JP5281228B2 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition which excels in impact resistance, dimension stability and rigidity, and also excels in appearance, fluidity and paint film adhesion property, and further which is very useful as manufacturing materials for exterior parts of automobile. A thermoplastic resin composition comprising component (A): a polyamide resin; component (B): a hydrogenated product of block copolymer comprising vinyl aromatic polymer block (a) and conjugated diene based polymer block (b), and/or ethylene-+--olefin based block copolymer; component (C): a modified hydrogenated product of block copolymer comprising the vinyl aromatic polymer block (a) and the conjugated diene based polymer block (b), which hydrogenated product is modified by addition of an unsaturated acid and/or derivative thereof; component (D): a plate-like and/or needle-like inorganic filler; and component (F): an ethylene-vinyl alcohol copolymer and/or a partial saponified product of ethylene-vinyl acetate copolymer.

Description

  The present invention relates to a thermoplastic resin composition that is particularly excellent in impact resistance, dimensional stability, rigidity, and in appearance, fluidity, and coating film adhesion, and includes electric machines, electronics, automobiles, and the like. It can be used in a wide range of fields. In particular, the present invention relates to a thermoplastic resin composition that is extremely useful as a manufacturing material for automobile exterior parts.

  Polyamide resin has excellent mechanical properties such as moldability, chemical resistance, tensile strength, bending strength, and wear resistance, so it can be used in a wide range of fields such as electrical / electronic parts, mechanical parts, and automotive parts. Has been. However, there is difficulty in dimensional stability (linear expansion coefficient) of the obtained molded product. For example, when a molded product obtained from a polyamide resin composition is used in combination with a metal part, the linear expansion coefficient of the resin molded product is low. There is a drawback that it is too large than that of a metal part and causes problems such as a dimensional difference and poor meshing in a high temperature use environment.

  Furthermore, when paint is applied to the surface of a plastic molded product and this plastic molded product is used in a high-temperature environment, the paint film on the surface of the molded product may peel off because the thermal expansion coefficient of the paint is different from that of the plastic material. There has been a problem that fine cracks are generated on the painted surface and the appearance and design are deteriorated.

  On the other hand, automobile exterior parts such as fenders, door panels, bonnets, and roof panels are becoming more plastic than conventional metal parts because they can be made lighter, have more freedom in design, and can be assembled into modules. In these applications, compared to conventional plastic parts, a high level of material is required in terms of impact resistance, dimensional stability (linear expansion coefficient), rigidity, fluidity, appearance, and the like.

  In order to improve the dimensional stability and rigidity of the polyamide resin, there is a method of adding an inorganic filler to the polyamide resin. However, the impact resistance is remarkably lowered and the appearance is also deteriorated. .

  In order to improve such a problem, for example, a rubbery polymer is widely added to improve the impact resistance of a polyamide resin. Moreover, in order to improve the compatibility between the polyamide resin and the rubber-like polymer, it is known as a known technique to modify the rubber-like polymer with an unsaturated carboxylic acid or a derivative thereof.

  For example, a composition comprising a polyamide resin and a modified hydrogenated block copolymer is disclosed, and it is described that an inorganic filler can be blended as an optional component (Patent Document 1). In addition, there is a description of a polyamide resin composition excellent in metal plating property or paint adhesion property composed of a polyamide resin, an inorganic filler, and a modified styrene / olefin copolymer (Patent Document 2). However, in the conventional technology as described above, the balance between impact resistance, dimensional stability and rigidity cannot be said to be sufficient. For example, if the amount of the rubber-like polymer is increased in order to improve impact resistance, dimensional stability In addition, since the rigidity is greatly reduced, it is necessary to improve the balance between impact resistance, dimensional stability, and rigidity.

  (A) polyamide resin, (B) hydrogenated block copolymer of vinyl aromatic compound polymer block a and olefin compound polymer block b, (C) carboxylic acid or its Polyamide resin composition consisting of a modified block copolymer with a derivative group added, excellent impact resistance, good balance of physical properties such as elastic modulus, heat resistance and weld strength, and improved moldability and appearance of molded products Product (Patent Document 3), (A) polyamide resin of specific end group, (B) hydrogenated block copolymer of vinyl aromatic compound and conjugated diene compound, (C) vinyl aromatic compound and conjugated diene compound A modified block copolymer in which a carboxylic acid group or a derivative group thereof is bonded to a hydrogenated block copolymer, (D) an ethylene-α-olefin copolymer, (E) There is a description of a polyamide resin composition (Patent Document 4) having improved low-temperature impact properties consisting of an olefin polymer having an acid anhydride group only at the end, and it is described that an inorganic filler can be blended as an optional component in these compositions. ing.

