provided at a position from L/D = 22, 28, and Particles were obtained in the same manner as in Example 1. In the case of screw rotation number = 200 rpm, resin temperature = 230 ° C, and melt viscosity = 500 Pa s, InL / L _{0 was} obtained in the same manner as in Example 1, and as a result, InL / L ₀ was 1.5. Using the obtained pellets, each characteristic was evaluated by the above method, and the results are shown in Table 2.

(industrial availability)

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

Claims (9)

A thermoplastic resin composition obtained by blending the following components: (A) (a1) a vinyl monomer having a reactive functional group (i) and (a2) an aromatic vinyl monomer and (a3) cyanide The copolymer of the vinyl monomer is 0.1 to 95 parts by mass, and the copolymer of (B) (b1) aromatic vinyl monomer and (b2) vinyl cyanide monomer is 0 to 94.9 parts by mass, and (C) is reactive. 5 to 40 parts by mass of the vinyl-based colloidal polymer of the functional group (ii), and 0 to 35 parts by mass of the (D) vinyl-based colloidal polymer (wherein (A), (B), (C) and (D) The total of the storage elastic modulus in the dynamic viscoelasticity measurement is the glass transition temperature of the above (C) vinyl-based colloidal polymer having a reactive functional group (ii) of +20 ° C or less, and (C) The ethylene-based colloidal polymer having a reactive functional group (ii) is dispersed at an average particle diameter of 0.6 μm or less. The thermoplastic resin composition according to the first aspect of the invention, wherein the (A) (a1) vinyl functional monomer having a reactive functional group (i) and (a2) an aromatic vinyl monomer and (a3) The weight average molecular weight of the copolymer of the vinyl cyanide monomer is 10,000 or more and 300,000 or less. The thermoplastic resin composition according to claim 1 or 2, which is further formulated with (E) a peroxide based on 100 parts by mass of the total of the above (A), (B), (C) and (D) 0.1 to 1 part by mass. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the weight of the copolymer of the above (B) (b1) aromatic vinyl monomer and (b2) vinyl cyanide monomer is The average molecular weight is 100,000 or more and 300,000 or less. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the above (A) (a1) has a reactive functional group (i) and a (a) aromatic vinyl The reactive functional group (i) in the copolymer of the monomer and the (a3) vinyl cyanide monomer is an epoxy group. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the (C) reactive functional group (ii) in the vinyl-based colloidal polymer having a reactive functional group (ii) is Anhydride group. A method for producing a thermoplastic resin composition, which is the production method according to any one of claims 1 to 6, wherein the following components are melt-kneaded by chaotic mixing using a twin-screw extruder: (A) (a1) 0.1 to 95 parts by mass of a copolymer of a vinyl monomer having a reactive functional group (i) and (a2) an aromatic vinyl monomer and (a3) a vinyl cyanide monomer, (B) (b1) 0 to 94.9 parts by mass of the copolymer of the aromatic vinyl monomer and the (b2) vinyl cyanide monomer, and (C) 5 to 40 parts by mass of the vinyl colloidal polymer having the reactive functional group (ii), and (D) The ethylene-based colloidal polymer is 0 to 35 parts by mass (wherein the total of (A), (B), (C), and (D) is 100 parts by mass). The method for producing a thermoplastic resin composition according to claim 7, wherein the chaotic mixing is performed by the particle tracking method, wherein the line length is (L) and the initial line length is (L ₀ ), and the imaginary line is The logarithm of the elongation (InL/L ₀ ) is 2 or more. The method for producing a thermoplastic resin composition according to claim 7 or 8, which comprises the steps of: melt-kneading at least the above (A) and (C) by chaotic mixing in a twin-screw extruder; Further, the above (B) and/or (D) are blended to carry out melt kneading.