JP5797423B2 - Resin composition and molded body thereof - Google Patents

Description

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

A polymer alloy (polyamide / polyphenylene ether alloy) in which polyamide is blended with polyphenylene ether combines the excellent mechanical strength and chemical resistance of polyamide with the excellent low water absorption, dimensional stability and impact resistance of polyphenylene ether. It is known that it is a material (see Patent Document 1). At present, various improvements have been made to this polymer alloy, and it is used in various applications as a metal substitute for electrical and electronic parts and automobile parts.
Among these, automobile parts, particularly automobile exterior materials, are required to have rigidity and a low linear expansion coefficient as metal substitutes.
In order to meet this requirement, for example, Patent Document 2 discloses a technique relating to a composition containing a thermoplastic resin and glass, ceramic, and carbon reinforcing agent having a surface coating made of polyphenylene ether functionalized with a polar group. Is disclosed.
Patent Documents 3 and 4 disclose a method of filling a resin with a fibrous or non-fibrous filler.
Furthermore, Patent Document 5 discloses a technique for improving impact resistance by covering the surface of a fine filler with an elastomer.

Japanese Patent Publication No. 45-997 Japanese Patent Laid-Open No. 5-86296 JP 2004-346245 A JP 2004-285136 A JP 2005-264028 A

In recent years, regarding automobile exterior materials, in addition to the above-described rigidity and low linear expansion coefficient, there is an increasing demand for materials having higher impact resistance from the viewpoint of pedestrian protection.
However, the characteristics of linear expansion and impact resistance are in a contradictory relationship, and the conventionally proposed techniques such as those disclosed in the above-mentioned patent document cannot escape this conflicting relationship, In reality, no material has been obtained that combines linear expansion and impact resistance at a high level.

  This invention is made | formed in view of the said situation, and it aims at providing the resin composition and molded object which also have a low linear expansion coefficient, improving impact resistance.

  The inventor has intensively studied to achieve the above object. As a result, surprisingly, in the polyamide / polyphenylene ether alloy in which a mixture of a fibrous filler and a plate-like and / or granular filler having an average primary particle diameter of 10 to 1000 nm is filled in polyphenylene ether and polyamide, the functional group is added. Adding impact modifiers that have a functional group and impact modifiers that do not have functional groups in a specific amount not only improves impact resistance, but also usually has a linear expansion coefficient that deteriorates due to the incorporation of impact modifiers. It has been found that it can be reduced, that is, the impact resistance and the linear expansion that are in a reciprocal relationship can be improved at the same time, and the present invention has been made.

That is, the present invention is as follows.
[1]
A resin composition comprising (A) polyphenylene ether, (B) polyamide, (C) impact modifier, and (D) inorganic filler,
10-50 mass% of said (A) component with respect to the total amount of said (A) component and said (B) component, 50-90 mass% of said (B) component is included,
As the component (C), (C1) an impact modifier having a functional group, and (C2) an impact modifier having no functional group,
The blending amount of the component (C1) is 0.5 to 30 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
As the component (D), (D1) wollastonite, and (D2) clay having an average primary particle size of 10 to 1000 nm,
The functional group is at least one selected from the group consisting of a carboxylic acid group, an acid anhydride group, an acrylic acid group, a hydroxyl group, a glycidyl group, an amide group, an amino group, and a thiophenol group;
The blending amount of the component (D1) and the component (D2) is 30 to 70% by mass of the component (D1) and 70 to 30% by mass of the component (D2) with respect to the total amount of the component (D). , Resin composition.
[2]
The component (C1) is an ethylene-α-olefin copolymer, an ethylene-α-olefin-diene copolymer, an ethylene-glycidyl methacrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-vinyl alcohol copolymer. A block having at least one polymer block mainly composed of an aromatic vinyl compound, and at least one polymer block mainly composed of a conjugated diene compound, and a polymer in which the functional group is added to any of the compounds The resin according to [1], which is at least one selected from the group consisting of a polymer having a functional group added to a copolymer and a polymer having a functional group added to a hydrogenated product of the block copolymer. Composition.
[3]
The block copolymer, wherein the component (C2) has at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound, and The resin composition according to the above [1] or [2], which is at least one selected from the group consisting of hydrogenated block copolymers.
[4]
A block copolymer having at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound contained in the component (C1) and the component (C2). The resin composition according to the above [2] or [3], wherein the polymer and / or the hydrogenated component of the block copolymer has a number average molecular weight (in terms of standard polystyrene) of 40,000 to 80,000. object.
[5]
Any of the above [1] to [4], wherein the blending amount of the component (C1) is 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). A resin composition as described above.
[6]
The resin composition according to any one of [1] to [5], wherein the reduced viscosity (measured with a 0.5 g / dL chloroform solution at 30 ° C.) of the component (A) is 0.21 to 0.40 dL / g. object.
[7]
The resin composition according to any one of [1] to [6], wherein the component (B) is polyamide 6,6 and / or polyamide 6.
[8]
Resin composition in any one of said [1]-[7] whose ratio (L / D) of the average fiber length L of the said (D1) component and the average fiber diameter D is 5-500.
[9]
The resin composition according to any one of [1] to [8], wherein the component (D2) is a plate-like and / or granular filler having an average primary particle diameter of 10 to 500 nm.
[10]
Said [1]-[] whose compounding quantity of said (D) component is 5-55 mass parts with respect to a total of 100 mass parts of said (A) component, said (B) component, and said (C) component. [9] The resin composition according to any one of [9].
[11]
The resin composition according to any one of [1] to [10], wherein the component (D) is present in a dispersed state in the continuous phase composed of the component (B).
[12]
(E) The resin composition according to any one of [1] to [11], further including at least one selected from the group consisting of conductive carbon black, graphite, and carbon fibrils as a conductivity imparting material.
[13]
The molded object obtained by injection-molding the resin composition in any one of said [1]-[12].
[14]
Charpy impact strength measured according to ISO 179 is 5.7 kJ / m ² or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The molded article according to the above [13], wherein the additive average value of the linear expansion coefficient measured in step MD and TD direction is less than 5.5 × 10 ⁻⁵ / ° C.
[15]
In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 25 cc / 10 min or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
And the molded object of said [13] description whose ratio TD / MD of the linear expansion coefficient of MD direction and TD direction is less than 1.3.
[16]
In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 30 cc / 10 min or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
And the molded object of said [13] description whose ratio TD / MD of the linear expansion coefficient of MD direction and TD direction is less than 1.3.
[17]
In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 30 cc / 10 min or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
And ratio TD / MD of the linear expansion coefficient of MD direction and TD direction is less than 1.3,
The molded article according to the above [13], wherein the flexural modulus measured according to ISO 178 is 3.5 MPa or more.
[18]
Volume resistivity measured using an electrometer after applying silver paint to a cross section of a molded piece having a cross-sectional area of 10 × 4 mm and a length of 50 mm produced by freezing and rupturing a multi-purpose specimen A type having a thickness of 4 mm in accordance with ISO294 Is less than 1 × 10 ⁵ Ω · cm,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The molded article according to the above [13], wherein the additive average value of the linear expansion coefficient measured in step MD in the MD direction and the TD direction is less than 5.5 × 10 ⁻⁵ / ° C.
[19]
In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 30 cc / 10 min or more,
Volume resistivity measured using an electrometer after applying silver paint to a cross section of a molded piece having a cross-sectional area of 10 × 4 mm and a length of 50 mm produced by freezing and rupturing a multi-purpose specimen A type having a thickness of 4 mm in accordance with ISO294 Is less than 1 × 10 ⁵ Ω · cm,
Charpy impact strength measured according to ISO179 is 5.7 kJ / m ² or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
Ratio TD / MD of linear expansion coefficient in MD direction and TD direction is less than 1.3,
And the molded object of said [13] description whose bending elastic modulus measured based on ISO178 is 3.5 Mpa or more.
[20]
The automotive exterior material which consists of a molded object in any one of said [13]-[19].
[21]
An automobile exterior material having an average thickness of 2 mm or less, comprising the molded article according to any one of [13] to [19].

  By this invention, the resin composition and molded object which have the outstanding impact resistance and a low linear expansion coefficient can be provided.