  However, these inventions only disclose the blending effect within the combination range of the specific component, and there is no specific example in which an inorganic filler is blended in Examples and the like, and therefore, the balance between impact resistance, dimensional stability, and rigidity. There is no mention or suggestion that it is necessary to add a specific inorganic filler in order to obtain a material having a good appearance while maintaining a high level of balance.

  Further, an impact-resistant polyamide composition comprising a polyamide resin, a functionalized (acid-modified) triblock copolymer, an unfunctionalized ethylene-propylene copolymer, and a fibrous filler is disclosed (Patent Document 5). ). However, in this invention, since the fibrous filler is used, there is a problem that the appearance of the obtained molded product is deteriorated. In addition, it is not mentioned at all that it is necessary to add a specific inorganic filler in order to obtain a good appearance while highly balancing the balance of impact resistance, dimensional stability and rigidity. Therefore, there has been a strong demand for providing a thermoplastic resin composition having an excellent balance between impact resistance, dimensional stability, and rigidity, and having an excellent appearance.

  Further, Patent Document 6 discloses that a polyamide resin (A) includes a copolymer of an olefin and a compound having both an unsaturated group and a polar group, such as an ethylene-acrylic acid copolymer and an ethylene-vinyl alcohol copolymer. A composition comprising a polymer (B) and a conductive substance (C) is disclosed, and the composition is described as having excellent electrical characteristics such as mechanical characteristics, fluidity, and conductivity. Has been.

  On the other hand, the present inventors have further studied to improve the releasability at the time of molding, to suppress residual mold release defects on the surface of the molded product, and to obtain a molded product having a good appearance. .

Japanese Examined Patent Publication No. 63-44784 Japanese Examined Patent Publication No. 8-11782 Japanese Patent Publication No. 7-26019 Japanese Patent No. 3330398 Japanese Examined Patent Publication No. 7-49522 JP 2003-64254 A

  The object of the present invention is to solve the above-mentioned problems of the prior art, exhibit good chemical resistance and heat resistance, and in particular, to increase the coefficient of linear expansion so that no malfunction occurs even when used in combination with metal parts. An object of the present invention is to provide a thermoplastic resin composition which is improved in dimensional stability by being lowered and excellent in impact resistance, rigidity and appearance. Furthermore, it is providing the thermoplastic resin composition excellent in the adhesiveness of the coating film by conductive coating etc.

  As a result of intensive studies to solve the above problems, the following resin composition was found to be excellent in dimensional stability, rigidity, impact resistance and appearance, and the present invention was completed.

That is, the first of the present invention is
Component (A): polyamide resin,
Component (B): hydrogenated block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b and / or ethylene-α-olefin copolymer,
Component (C): Hydrogenated product of block polymer with unsaturated acid and / or derivative thereof as hydrogenated product of block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b A modified hydrogenated block copolymer added to 0.3 to 2.5 parts by weight with respect to 100 parts by weight,
Component (D): Plate-like and / or needle-like inorganic filler having an average particle size of 8 μm or less, and
Component (F): In a composition comprising a partially saponified product of ethylene-vinyl alcohol copolymer and / or ethylene-vinyl acetate copolymer, each of the above components is divided into component (A) and component (B), The weight ratio (A) / ((B) + (C)) of (C) is 90 / 10-60 / 40, and the weight ratio (B) / (C) of component (B) to component (C) is 10/90 to 90/10, and
The amount of component (D) is 5 to 60 parts by weight with respect to a total of 100 parts by weight of components (A), (B), and (C), and the amount of component (F) is component (A), (B), ( The thermoplastic resin composition is characterized by being blended at a ratio of 0.5 to 20 parts by weight with respect to 100 parts by weight of the total of C) and (D).