It is the figure which plotted the relationship between the volume resistivity which concerns on Comparative Examples 1-3, and an average linear expansion coefficient. An arrow (→) in the figure indicates the direction of change in physical properties when (C1) component is not added → added. It is the figure which plotted the relationship between Examples 1-3 and the volume resistivity which concerns on the comparative example 4, and an average linear expansion coefficient. An arrow (→) in the figure indicates the direction of change in physical properties when (C1) component is not added → added. It is the figure which plotted the relationship between the Charpy impact strengths and the average linear expansion coefficients according to Examples 1 to 3 and Comparative Example 4. An arrow (→) in the figure indicates the direction of change in physical properties when (C1) component is not added → added.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to the following embodiment, and various modifications can be made without departing from the gist of the present invention.

The resin composition of the present embodiment is
A resin composition comprising (A) polyphenylene ether, (B) polyamide, (C) impact modifier, and (D) inorganic filler,
10-50 mass% of said (A) component with respect to the total amount of said (A) component and said (B) component, 50-90 mass% of said (B) component is included,
As the component (C), (C1) an impact modifier having a functional group, and (C2) an impact modifier having no functional group,
The blending amount of the component (C1) is 0.5 to 30 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
The component (D) is a resin composition containing (D1) fibrous filler and (D2) a plate-like and / or granular filler having an average primary particle diameter of 10 to 1000 nm.

[Polyphenylene ether (PPE)]
The polyphenylene ether (A) according to this embodiment is a homopolymer and / or copolymer having a repeating structural unit represented by the following general formula (1).

  Here, in formula (1), each R is independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, or a haloalkyl having 1 to 7 carbon atoms. Group, an aminoalkyl group having 1 to 7 carbon atoms, a hydrocarbyloxy group having 1 to 7 carbon atoms, or a halohydrocarbyloxy group having 1 to 7 carbon atoms (wherein at least two carbon atoms are a halogen atom and an oxygen atom) It is separated from atoms.)

  Specific examples of the polyphenylene ether according to this embodiment include homopolymers such as poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), and poly (2,6-dichloro-1,4-phenylene ether). As the copolymer, for example, a copolymer of 2,6-dimethylphenol and another phenol compound (for example, 2,6-dimethylphenol and 2,3 described in JP-B-52-17880). , 6-trimethylphenol copolymer, 2,6-dimethylphenol and 2-methyl-6-butylphenol copolymer).

  Of these, particularly preferred polyphenylene ethers are poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol. Or a mixture thereof.

  When a copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol is used as the polyphenylene ether, the total amount of the copolymer is 100 mass. %, It is preferable that 10 to 30% by mass of 2,3,6-trimethyl-1,4-phenol is contained as a monomer unit, more preferably 15 to 25% by mass, and still more preferably 20 to Contains 25% by mass.

  Further, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol is preferable. The molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn), also referred to as dispersity) is in the range of 2.5 to 4.0. The molecular weight distribution is more preferably in the range of 2.5 to 3.8, and still more preferably in the range of 2.5 to 3.5. When the molecular weight distribution is in the above range, it is preferable from the viewpoint of fluidity in the mold during molding. Here, the weight average molecular weight and the number average molecular weight are values measured with an ultraviolet spectroscopic detector using a gel permeation chromatography measuring apparatus (GPC) and converted into standard polystyrene.

  It does not specifically limit as a manufacturing method of the polyphenylene ether which concerns on this embodiment, A well-known method can be used. Polyphenylene ethers include, for example, U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357 and 3,257,358, JP-A-50-51197, and JP-B-52-17880. It can be obtained by the production method described in Japanese Patent Publication No. 63-152628.

  The reduced viscosity (ηsp / C: 0.5 g / dL chloroform solution, 30 ° C., measured with an Ubbelohde type viscosity tube) of the polyphenylene ether according to this embodiment is in the range of 0.15 to 0.55 dL / g. preferable. A more preferable lower limit value is 0.20 dL / g or more, still more preferably 0.21 dL / g or more, still more preferably 0.25 dL / g or more, particularly preferably 0.27 dL / g or more. The upper limit value is more preferably 0.50 dL / g or less, further preferably 0.45 dL / g or less, particularly preferably 0.40 dL / g or less. From the viewpoint of suppressing thermal deformation of the resin composition of the present embodiment in a high temperature environment, the lower limit value of the reduced viscosity of the polyphenylene ether is preferably 0.15 dL / g or more, and has compatibility with an impact modifier described later. From the viewpoint of preventing deterioration, the upper limit value is preferably 0.55 dL / g or less.

  In the present embodiment, a mixture obtained by blending two or more polyphenylene ethers having different reduced viscosities may be used. Examples of the mixture obtained by blending such polyphenylene ether include a mixture of polyphenylene ether having a reduced viscosity of 0.35 dL / g or less and polyphenylene ether having a reduced viscosity of 0.50 dL / g or more, and a reduced viscosity of 0.35 dL / g or less. A mixture of a low molecular weight polyphenylene ether and a polyphenylene ether having a reduced viscosity of 0.45 dL / g or more is included, but of course, the present invention is not limited thereto.

  The polyphenylene ether according to the present embodiment is preferably functionalized with a compatibilizing agent in order to improve the compatibility with the (B) polyamide in the present embodiment described later. As the compatibilizing agent, for example, those described in detail in WO 01/81473 can be used. Among these compatibilizers, maleic acid, fumaric acid, citric acid and their anhydrides and mixtures thereof are preferred, and maleic acid and / or its anhydride are more preferred.

  The amount of the compatibilizing agent used is preferably in the range of 0.01 to 8 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0. 0 to 100 parts by mass of (A) polyphenylene ether. It is 05-3 mass parts. From the viewpoint of not reducing the impact resistance of the resin composition (or molded product), the amount of the compatibilizer used is preferably 0.01 parts by mass or more, generation of silver streaks during injection molding, and mechanical properties. From the viewpoint of suppressing the decrease in the amount, it is preferably 8 parts by mass or less.

  In addition, various known stabilizers may be used to stabilize the polyphenylene ether. Examples of the stabilizer include organic stabilizers such as hindered phenol stabilizers, phosphate ester stabilizers, and hindered amine stabilizers. The blending amount of the stabilizer is preferably less than 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether.

  Furthermore, other known additives that can be added to the polyphenylene ether may be added in an amount of preferably less than 10 parts by mass with respect to 100 parts by mass of the polyphenylene ether.

[Polyamide (PA)]
The polyamide (B) according to this embodiment is not particularly limited as long as it has an amide bond (—NH—C (═O) —) in the repeating structure of the polymer main chain. (B) Specific examples of the polyamide include, for example, polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, Polyamide 6/6, Polyamide MXD (m-xylylenediamine) · 6, Polyamide 6, T, Polyamide 6, I, Polyamide 6/6, T, Polyamide 6/6, I, Polyamide 6,6 / 6 T, polyamide 6,6 / 6, I, polyamide 6, T / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6 , T, polyamide 6, 6/12/6, T, polyamide 6/12/6, I, polyamide 6, 6/12/6, I, polyamide 9, T, and mixtures thereof. Here, for example, polyamide 6, I means a polymerized polyamide resin of hexamethylenediamine and isophthalic acid, and polyamide 6/6, T means a co-polymer of ε-aminocaproic acid, hexamethylenediamine and terephthalic acid. It means a polymerized polyamide resin. Furthermore, polyamides obtained by further copolymerizing with two or more of these polyamide resins using an extruder or the like can also be used.

  Of the above, preferred polyamides are polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, polyamide 6 / 6,12. Aliphatic polyamides, and mixtures thereof. Among the above, polyamide 6, polyamide 6,6, or a mixture thereof is more preferable. By using an aliphatic polyamide, excellent impact resistance and ductility can be maintained, and moldability tends to be facilitated. Furthermore, by using polyamide 6, polyamide 6,6, or a mixture thereof, for example, there is a tendency that a decrease in impact resistance when filled with a conductivity imparting agent described later can be suppressed.

  The method for producing the polyamide (B) according to this embodiment is not particularly limited, but methods such as ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like. Can be mentioned. As another production method, a method of obtaining a polyamide by polymerizing lactams, diamines, dicarboxylic acids, and / or aminocarboxylic acids to a low molecular weight oligomer stage in a polymerization reactor and further increasing the molecular weight in an extruder or the like. Also mentioned.

  Examples of lactams include ε-caprolactam, enantolactam, and ω-laurolactam.