Moreover, the thermoplastic resin composition of the present invention may contain a specific conductive filler. That is, the second of the present invention is
Component (A): polyamide resin,
Component (B): hydrogenated block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b and / or ethylene-α-olefin copolymer,
Component (C): Hydrogenated product of block polymer with unsaturated acid and / or derivative thereof as hydrogenated product of block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b A modified hydrogenated block copolymer added to 0.3 to 2.5 parts by weight with respect to 100 parts by weight,
Component (D): Plate-like and / or needle-like inorganic filler having an average particle size of 8 μm or less,
Component (E): conductive carbon black and / or hollow carbon fibril, and
Component (F): In a composition comprising a partially saponified product of ethylene-vinyl alcohol copolymer and / or ethylene-vinyl acetate copolymer, each of the above components is divided into component (A) and component (B), The weight ratio (A) / ((B) + (C)) of (C) is 90 / 10-60 / 40, and the weight ratio (B) / (C) of component (B) to component (C) is 10/90 to 90/10, and
The amount of component (D) is 5 to 60 parts by weight based on 100 parts by weight of the total of components (A), (B) and (C), and the amount of component (E) is 100 parts by weight of component (A). 1 to 15 parts by weight, and the amount of component (F) is 0.5 to 20 parts by weight with respect to 100 parts by weight in total of components (A), (B), (C), (D) and (E) It exists in the thermoplastic resin composition characterized by being mix | blended by the ratio.

  Since the thermoplastic resin composition of the present invention has an excellent balance of impact resistance, dimensional stability, and rigidity, and has an excellent appearance, it can be used in a wide range of fields such as electric / electronic parts, mechanical parts, and automobile parts. It is particularly useful as a material for automobile exterior parts. Moreover, about the 2nd of this invention, since it is excellent also in electroconductivity combined with coating film adhesiveness, application of electrostatic coating in a large molded article becomes effective.

  In particular, by including a partially saponified product of component (F): ethylene-vinyl alcohol copolymer and / or ethylene-vinyl acetate copolymer, without impairing the melt fluidity and releasability of the composition, The adhesion of the coating film on the surface of the molded article made of the composition is remarkably improved.

Hereinafter, the present invention will be described in detail.
<Polyamide resin>
The polyamide resin of component (A) used in the thermoplastic resin composition of the present invention is an aliphatic polyamide resin having a -CONH- bond in the main chain and capable of being melted by heating. Typical examples include nylon-4, nylon-6, nylon-6.6, nylon-4.6, nylon-12, nylon-6.10, and other known monomers such as diamines and dicarboxylic acids. Examples thereof include polyamide resins containing components. Preferred polyamide resins are nylon-6 and nylon-6.6.

The polyamide resin preferably has a relative viscosity of 2.1 to 3.5 as measured at a temperature of 23 ° C. and a concentration of 1% by weight in 98% by weight concentrated sulfuric acid. If the relative viscosity is less than 2.1, rigidity, dimensional stability, impact resistance and appearance may be deteriorated. If it exceeds 3.5, moldability tends to be deteriorated, and appearance may be deteriorated. is there. The terminal group concentration is preferably a terminal carboxyl group content of 100 μeq / g or less, and the ratio of the terminal carboxyl group content to the terminal amino group content (terminal carboxyl group content / terminal amino group content) is 0.8 to The range of 4 is preferable. If this ratio is less than 0.8, the fluidity may be lowered or the appearance may be insufficient. If it exceeds 4, the impact resistance and rigidity may be insufficient.
<Hydrogenated block copolymer>
The hydrogenated product of the block copolymer of component (B) and component (C) used in the thermoplastic resin composition of the present invention is a vinyl aromatic compound polymer block a, a conjugated diene compound polymer block b, and The block copolymer is a hydrogenated product, and is a block copolymer in which the number of aliphatic unsaturated bonds in the block b is mainly reduced by hydrogenation.

  In addition, the hydrogenated product of the block copolymer of component (B) and component (C) may be the same or different, and the hydrogenated product of the block copolymer of component (B) is a functional group. It has not been modified. The arrangement of the block a and the block b includes a linear structure or a branched structure (radial teleblock). Further, some of these structures may contain a random chain derived from a random copolymerized portion of a vinyl aromatic compound and a conjugated diene compound. Among these structures, those having a linear structure are preferable, those having an aba type triblock structure are particularly preferable in terms of impact resistance, and those having an ab type diblock structure are included. Also good.

  The monomer constituting the vinyl aromatic compound polymer block a of component (B) and component (C), the vinyl aromatic compound is preferably styrene, α-methylstyrene, paramethylstyrene, vinyltoluene, vinylxylene, etc. More preferably, it is styrene. The monomer and conjugated diene compound constituting the conjugated diene compound polymer block b are preferably 1,3-butadiene and 2-methyl-1,3-butadiene.

  The proportion of the repeating unit derived from the vinyl aromatic compound in the hydrogenated product of these block copolymers is preferably in the range of 10 to 70% by weight, and more preferably in the range of 10 to 40% by weight. Looking at the unsaturated bonds that the hydrogenated product of the block copolymer has, the proportion of the aliphatic unsaturated bonds derived from the conjugated diene compound remaining without being hydrogenated is 20% or less. Preferably, 10% or less is more preferable. Further, about 25% or less of the aromatic unsaturated bond derived from the vinyl aromatic compound may be hydrogenated.

  As the hydrogenated product of such a block copolymer, when the monomer constituting the conjugated diene compound polymer block b and the conjugated diene compound are 1,3-butadiene, styrene-ethylene / butylene- It is called a styrene copolymer (SEBS), and in the case of 2-methyl-1,3-butadiene, it is called a styrene-ethylene / propylene-styrene copolymer (SEPS), and has various aba types. The triblock structure is commercially available and easily available.

In these components (B) and (C), the number average molecular weight of the hydrogenated product of the block copolymer is preferably 180,000 or less, more preferably 120,000. When the molecular weight exceeds 180,000, molding processability tends to be lowered, and the appearance may be deteriorated.
<Ethylene-α-olefin copolymer>
The component (B) ethylene-α-olefin copolymer used in the thermoplastic resin composition of the present invention is a rubbery copolymer containing ethylene and α-olefin as essential components, and is modified with a functional group. Point to something not. The proportion (weight ratio) of copolymerization of ethylene and α-olefin is usually 90:10 to 20:80, preferably 75:25 to 40:60.

  The α-olefin used for copolymerization is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms. Specific examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1 -Decene, 3-methylbutene-1, 4-methylpentene-1, and the like, preferably a linear α-olefin having 3 to 10 carbon atoms, particularly preferably propylene, 1-butene, 1- Octene.

  The ethylene-α-olefin copolymer of component (B) used in the thermoplastic resin composition of the present invention is not contained in a polymer obtained by copolymerizing a diene compound in addition to ethylene and the α-olefin. What introduced the saturated group can be used. The types of diene compounds used are alkenyl norbornenes, cyclic dienes, and aliphatic dienes, preferably 5-ethylidene-2-norbornene and dicyclopentadiene.

As these ethylene-α-olefin copolymers, the melt flow rate (MFR) (ASTM-D1238, temperature 230 ° C., load 2.16 kg) is preferably in the range of 0.05 to 150 g / 10 min. A range of 1 to 50 g / 10 min is more preferable. If the MFR value is lower than 0.05, the moldability tends to be lowered, and if it is 150 or more, the impact resistance may be insufficient.
<Modified hydrogenated block copolymer>
Of the graft modifier, unsaturated acid and / or derivative thereof for obtaining the modified hydrogenated block copolymer of component (C) used in the thermoplastic resin composition of the present invention, the unsaturated acid is specifically Examples thereof include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and nadic acid. The derivatives include acid anhydrides, acid halides, amides, imides, esters, and the like of the above-mentioned various unsaturated acids. Specifically, maleyl chloride, maleimide, maleic anhydride, itaconic anhydride, citraconic anhydride , Monomethyl maleate, dimethyl maleate and the like.

  In these, unsaturated dicarboxylic acid or its acid anhydride is preferable, and especially maleic acid, itaconic acid, or these acid anhydrides are suitable. These unsaturated acids or derivatives thereof are used alone or in combination.

  In component (C), the amount of the unsaturated acid and / or derivative thereof added to the modified block copolymer is 0.3 to 2.5 parts by weight with respect to 100 parts by weight of the hydrogenated product of the block copolymer. It is. If the addition amount is less than 0.3 parts by weight, the impact resistance of the thermoplastic resin composition is inferior, and if it exceeds 2.5 parts by weight, the dimensional stability and fluidity deteriorate, which is not preferable.