  Examples of diamines include aliphatic diamines, alicyclic diamines, and aromatic diamines. Specific examples thereof include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 2, 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, Examples include p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

  Dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid. , Isophthalic acid, naphthalenedicarboxylic acid, and dimer acid.

  Examples of the aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecanoic acid. Can be mentioned.

  As a lower limit of the viscosity number [VN] of (B) polyamide which concerns on this embodiment, 45 mL / g or more is preferable, More preferably, it is 50 mL / g or more. The upper limit is preferably 180 mL / g or less, more preferably 160 mL / g or less, still more preferably 150 mL / g or less, and particularly preferably 140 mL / g or less. From the viewpoint of not reducing the fluidity of the resin composition, the upper limit is preferably 180 mL / g or less, and from the viewpoint of not reducing the toughness of the resin composition, the lower limit is preferably 45 mL / g or more. The viscosity number here is a viscosity number [VN] measured in 96% sulfuric acid specified by ISO 307: 1997.

  The lower limit value of the terminal amino group concentration of the polyamide (B) according to this embodiment is preferably 3 μmol / g or more, more preferably 5 μmol / g or more. The upper limit of the concentration is preferably 80 μmol / g or less, more preferably 70 μmol / g or less, still more preferably 60 μmol / g or less, and particularly preferably 50 μmol / g or less.

  Although there is no restriction | limiting in particular in the terminal carboxyl group density | concentration of (B) polyamide which concerns on this embodiment, As a lower limit, 20 micromol / g or more is preferable, More preferably, it is 30 micromol / g or more. Moreover, as an upper limit of a density | concentration, 150 micromol / g or less is preferable, More preferably, it is 120 micromol / g or less.

  In the present embodiment, the molar ratio between the terminal amino group concentration and the terminal carboxyl group concentration of the polyamide (terminal amino group concentration / terminal carboxyl group concentration) can affect the mechanical properties of the molded article, and therefore has a preferable range. Exists. The molar ratio between the terminal amino group concentration and the terminal carboxyl group concentration is preferably 1.0 or less, more preferably 0.9 or less, still more preferably 0.8 or less, and particularly preferably 0.7. It is as follows. The lower limit of the molar ratio is not particularly limited, but is preferably 0.1 or more.

  As a method for adjusting the end group concentration of the polyamide, a known method can be used. For example, terminal amino groups such as diamine, monoamine, dicarboxylic acid, monocarboxylic acid, acid anhydride, monoisocyanate, monoacid halide, monoester, monoalcohol, etc. The method of adding the 1 type (s) or 2 or more types of the terminal regulator which reacts with the terminal regulator which reacts and / or a terminal carboxyl group is mentioned.

  Examples of terminal regulators that react with terminal amino groups include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid. Aliphatic monocarboxylic acids such as cycloaliphatic carboxylic acids; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid Carboxylic acid; and a plurality of mixtures arbitrarily selected from these. Among these, from the viewpoint of reactivity, stability of the sealing end, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid Benzoic acid is preferred, and benzoic acid is particularly preferred.

  Examples of the terminal regulator that reacts with the terminal carboxyl group include aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Examples thereof include monoamines; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; and a plurality of mixtures arbitrarily selected from these. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferable from the viewpoints of reactivity, boiling point, sealing end stability, price, and the like.

The concentration of the amino terminal group and the carboxyl terminal group can be determined from the integral value of the characteristic signal corresponding to each terminal group by ¹ H-NMR. As a method for obtaining the concentration of these end groups, specifically, the method described in JP-A-7-228775 can be used. When this method is used, deuterated trifluoroacetic acid is useful as a measurement solvent. In addition, the number of ¹ H-NMR integrations is required to be at least 300 scans even when measured with an instrument having sufficient resolution.

  The polyamide according to this embodiment preferably has a moisture content in the range of 500 ppm to 3000 ppm, more preferably 500 ppm to 2000 ppm. From the viewpoint of suppressing the deterioration of the color tone of the resin composition, the water content is preferably 500 ppm or more, and from the viewpoint of suppressing a decrease in viscosity during processing, the water content is preferably 3000 ppm or less.

  Moreover, the resin composition of this embodiment may mix | blend a styrene-type thermoplastic resin if it is the quantity of less than 50 mass parts with respect to a total of 100 mass parts of polyamide and polyphenylene ether. Examples of the styrenic thermoplastic resin include homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), and the like.

  In the present embodiment, the blending amount of (A) polyphenylene ether and (B) polyamide is 10 to 50% by mass of (A) polyphenylene ether with respect to the total amount of (A) polyphenylene ether and (B) polyamide, Preferably it contains 20-40 mass%, (B) Polyamide 50-90 mass%, Preferably it contains 60-80 mass%. When the blending amount of the component (A) is less than 10% by mass, the impact resistance is inferior, and when it exceeds 50% by mass, the fluidity is inferior.

[Impact modifier]
In this embodiment, an impact improving material is included as the component (C). The impact modifier as referred to in the present embodiment is an impact modifier having substantially no polymer block mainly composed of an aromatic vinyl compound, at least one polymer block mainly composed of an aromatic vinyl compound, One or more selected from the group consisting of a block copolymer having at least one polymer block mainly comprising a conjugated diene compound, and a hydrogenated product of the block copolymer, and a functional group added thereto It is preferable that it is a polymer.

  According to this embodiment, “substantially does not have a polymer block mainly composed of an aromatic vinyl compound” means that when the amount of the component (C) is 100% by mass, the main component is an aromatic vinyl compound. It means that the ratio of the polymer block is less than 5% by mass. Examples of impact modifiers having substantially no polymer block mainly composed of aromatic vinyl compounds include ethylene-α-olefin copolymers, ethylene-α-olefin-diene copolymers, and ethylene. -The polymer which the said functional group added to the glycidyl methacrylate copolymer, the ethylene-ethyl acrylate copolymer, the ethylene-vinyl alcohol copolymer etc. is mentioned. Among these, an ethylene-ethyl acrylate copolymer and an ethylene-α-olefin copolymer are preferable, and an ethylene-α-olefin copolymer is particularly preferable.

  “Mainly” in the polymer block mainly composed of the aromatic vinyl compound according to the present embodiment means that 50% by mass or more of the block is an aromatic vinyl compound, and preferably 70% in the block. More than mass% is an aromatic vinyl compound, More preferably, it is 80 mass% or more, More preferably, 90 mass% or more is an aromatic vinyl compound.

  Further, “mainly” in a polymer block mainly composed of a conjugated diene compound means that 50% by mass or more of the block is a conjugated diene compound, and preferably 70% by mass or more is conjugated in the block. It is a diene compound, More preferably, 80 mass% or more, More preferably, 90 mass% or more is a conjugated diene compound.

  Here, even when a small amount of a conjugated diene compound or other compound is randomly bonded to a polymer block mainly composed of an aromatic vinyl compound, 50% by mass or more of the block is an aromatic vinyl compound. If it is formed from, it is regarded as a block copolymer mainly composed of an aromatic vinyl compound. The same applies to the case of a conjugated diene compound.

  As a specific example of the aromatic vinyl compound, for example, one or more compounds selected from the group consisting of styrene, α-methylstyrene and vinyltoluene are preferable, and styrene is particularly preferable among them. As a specific example of the conjugated diene compound, one or more compounds selected from the group consisting of butadiene, isoprene, piperylene and 1,3-pentadiene are preferable, and butadiene, isoprene and a combination thereof are particularly preferable.

It is known that there are three types of conjugated diene compounds, 1,2-vinyl bond, 3,4-vinyl bond and 1,4-vinyl bond. The microstructure of the conjugated diene compound block portion of the block copolymer in the present embodiment has a 1,2-vinyl bond amount or a total amount of 1,2-vinyl bond amount and 3,4-vinyl bond amount of 5 It is preferably -80%, more preferably 10-50%, and still more preferably 20-40%. When the vinyl bond amount is in the above range, the impact resistance and the low temperature impact resistance tend to be better. The vinyl bond amount here indicates the ratio of the bond form of the conjugated diene compound in the three bond forms. For example, the 1,2-vinyl bond amount is the sum of the three bond forms. It means the ratio of 1,2-vinyl bond to. Here, the amount of each vinyl bond can be measured by ¹ H-NMR.

  In the block copolymer in the present embodiment, the polymer block [A] mainly composed of an aromatic vinyl compound and the polymer block [B] mainly composed of a conjugated diene compound are AB type, AB It is preferably a block copolymer having a bonding form selected from the -A type and the ABAB type, and may be a mixture thereof. Among the above, the ABA type, the ABAB type, or a mixture thereof is more preferable, and the ABA type is more preferable.

The block copolymer is more preferably a hydrogenated block copolymer. The hydrogenated block copolymer is an aliphatic double polymer block composed mainly of a conjugated diene compound by hydrogenating the block copolymer of the aromatic vinyl compound and the conjugated diene compound. The bond is controlled in the range of more than 0% and not more than 100%. A preferable hydrogenation rate of the hydrogenated block copolymer is 80% or more, and more preferably 98% or more. Here, the hydrogenation rate can be measured by ¹ H-NMR.

These block copolymers may be a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer.
In addition, these aromatic vinyl compound-conjugated diene compound block copolymers have different bond types, different types of aromatic vinyl compounds, and different types of conjugated diene compounds unless the effects of the present invention are impaired. A mixture of two or more selected from different ones, those having different total amounts of 1,2-bonded vinyl content and 3,4-bonded vinyl content, and those having different aromatic vinyl compound content are used. May be.

  Moreover, as the block copolymer of this embodiment, you may use what mixed beforehand the oil which has a paraffin as a main component in a block copolymer. By previously mixing an oil mainly composed of paraffin into the block copolymer, the processability of the resin composition tends to be improved.

  The number average molecular weight of the block copolymer according to this embodiment is preferably 250,000 or less as an upper limit. More preferably, it is 150,000 or less, More preferably, it is 80,000 or less. On the other hand, the lower limit is preferably 40,000 or more. When the number average molecular weight of the block copolymer is within the above range, there is a tendency to reduce the risk of problems during extrusion and deterioration of fluidity.

  The block copolymer may be a mixture of a low molecular weight block copolymer and a high molecular weight block copolymer. Examples of such a mixture include, but are not limited to, a mixture of a low molecular weight block copolymer having a number average molecular weight of less than 80,000 and a high molecular weight block copolymer having a number average molecular weight of 200,000 or more. It will never be done.

  The number average molecular weight of the block copolymer refers to the number average molecular weight measured with an ultraviolet spectroscopic detector using a gel permeation chromatography measuring device (GPC) and converted to standard polystyrene. At this time, a low molecular weight component due to catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the molecular weight calculation.

  The number average molecular weight of the polymer block mainly composed of one aromatic vinyl compound in the block copolymer is more preferably in the range of 4000 to 50,000.

The number average molecular weight of the polymer block n mainly composed of one aromatic vinyl compound in the block copolymer can be obtained by the following formula (2) using the number average molecular weight of the block copolymer described above. .
Mn (a), n = {Mn × a / (a + b)} / N (a) (2)
Here, in the above formula (2), Mn (a), n is the number average molecular weight of a polymer block mainly composed of one aromatic vinyl compound in the block copolymer n, and Mn is the block copolymer n. The number average molecular weight of a, a is the mass% of the polymer block mainly composed of the aromatic vinyl compound in the block copolymer n, and b is the mass of the polymer block mainly composed of the conjugated diene compound in the block copolymer n. % And N (a) represent the number of polymer blocks mainly composed of an aromatic vinyl compound in the block copolymer n.

  In the present embodiment, the component (C) includes two types of impact modifiers: (C1) an impact modifier having a functional group, and (C2) an impact modifier having no functional group.

  Specific examples of the functional group of the impact improving material having a (C1) functional group according to the present embodiment include a carboxylic acid group, an acid anhydride group, an acrylic acid group, a hydroxyl group, a glycidyl group, an amide group, an amino group, and a thiophenol. Groups and the like. Among these functional groups, an acid anhydride group and a glycidyl group are more preferable, and an acid anhydride group is particularly preferable. Examples of preferred acid anhydride groups include maleic anhydride.

These functional groups may be in the repeating structural unit of the impact modifier, or may be in the form of being grafted to the molecular chain of the impact modifier, for example.
An impact modifier in which a functional group is grafted to the molecular chain of the impact modifier is an impact modifier that has no functional group in the repetitive structural unit but is chemically added to the functional group by post-treatment. Point to.

As a method for producing an impact modifier having a functional group grafted on the molecular chain of the impact modifier,
(1) A method in which an impact modifier is melt-kneaded and reacted with a modifying compound at a temperature equal to or higher than the softening point temperature of the impact modifier in the presence or absence of a radical initiator,
(2) A method of reacting an impact modifier and a modifying compound in a solution at a temperature lower than the softening point temperature of the impact modifier in the presence or absence of a radical initiator,
(3) A method of reacting the impact modifier and the modifying compound without melting at a temperature equal to or lower than the softening point temperature of the impact modifier in the presence or absence of a radical initiator,
Etc. Any of these methods may be used, but the method (1) is preferable, and among the methods (1), the method performed in the presence of a radical initiator is particularly preferable.

  The addition ratio of the functional group to be grafted to the molecular chain of the impact modifier is preferably in the range of 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, but is not limited thereto. Never happen.

  In the present embodiment, (C1) the impact modifier having a functional group may be a polymer, aromatic or fragrance, wherein the functional group is added to an impact modifier that does not have a polymer block that is essentially composed of an aromatic vinyl compound. A polymer obtained by adding the functional group to a block copolymer having at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound; and 1 or more types chosen from the group which consists of the polymer which the said functional group added to the hydrogenated substance of the said block copolymer are preferable.

  (C1) As the impact modifier having a functional group, specifically, a styrene-butadiene-styrene block copolymer, a polymer obtained by adding the functional group to a hydrogenated product of the block copolymer, ethylene-α -Olefin copolymer, ethylene-α-olefin-diene copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer, etc. Coalescence is mentioned. Among them, styrene-butadiene-styrene block copolymers, polymers obtained by adding the functional groups to hydrogenated products of the block copolymers, ethylene-α-olefin copolymers, ethylene-ethyl acrylate copolymers A polymer having a functional group added is preferred, and a polymer having a functional group added to an ethylene-α-olefin copolymer is particularly preferred. Moreover, you may use together the impact improving material which has the said functional group.

  In this embodiment, the blending amount of the impact modifier (C1) having a functional group is 0.5 to 30 parts by mass with respect to 100 parts by mass in total of (A) polyphenylene ether and (B) polyamide. Preferably it is 0.5-25 mass parts, More preferably, it is 0.5-20 mass parts, Most preferably, it is 0.5-9 mass parts. The blending amount of the component (C1) is 30 parts by mass or less from the viewpoint of suppressing deterioration in fluidity during injection molding, and 0.5 parts by mass or more from the viewpoint of obtaining effects of imparting impact resistance and reducing linear expansion. It is.

  (C2) The impact modifier having no functional group includes an impact modifier substantially free of a polymer block mainly comprising an aromatic vinyl compound, and at least one heavy agent mainly comprising an aromatic vinyl compound. A block copolymer having a combined block and at least one polymer block mainly composed of a conjugated diene compound, and at least one selected from the group consisting of hydrogenated products of the block copolymer It is preferable. By using the above-described impact modifier, block copolymer and / or hydrogenated product thereof as the component (C2), the compatibility between the component (C2) and polyphenylene ether is improved, and the impact strength tends to be improved. .

  The blending amount of the component (C2) is the total amount of the impact modifier (C1) having a functional group and the impact modifier (C2) having no functional group. (A) Polyphenylene ether and (B) polyamide Is preferably more than 5 parts by weight, more preferably more than 5 parts by weight and more than 30 parts by weight, and still more preferably more than 10 parts by weight and 30 parts by weight. For example, when (A1) polyphenylene ether and (B) polyamide total 100 parts by mass, and (C1) the impact modifier having a functional group is 10 parts by mass, (C2) the impact having no functional group The upper limit of the preferable compounding amount of the improving material is 30 parts by mass. From the viewpoint of suppressing deterioration of fluidity during injection molding, the total amount of the impact modifier (C1) having a functional group and the impact modifier (C2) having no functional group is preferably 40 parts by mass or less. On the other hand, from the viewpoint of imparting better impact resistance, the total amount of the (C1) impact modifier having a functional group and the (C2) impact modifier having no functional group is preferably more than 5 masses.