  To efficiently obtain a modified hydrogenated block copolymer by adding the above-mentioned graft modifier, unsaturated acid and / or derivative thereof to the hydrogenated block copolymer of component (C) described above. It is preferable to use a radical generator. Examples of the radical generator include organic peroxides and azo compounds.

  Specifically, as the organic peroxide, (i) hydroperoxides: for example, t-butyl-hydroperoxide, cumene-hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl-hydroperoxide, p-menthane-hydroperoxide, diisopropylbenzene hydroperoxide, etc .; (b) Di-alkyl peroxides: for example, 2,5-dimethyl -2,5-di (t-butylperoxy) hexyne-3, di-t-butyl-peroxide, t-butyl-cumyl-peroxide, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexane, di-cumyl peroxide, etc .; (c) peroxyketals: for example, 2,2- Tert-butylperoxy-butane, 2,2-bis-tert-butyl-peroxy-octane, 1,1-bis-tert-butylperoxy-cyclohexane, 1,1-bis-tert-butylperoxy- 3,3,5-trimethylcyclohexane and the like; (d) peroxyesters: for example, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, t-butylperoxyacetate, 2,5-di- Methyl-2,5-di-benzoylperoxy-hexane, t-butylperoxyisopropyl carbonate, t-butylperoxyisobutyrate and the like; (e) diacyl peroxides: for example, benzoyl peroxide, m-toluoyl There are peroxide, acetyl peroxide, lauroyl peroxide and the like.

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1 -[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2 , 2'-azobis (2-methylpropane).

  Dicumyl can be mentioned as another radical generator.

Of these radical generators, particularly preferred are radical generators having a half-life temperature of 120 ° C. or more in 10 hours. Those having a half-life temperature of less than 120 ° C. in 10 hours are not preferable in terms of dimensional stability and impact resistance.
<Inorganic filler>
In the present invention, the shape of the inorganic filler is clearly distinguished into a spherical shape, a plate shape, a needle shape, and a fiber shape as follows.

  The spherical shape includes not only a true spherical shape but also an elliptical shape to a certain extent and an aspect ratio close to 1. The term “plate-like” refers to a plate-like shape having an aspect ratio (longest length of plate-like surface of plate-like powder / thickness of plate-like powder) in the range of 2 to 100. The needle shape refers to those having a length of 100 μm or less and an aspect ratio in the range of 2 to 20, and the fiber shape refers to those having a length exceeding 100 μm. These can be easily distinguished by electron micrographs.

  The inorganic filler of the component (D) used in the thermoplastic resin composition of the present invention is a plate-like and / or needle-like one having an average particle diameter of 8 μm or less, and is a fibrous material such as glass fiber or carbon fiber, In addition, it refers to a non-spherical material such as silica, glass beads, and carbon black. When the shape of the inorganic filler is fibrous, the appearance of the finally obtained molded product is deteriorated, and when it is spherical, the dimensional stability and rigidity are inferior.

  Specifically, for example, the plate-like filler includes magnesium silicate such as talc, clay, mica, graphite, sericite, montmorillonite, plate-like calcium carbonate, plate-like alumina, glass flake, etc. And calcium silicates such as wollastonite, moss heidi, zonotlite, calcium titanate, aluminum borate, acicular calcium carbonate, acicular titanium oxide, and tetrapot type zinc oxide.

  Among these inorganic fillers, magnesium silicate and calcium silicate are preferable in terms of balance between impact resistance, dimensional stability, rigidity, and appearance, and talc and wollastonite are particularly preferable. One type of inorganic filler (D) can be used alone, or two or more types can be used in combination.

  In addition, the average particle diameter as used in the field of this invention means D50 measured by the liquid phase sedimentation method by X-ray permeation, and in the case of a plate-shaped filler, it is the width | variety and length among the width | variety, length, and thickness of a board | plate. Is the average particle system, and in the case of a needle-like filler, the diameter of the needle. As a specific example of an apparatus for performing such measurement, a Sedigraph particle size analyzer (manufactured by Micromeritics Instruments, model 5100) can be cited.

  That is, in order to improve the dimensional stability and rigidity of a molded product finally obtained using the resin composition of the present invention and obtain a good appearance, the average particle diameter measured as described above is 8 μm or less, preferably 5 μm or less, more preferably magnesium silicate and / or calcium silicate having an average particle diameter of 5 μm or less, particularly preferably magnesium silicate having an average particle diameter of 4 μm or less. And / or calcium silicate.