[Inorganic filler]
The (D) inorganic filler according to the present embodiment includes (D1) a fibrous filler and (D2) a plate-like and / or granular filler having an average primary particle diameter of 10 to 1000 nm.

[(D1) Fibrous filler]
The (D1) fibrous filler according to this embodiment is selected from the group consisting of glass fiber, carbon fiber, metal fiber, wollastonite, silicon carbide whisker, silicon nitride whisker, fibrous aluminum oxide, and acicular titanium oxide. There may be mentioned at least one inorganic filler. Among the above, wollastonite, silicon carbide whisker, and silicon nitride whisker are preferable, and wollastonite is more preferable. The said inorganic filler is used individually by 1 type or in combination of 2 or more types. The average fiber length L and the average fiber diameter D of the fibrous filler and the ratio (L / D) thereof are not particularly limited as long as the effects of the present invention are not impaired, but are preferably 5 to 500, and more. Preferably it is 5-300, More preferably, it is 5-100. When L / D is 5 or more, better rigidity tends to be obtained, and when L / D is 500 or less, anisotropy tends to be suppressed within a suitable range. In the case of wollastonite, those having an average fiber diameter D of 3 to 30 μm, an average fiber length L of 10 to 500 μm, and (L / D) of 5 to 100 are preferably used.

Here, the average fiber length L and the average fiber diameter D of the fibrous filler can be determined as follows.
The fibrous filler is dispersed in water, transferred onto a glass slide, and observed under an optical microscope. Using an image analysis device, the length of 400 arbitrarily selected fibrous fillers is measured and determined by the following equation.
Average fiber diameter D = ΣLi / n (number average)
Average fiber length L = ΣLi ² / ΣLi (weight average)
Here, in the formula, Li represents the length of each fibrous filler (L1, L2,..., L400), and Li ² represents the length of each corresponding fibrous filler. Square (L1 ² , L2 ² ,..., L400 ² ) and n indicate the number of fibrous fillers observed.

[(D2) Plate-like and / or granular filler]
The plate-like and / or granular filler (D2) having an average primary particle diameter of 10 to 1000 nm according to this embodiment is at least one selected from the group consisting of clay, bentonite, talc, calcium carbonate, silica, and titanium oxide. Inorganic fillers. Among these, clay is more preferable. Among clays, kaolin, layered smectite, and layered synthetic mica are preferable. Furthermore, in kaolin, kaolin having a primary average particle diameter of 500 nm or less is preferable, in layered smectite, montmorillonite or hectorite having a thickness of 5 nm or less is preferable, and in layered synthetic mica, Synthetic mica that is 5 nm or less is preferred. Among the above, synthetic mica having a thickness of 3 nm or less is particularly preferable.

  (D2) The average primary particle diameter of the plate-like and / or granular filler is 10 to 1000 nm, preferably 10 to 500 nm, more preferably 10 to 400 nm, and still more preferably 10 to 300 nm. Here, the average primary particle diameter is a weight average value obtained by taking a photo several tens of thousands of times with an electron microscope having a resolution of at least 1.5 to 2 nm and measuring the major axis of 2,000 or more particles. .

  The inorganic fillers (D1) and (D2) according to this embodiment are selected from the group consisting of a hydroxyl group, an amide group, an amino group, a carboxyl group, a mercapto group, a glycidyl group, an acid anhydride group, and derivatives thereof. The surface treatment may be performed with one or more known surface treatment agents. Among the above, it is preferable that the surface treatment is performed with an acid anhydride group or a mercapto group. As a usage-amount of a surface treating agent, it is preferable that it is 0.05-5 mass parts with respect to 100 mass parts of inorganic fillers.

  In this embodiment, the blending amount of (D) inorganic filler is (A) polyphenylene ether, (B) polyamide, (C1) impact modifier having a functional group, and (C2) impact modifier having no functional group. Preferably it is 5-55 mass parts with respect to 100 mass parts of total amounts, More preferably, it is 10-55 mass parts, More preferably, it is 15-55 mass parts, Most preferably, it is 20-50 mass parts. From the viewpoint of suppressing an increase in the linear expansion coefficient, it is preferably 5 parts by mass or more, and from the viewpoint of suppressing a decrease in impact resistance and an appearance defect on the surface of the molded body, it is preferably 55 parts by mass or less.

  In the present embodiment, (D1) fibrous filler and (D2) a plate-like and / or granular filler having an average primary particle diameter of 10 to 1000 nm are used in combination, and the ratio is anisotropic or fluid. May have an impact. The preferred ratio of the component (D1) and the component (D2) is (D1) 30 to 70% by mass and (D2) 70 to 30% by mass with respect to the total amount of the (D1) and (D2) components. is there. Further preferred ratios are (D1) 30 to 65% by mass and (D2) 70 to 35% by mass. From the viewpoint of suppressing the deterioration of fluidity in the mold during injection molding, the ratio of (D1) is preferably 30% by mass or more, and from the viewpoint of suppressing an increase in anisotropy, the ratio of (D1) is It is preferable that it is 70 mass% or less.

  The morphology of the resin composition of the present embodiment can be observed with a transmission microscope using, for example, a known staining agent. As the morphology, (A) polyphenylene ether and (C1) and / or (C2) impact modifier is dispersed phase, (B) polyamide forms continuous phase, (D1) and / or (D2) inorganic filler However, (B) the form which disperse | distributes and exists in a polyamide continuous phase is preferable. When the resin composition has the above morphology, it tends to have both the impact resistance effect of the PPE / SEBS compatible domain and the rigidity of the PA / filler phase. From the viewpoint of maintaining excellent rigidity and a low linear expansion coefficient, it is preferable to have a morphology in which (D) component is not localized on the surface of (D) inorganic filler.

[Conductivity imparting material]
In this embodiment, the resin composition may further include (E) a conductivity imparting material. The blending amount of the (E) conductivity imparting material in the present embodiment is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass when the entire resin composition is 100% by mass. %, And more preferably 1 to 3% by mass.

  (E) The conductivity imparting material is preferably at least one selected from the group consisting of conductive carbon black, graphite, and carbon fibrils from the viewpoint of achieving both impact resistance and conductivity. Among these, it is more preferable that conductive carbon black is included.

  (E) When conductive carbon black is used as the conductivity imparting material, conductive carbon black having a dibutyl phthalate (DBP) oil absorption of 250 mL / 100 g or more is preferable. More preferably, the conductive carbon black has a DBP oil absorption of 300 mL / 100 g or more, and more preferably 350 mL / 100 g or more. The DBP oil absorption referred to here is a value measured by a method defined in ASTM D2414.

The conductive carbon black preferably has a BET specific surface area (JIS K6221-1982) of 200 m ² / g or more, more preferably 400 m ² / g or more. Examples of commercially available products include Ketjen Black EC and Ketjen Black EC-600JD available from Ketjen Black International, and Printex XE and XE-2B available from Evonik Degussa.

  (E) Although there is no restriction | limiting in particular regarding the addition method of electroconductivity imparting material, The method of adding electroconductivity imparting material in the melt mixture of polyamide and polyphenylene ether, melt-kneading, and adding electroconductivity imparting material in resin beforehand The method of adding with the form of the mix | blended masterbatch is mentioned. Examples of the resin used in the master batch in which the conductivity imparting material is blended include one or more selected from the group consisting of polyamide, polyphenylene ether, and impact modifier, and among them, polyamide is particularly preferable.

  As a compounding quantity of the electroconductivity imparting material in a masterbatch, when a masterbatch is 100 mass%, it is preferable that the compounding quantity of a electroconductivity imparting material is 5-25 mass%. When conductive carbon black is used as the conductivity imparting material, the blending amount of conductive carbon black in the masterbatch is preferably 5% by mass to 15% by mass, more preferably 8% by mass to 12% by mass. is there. When graphite or carbon fibrils are used as the conductivity imparting material, the blending amount of graphite or carbon fibrils in the master batch is preferably 15% by mass to 25% by mass, more preferably 18% by mass to 23%. % By mass.

There is no restriction | limiting in particular as a manufacturing method of the masterbatch (henceforth "conductivity masterbatch") which mix | blended the electroconductivity imparting material, A well-known method can be used. The following method is mentioned as an example of the manufacturing method of an electroconductive masterbatch.
Using a twin screw extruder having one supply port in the upstream part and one supply port in the downstream part, a part of the polyamide is supplied from the upstream part supply port, and a part of the polyamide is heated at a temperature equal to or higher than the melting point of the polyamide. This is a production method in which after the melt-kneading, a mixture obtained by mixing the remaining polyamide and the conductivity-imparting material without melting from the downstream supply port is added and further melt-kneaded. Moreover, there is no restriction | limiting in particular as a cylinder setting temperature of the processing machine at the time of manufacturing these masterbatch, As long as it is the temperature more than melting | fusing point of polyamide as mentioned above, there is no problem, but as a preferable range 240-330 degreeC More preferably, it is the range of 240 degreeC-300 degreeC.

[Additive]
In addition to the components (A) to (E) described above, the resin composition according to the present embodiment may be blended with various additives as required within a range that does not impair the effects of the present invention. Can do. Examples of such additives include anti-dripping agents, plasticizers, lubricants, colorants, antistatic agents, various peroxides, antioxidants, ultraviolet absorbers, and light stabilizers. The amount of these additives is preferably in a range not exceeding 15% by mass with respect to the resin composition.

  In the resin composition of the present embodiment, a compatibilizing agent may be added during the production of the composition. The main purpose of using the compatibilizer is to improve the physical properties of the polyamide-polyphenylene ether mixture. The compatibilizing agent that can be used in the present embodiment refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. Polyamide-polyphenylene ether mixtures obtained using compatibilizers tend to exhibit improved compatibility.

  Examples of the compatibilizer are described in detail in JP-A-8-48869 and JP-A-9-124926, and all of these known compatibilizers can be used, or they can be used alone. You may use together. Among these various compatibilizers, examples of particularly suitable compatibilizers include maleic acid, maleic anhydride, and citric acid.

  The amount of the compatibilizer is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the mixture of polyamide and polyphenylene ether.

  The resin composition according to the present embodiment preferably contains a compound containing a phosphorus element as a heat stabilizer for polyamide. Examples of the compound containing phosphorus element include a metal phosphate, a metal phosphite, and a metal hypophosphite. The preferred compounding amount of the compound containing phosphorus element is preferably 1 to 5000 ppm, more preferably 5 to 2500 ppm, still more preferably 50 to 2000 ppm in terms of phosphorus element with respect to the total amount of polyamide contained in the resin composition. is there.

Further, the resin composition according to the present embodiment may contain a metal stabilizer as described in JP-A-1-163262 for the purpose of improving the heat resistance stability of the polyamide. Examples of the metal stabilizer include CuI, CuCl ₂ , copper acetate, and cerium stearate. Among the above, copper compounds represented by CuI, copper acetate and the like are preferable, and CuI is more preferable.

  As a compounding quantity of a copper compound, Preferably it is 1-400 ppm as a copper element with respect to the whole quantity of the polyamide contained in the resin composition of this embodiment, More preferably, it is 1-300 ppm, More preferably, it is 1-100 ppm. is there.

[Production method]
Next, an example of the manufacturing method of the resin composition of this embodiment is demonstrated below.
The method for producing the resin composition of the present embodiment is not particularly limited as long as the effects of the present invention are not impaired.
(1) Using a twin screw extruder equipped with an upstream supply port and a downstream supply port, (A) polyphenylene ether and (C2) an impact modifier having no functional group are supplied from the upstream supply port and melt kneaded. After that, (B) polyamide, (C1) impact modifier having a functional group, (D1) fibrous filler, (D2) plate-like and / or granular filler, and optionally a conductive masterbatch (( B) Masterbatch of polyamide and (E) conductivity imparting material) and melt kneading method,
(2) Equipped with an upstream supply port and two or more downstream supply ports (of the downstream supply ports, the upstream side is the downstream first supply port and the downstream side is the downstream second supply port) (A) polyphenylene ether and (C2) impact modifier having no functional group are supplied from the upstream supply port and melt-kneaded, and then (B) polyamide from the downstream first supply port. , (C1) an impact modifier having a functional group, (D2) a plate-like and / or granular filler, optionally a conductive masterbatch, melt kneaded, and (D1) a fibrous filler from the downstream second supply port A method of supplying and further melt-kneading,
Etc.

  Here, it is preferable to supply the impact improving material having (B) polyamide and (C1) functional group from the same supply port. This tends to improve the impact resistance and the linear expansion coefficient.

  Further, (D2) the plate-like and / or granular filler is preferably supplied from a supply port located on the upstream side of the extruder, such as an upstream supply port and a downstream first supply port, and (D1) the fibrous filler is It is preferable to supply from a supply port located on the downstream side of the extruder, such as a downstream second supply port. (D2) By supplying the plate-like and / or granular filler from the supply port located on the upstream side of the extruder, the filler that has become an aggregate due to the shearing force of the extruder is mechanically brought close to the primary particle diameter. By pulverizing and / or dispersing, a decrease in impact resistance can be suppressed. Moreover, (D1) By supplying a fibrous filler from the supply port located in the downstream of an extruder, the fall of L / D can be suppressed and, thereby, rigidity and a low linear expansion coefficient can be hold | maintained.

The resin composition of the present embodiment can be molded as a molded body of various parts by various conventionally known methods such as injection molding.
The molded body of the present embodiment maintains a preferable physical property balance between linear expansion coefficient and impact resistance, and / or maintains a preferable physical property balance between linear expansion coefficient and fluidity. Specifically, in accordance with ISO 11359-2, after holding at 130 ° C. for 3 minutes and performing an annealing treatment at a temperature drop rate = 5 ° C./min, a temperature rise rate = 5 ° C./min, a load = 10 mN, The average of the linear expansion coefficient measured at −30 to 80 ° C. in the MD direction and the TD direction is less than 5.5 × 10 ⁵ / ° C., and the Charpy impact strength measured in accordance with ISO 179 is 5.7 kJ / m. ² or more and / or
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average value of the linear expansion coefficients measured in the MD direction and the TD direction is 5.0 × 10 ⁵ / ° C. or less, the ratio TD / MD of the linear expansion coefficients in the MD direction and the TD direction is less than 1.3, and ISO 1133 In conformity, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 25 cc / 10 min or more, preferably 30 cc / 10 min or more. A molded article having these physical properties can be obtained by injection molding a resin composition containing (D) a specific inorganic filler and (C1) an impact modifier having a functional group.

  Moreover, it is preferable that the molded object of this embodiment is excellent in rigidity. Specifically, the flexural modulus measured according to ISO 178 is preferably 3.5 MPa or more. This includes (D1) component, (D1) fibrous filler, and (D2) a plate-like and / or granular filler having an average primary particle diameter of 10 to 1000 nm, and the blending amounts of (D1) and (D2) It can obtain by making it the preferable range of this embodiment, and the molded object obtained has the preferable physical property balance of rigidity, fluidity | liquidity, and anisotropy.

Furthermore, it is preferable that the molded body of this embodiment is excellent in conductivity. Specifically, in accordance with ISO 294, a 4 mm thick multipurpose test piece A type was frozen and fractured, and a cross section of 10 × 4 mm and a 50 mm long molded piece was coated with silver paint and measured using an electrometer. The volume resistivity is preferably less than 1 × 10 ⁵ Ω · cm. This can be obtained by blending one type selected from (E) conductive carbon black, graphite and carbon fibrils as the conductivity imparting material, and the resulting molded product has conductivity, linear expansion coefficient, resistance to resistance. It maintains a favorable balance of physical properties for impact.

By maintaining the above physical property balance, these molded bodies are, for example, IC tray materials, chassis such as various disk players, electrical / electronic parts such as cabinets, OA parts and machine parts such as various computers and peripheral devices, Furthermore, it can be suitably used for motorcycle cowls, automobile exterior materials, interior materials, and the like. Among the above, it can be suitably used for an automobile exterior material to be electrostatically coated, especially an automobile exterior material that passes through a drying process of an electrodeposition paint together with a steel plate.
Above all, as automobile exterior materials, the weight reduction of the car body is progressing with the tightening of fuel efficiency regulations in each country, and there is a strong demand for thinner exterior materials and interior materials. Since the molded body of the present embodiment maintains the above physical property balance, it can be filled with a thin mold, and surface impact properties, linear expansibility, and rigidity that are preferable as a thin molded body can be obtained. Thereby, the molded object of this embodiment can be conveniently used also as an automotive exterior material having an average thickness of 2 mm or less.

Hereinafter, the present embodiment will be described more specifically by way of examples. However, the present embodiment is not limited to these examples.
The raw materials used are as follows.

(Raw materials used)
1. (A) Polyphenylene ether (PPE)
Poly (2,6-dimethyl-1,4-phenylene ether), reduced viscosity: 0.29 dL / g (0.5 g / dL, measured in chloroform solution at 30 ° C.)

2. (B) Polyamide (PA)
Polyamide 6, terminal amino group concentration: 25 μmol / g, terminal carboxyl group concentration: 108 μmol / g, sulfuric acid solution viscosity VN: 56 mL / g

3. (C1) Impact modifier having functional group (C1-1) Maleic anhydride modified ethylene-octene copolymer (M-EOR), trade name “MN493D”, manufactured by DuPont (C1-2) Maleic anhydride modified polystyrene -Hydrogenated polybutadiene-polystyrene block copolymer (M-SEBS), trade name "M1913"

4). (C2) Impact modifier having no functional group Polystyrene-hydrogenated polybutadiene-polystyrene block copolymer (SEBS), number average molecular weight: 76800

5. (D) Inorganic fiber (D1) Fibrous filler Wollastonite, trade name “NYGLOS8”, manufactured by NYCominals, average fiber length L = 136 μm, average fiber diameter D = 8 μm, L / D = 17
(D2) Plate-like and / or particulate filler Kaolin, trade name “NUCAP290 (mercaptosilane treated product)”, M.M. Huber (US), average primary particle size = 200 nm, single layer thickness = 2 nm

6). (E) Conductivity imparting material Conductive carbon black (CB), trade name “Printex XE2-B”, manufactured by Evonik Degussa Japan, DBP oil absorption 420 mL / 100 g

7). Compatibilizer Maleic anhydride (MAH), trade name “CRYSTALMAN-AB”, manufactured by NOF Corporation

The evaluation method of each physical property is as follows.
(Evaluation method)
<Measurement of melt volume rate (MVR)>
The resin composition pellets obtained in the examples and comparative examples were measured under the conditions of 280 ° C. and 5 kg load according to ISO1133. In the measurement, an MVR value was obtained by averaging three points.

<Measurement of Charpy impact strength>
The resin composition pellets obtained in the examples and comparative examples were dried at 80 ° C. for 3 hours, and then the ISO 294 was used with a Toshiba IS-80EPN molding machine (cylinder temperature set to 300 ° C. and mold temperature set to 100 ° C.). Accordingly, a multipurpose test piece A type (length 150 mm, narrow portion width 10.0 mm) having a thickness of 4 mm was molded. The obtained test piece was processed into a shape of 80 × 10 × 4 mm, a notch was given to the processed test piece, and Charpy impact strength was measured according to ISO179. For the measurement, five different test pieces were used, and the addition average was taken as the Charpy impact strength.

<Measurement of tensile elongation>
The resin composition pellets obtained in the examples and comparative examples were dried at 80 ° C. for 3 hours, and then the ISO 294 was used with a Toshiba IS-80EPN molding machine (cylinder temperature set to 300 ° C. and mold temperature set to 100 ° C.). Accordingly, a multipurpose test piece A type (length 150 mm, narrow portion width 10.0 mm) having a thickness of 4 mm was molded. The obtained test piece was subjected to a tensile test according to ISO 527-1, and the tensile elongation was measured. The measurement was performed using five different test pieces, and the average value was taken as the tensile elongation.

<Measurement of linear expansion coefficient>
The resin composition pellets obtained in the examples and comparative examples were dried at 80 ° C. for 3 hours and then injected with a Toshiba IS-80EPN molding machine (cylinder temperature set to 300 ° C. and mold temperature set to 100 ° C.) with an injection time of 20 A flat plate test piece of 50 × 90 × 3 mm was prepared at a cooling time of 20 seconds, and the test was performed. For each example, 10 × 4 × 4 mm test pieces were cut out from the center portion of the flat plate in the resin flow direction during injection molding (MD direction) and the direction perpendicular to the flow direction (TD direction), respectively. -2 in accordance with TMA-7 (manufactured by PerkinElmer Co., Ltd.), held at 130 ° C. for 3 minutes and annealed at a temperature drop rate of 5 ° C./min, and then a temperature rise rate of 5 ° C. / The linear expansion coefficient of −30 to 80 ° C. was measured at a load of 10 mN. The measurement was performed using three different test pieces for each direction (MD direction, TD direction), and the average value of the addition was taken as the linear expansion coefficient.

<Anisotropy>
When the ratio TD / MD of the linear expansion coefficient in the MD direction and the TD direction was calculated, those exceeding 1.3 were judged to have anisotropy and those less than 1.3 were judged to have no anisotropy.

<Measurement of volume resistivity>
The resin composition pellets obtained in the examples and comparative examples were dried at 80 ° C. for 3 hours, and then the ISO 294 was used with a Toshiba IS-80EPN molding machine (cylinder temperature set to 300 ° C. and mold temperature set to 100 ° C.). Accordingly, a multipurpose test piece A type (length 150 mm, narrow portion width 10.0 mm) having a thickness of 4 mm was molded. Both ends of this test piece were broken to obtain a test piece having a uniform cross-sectional area of 10 × 4 mm, a length of 50 mm, and fractured surfaces at both ends. About how to fold a test piece, it carried out by the method of breaking after immersing the test piece which gave the scratch beforehand with the cutter knife in -190-200 degreeC liquid nitrogen for 1 hour. Silver paint was applied to the fracture surfaces at both ends, and the volume resistivity between both fracture surfaces was measured with an applied voltage of 250 V using an electrometer (manufactured by Advantest, Japan, R8340A). The measurement was performed using five different test pieces, and the average value was defined as the volume resistivity.

<Measurement of flexural modulus>
The resin composition pellets obtained in the examples and comparative examples were dried at 80 ° C. for 3 hours, and then the ISO 294 was used with a Toshiba IS-80EPN molding machine (cylinder temperature set to 300 ° C. and mold temperature set to 100 ° C.). Accordingly, a multipurpose test piece A type (length 150 mm, narrow portion width 10.0 mm) having a thickness of 4 mm was molded. The obtained test piece was processed into a shape of 80 × 10 × 4 mm, and its flexural modulus was measured according to ISO178.

[Comparative Example 1]
The resin composition was produced as follows using the twin-screw extruder (Toshiba machine "TEM-58SS"). One supply port was provided on the upstream side and one on the downstream side. Here, out of the downstream supply ports, the upstream side is the downstream first supply port, and the downstream side is the downstream second supply port.
First, (A) polyphenylene ether powder and maleic anhydride were stirred with a tumbler for 20 minutes to obtain a premix. The preliminary mixture and (C2) impact modifier having no functional group are supplied from the upstream supply port of the twin-screw extruder, melt-kneaded, and then (B) polyamide, conductive master from the downstream first supply port. The batch was supplied, further kneaded and extruded, and pelletized to obtain pellets. The cylinder temperature of the extruder at that time was set to 320 ° C. from the upstream supply port to the downstream supply port, 280 ° C. from the downstream supply port to the die, and 300 ° C. to the die head. At this time, the discharge amount of the kneaded material was 300 kg / hour, and the screw rotation speed was 550 rpm.
Table 1 shows the types and mixing ratios of the raw materials in the above steps. Each evaluation mentioned above was performed using the obtained pellet. The results are shown in Table 1.

[Comparative Examples 2 and 3]
Pellets were obtained in the same manner as in Comparative Example 1 except that (C1) the impact modifier having a functional group was supplied from the downstream supply port.
Table 1 shows the types and mixing ratios of the raw materials in the above steps. Each evaluation mentioned above was performed using the obtained pellet. The results are shown in Table 1.

[Examples 1 to 3]
The resin composition was produced as follows using the twin-screw extruder (Toshiba machine "TEM-58SS").
First, (A) polyphenylene ether powder and maleic anhydride were stirred with a tumbler for 20 minutes to obtain a premix. The preliminary mixture and (C2) impact modifier having no functional group are supplied from the upstream supply port of the twin-screw extruder, melt-kneaded, and then (B) polyamide, (C1) from the downstream first supply port Supply impact modifier with functional group, conductive masterbatch, (D2) plate and / or granular filler, supply (D1) fibrous filler from downstream second supply port, knead and extrude And pelletized to obtain pellets. The cylinder temperature of the extruder at that time was set to 320 ° C. from the upstream supply port to the downstream supply port, 280 ° C. from the downstream supply port to the die, and 300 ° C. to the die head. At this time, the discharge amount of the kneaded material was 300 kg / hour, and the screw rotation speed was 550 rpm.
Table 2 shows the types and mixing ratios of the raw materials in the above steps. Each evaluation mentioned above was performed using the obtained pellet. The results are shown in Table 2.

[Comparative Example 4]
Pellets were obtained in the same manner as in Examples 1 to 3, except that (C1) the impact modifier having a functional group was not supplied from the downstream first supply port.
Table 2 shows the types and mixing ratios of the raw materials in the above steps. Each evaluation mentioned above was performed using the obtained pellet. The results are shown in Table 2.

[ Reference Examples 1 and 5]
Pellets were obtained in the same manner as in Example 1 except that the ratio of (D2) plate-like and / or granular filler supplied from the downstream first supply port and (D1) fibrous filler was changed.
Table 3 shows the types and mixing ratios of the raw materials in the above steps. Each evaluation mentioned above was performed using the obtained pellet. The results are shown in Table 3.

About the said Comparative Examples 1-3, the plot figure which shows the correlation with the average linear expansion coefficient and volume low efficiency which compared the difference of the presence or absence of (C1) component is shown in FIG.
FIG. 2 shows a plot showing the correlation between the average linear expansion coefficient and the volume resistivity, in which the difference in the presence or absence of the component (C1) is compared for Examples 1 to 3 and Comparative Example 4.
FIG. 3 shows a plot showing the correlation between the average linear expansion coefficient and the Charpy impact strength, comparing the difference in the presence or absence of the component (C1) for Examples 1 to 3 and Comparative Example 4.

  From the results of Comparative Examples 1 to 3, it can be seen that the linear expansion coefficient tends to be significantly deteriorated by adding the component (C1) to the system not containing the specific inorganic filler of the present embodiment.

  In Examples 1 to 3 of this embodiment, a phenomenon opposite to the results in Table 1 was observed by including the component (C1). That is, the linear expansion coefficient became small (good). Not only that, but also the impact resistance is improved and the conductivity is improved.

  Since the resin composition of the present invention has excellent impact resistance and a low linear expansion coefficient, it has industrial applicability to electrical and electronic parts, automobile exterior parts, and the like.

Claims (21)

A resin composition comprising (A) polyphenylene ether, (B) polyamide, (C) impact modifier, and (D) inorganic filler,
10-50 mass% of said (A) component with respect to the total amount of said (A) component and said (B) component, 50-90 mass% of said (B) component is included,
As the component (C), (C1) an impact modifier having a functional group, and (C2) an impact modifier having no functional group,
The blending amount of the component (C1) is 0.5 to 30 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
As the component (D), (D1) wollastonite and, seen containing a and (D2) having an average primary particle size of 10~1000nm clay,
The functional group is at least one selected from the group consisting of a carboxylic acid group, an acid anhydride group, an acrylic acid group, a hydroxyl group, a glycidyl group, an amide group, an amino group, and a thiophenol group;
The blending amount of the component (D1) and the component (D2) is 30 to 70% by mass of the component (D1) and 70 to 30% by mass of the component (D2) with respect to the total amount of the component (D). , Resin composition. The component (C1) is an ethylene-α-olefin copolymer, an ethylene-α-olefin-diene copolymer, an ethylene-glycidyl methacrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-vinyl alcohol copolymer. A block having at least one polymer block mainly composed of an aromatic vinyl compound, and at least one polymer block mainly composed of a conjugated diene compound, and a polymer in which the functional group is added to any of the compounds The resin composition according to claim 1, wherein the resin composition is at least one selected from the group consisting of a polymer having a functional group added to a copolymer and a polymer having a functional group added to a hydrogenated product of the block copolymer. object. The block copolymer , wherein the component (C2) has at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound, and The resin composition according to claim 1 or 2 , wherein the resin composition is at least one selected from the group consisting of hydrogenated products of block copolymers. A block copolymer having at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound contained in the component (C1) and the component (C2). The resin composition of Claim 2 or 3 whose number average molecular weights (standard polystyrene conversion) of the polymer and / or the hydrogenated component of the said block copolymer are 40,000-80,000. The compounding quantity of the said (C1) component is 0.5-20 mass parts with respect to a total of 100 mass parts of the said (A) component and the said (B) component, Any one of Claims 1-4. The resin composition as described. The resin composition according to any one of claims 1 to 5 , wherein the reduced viscosity of the component (A) (measured with a 0.5 g / dL chloroform solution at 30 ° C) is 0.21 to 0.40 dL / g. . The resin composition according to any one of claims 1 to 6 , wherein the component (B) is polyamide 6,6 and / or polyamide 6. The resin composition according to any one of claims 1 to 7 , wherein a ratio (L / D) of the average fiber length L and the average fiber diameter D of the component (D1) is 5 to 500. The resin composition according to any one of claims 1 to 8 , wherein the component (D2) is a plate-like and / or granular filler having an average primary particle diameter of 10 to 500 nm. Amount of the component (D), the component (A) to the component (B) and a total of 100 parts by weight of the component (C) is 5 to 55 parts by weight, of claim 1-9 The resin composition of any one of Claims. The resin composition according to any one of claims 1 to 10 , wherein the component (D) is dispersed in a continuous phase comprising the component (B). (E) as a conductivity-imparting material, conductive carbon black, further comprising one or more selected from the group consisting of graphite and carbon fibrils, any one resin composition as claimed in claim 1-11. Molded article obtained by injection-molding the resin composition of any one of claims 1 to 12. Charpy impact strength measured according to ISO 179 is 5.7 kJ / m ² or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The molded product according to claim 13 , wherein the mean value of the linear expansion coefficient measured in step MD in the MD direction and the TD direction is less than 5.5 x ^10-5 / ° C. In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 25 cc / 10 min or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
And the molded object of Claim 13 whose ratio TD / MD of the linear expansion coefficient of MD direction and TD direction is less than 1.3. In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 30 cc / 10 min or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
And the molded object of Claim 13 whose ratio TD / MD of the linear expansion coefficient of MD direction and TD direction is less than 1.3. In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 30 cc / 10 min or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
And ratio TD / MD of the linear expansion coefficient of MD direction and TD direction is less than 1.3,
The molded object of Claim 13 whose bending elastic modulus measured based on ISO178 is 3.5 Mpa or more. Volume resistivity measured using an electrometer after applying silver paint to a cross section of a molded piece having a cross-sectional area of 10 × 4 mm and a length of 50 mm produced by freezing and rupturing a multi-purpose specimen A type having a thickness of 4 mm in accordance with ISO294 Is less than 1 × 10 ⁵ Ω · cm,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The molded product according to claim 13 , wherein the mean value of the linear expansion coefficient measured in step MD in the MD direction and the TD direction is less than 5.5 x ^10-5 / ° C. In accordance with ISO 1133, the melt volume rate (MVR) measured under the conditions of 280 ° C. and 5 kg load is 30 cc / 10 min or more,
Volume resistivity measured using an electrometer after applying silver paint to a cross section of a molded piece having a cross-sectional area of 10 × 4 mm and a length of 50 mm produced by freezing and rupturing a multi-purpose specimen A type having a thickness of 4 mm in accordance with ISO294 Is less than 1 × 10 ⁵ Ω · cm,
Charpy impact strength measured according to ISO179 is 5.7 kJ / m ² or more,
In accordance with ISO11359-2, after holding at 130 ° C. for 3 minutes and annealing at a temperature drop rate = 5 ° C./min, temperature increase rate = 5 ° C./min, load = 10 mN, −30 to 80 ° C. The average addition value in the MD direction and the TD direction of the linear expansion coefficient measured in 1 is 5.0 × 10 ⁻⁵ / ° C. or less,
Ratio TD / MD of linear expansion coefficient in MD direction and TD direction is less than 1.3,
And the molded object of Claim 13 whose bending elastic modulus measured based on ISO178 is 3.5 Mpa or more. Automotive exterior material made of molded bodies of any of claims 13-19. An automobile exterior material having an average thickness of 2 mm or less, comprising the molded body according to any one of claims 13 to 19 .