The preferred magnesium silicate used in the present invention, talc in a finely divided amorphous platelets, the chemical composition is a hydrous magnesium silicate, the normal SiO ₂ 58 to 66 wt%, the MgO 28 to 35% by weight, It contains about 5% by weight of H ₂ O and is called talc. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, and the specific gravity is about 2.7. The aspect ratio is usually 5-20.

Next, calcium silicate preferably used in the present invention is a natural white mineral having needle-like crystals, represented by the chemical formula CaSiO ₃ , usually 50% by weight of SiO ₂ , 47% by weight of CaO, and other minor components. Fe ₂ O ₃ , Al ₂ O _{3 and the} like, and the specific gravity is 2.9. Such an inorganic filler mainly composed of calcium silicate anhydrous salt is usually referred to as wollastonite. Commercially available products are, for example, those marketed as Kawasaki Mining Co., Ltd. as PH330 and PH450, Naiko Co., Ltd. as Nigros 4 and Nigros 5, and those having an average aspect ratio of 3 to 20 are preferred.

The inorganic filler may be left untreated, but for the purpose of increasing the affinity with the resin component or the interfacial bond strength, an inorganic surface treatment agent, a derivative such as a higher fatty acid or an ester salt thereof, or a coupling agent What was processed by etc. is preferable. When the surface treatment is carried out, a combination of various surfactants such as non-ion, cation and anion types, and dispersants such as various resins, improves mechanical strength and kneadability. More preferable from the viewpoint.
<Conductive carbon black and / or hollow carbon fibril>
In the present invention, in order to impart conductivity to the thermoplastic resin composition comprising the components (A), (B), (C), (D) and the component (F) described later, a component (E ) Can contain conductive carbon black and / or hollow carbon fibrils. These conductive agents are preferably used in terms of a balance between conductivity and impact resistance.

  The conductive carbon black preferably has a dibutyl phthalate (DBP) oil absorption measured according to ASTM D2414 of 200 ml / 100 g or more from the viewpoint of conductivity, and more preferably 300 ml / 100 g or more. Unlike the carbon black for pigments added to paints or the like for coloring purposes, the conductive carbon black having such physical properties has a form in which fine particles are connected. Preferable conductive carbon black includes acetylene black obtained by pyrolyzing acetylene gas, ketjen black produced by crude incomplete combustion using crude oil as a raw material, and the like.

Hollow carbon fibrils have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms and an inner hollow region, with each layer and the hollow region being arranged substantially concentrically. It is essentially a columnar fibril. Further, it is preferable that the regularly arranged carbon atoms in the outer region are graphite-like and the hollow region has a diameter in the range of 2 to 20 nm. Such hollow carbon fibrils are described in detail in Japanese Patent Publication No. 62-5000943 and US Pat. No. 4,663,230. As described in detail in the latter US patent specification, for example, transition metal-containing particles such as iron, cobalt, and nickel-containing particles supported by alumina are used as carbon monoxide, hydrocarbons, and the like. The carbon-containing gas is contacted at a high temperature of 850 to 1200 ° C., and carbon generated by thermal decomposition is grown in a fibrous form starting from the transition metal. Further, this type of hollow carbon fibril is sold by Hyperion Catharsis under the trade name of graphite fibril and can be easily obtained.
<Ethylene-vinyl alcohol copolymer>
The component (F) ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as (F1)) used in the thermoplastic resin composition of the present invention is a partially saponified product of an ethylene-vinyl acetate copolymer. The saponification degree of the vinyl acetate residue contained in the copolymer is 97 mol% or more. The content of ethylene residues in (F1) is preferably in the range of 10 to 98 mol%, more preferably in the range of 20 to 70 mol%. When the ethylene residue content exceeds 98 mol%, the coating film adhesion of a molded product obtained from the resin composition containing the copolymer (F1) may be deteriorated. There is a possibility that the thermal stability of the resin composition may be insufficient, and the flexibility may be lowered.
<Partially saponified ethylene-vinyl acetate copolymer>
The partially saponified product of the ethylene-vinyl acetate copolymer of component (F) used in the thermoplastic resin composition of the present invention (hereinafter sometimes referred to as (F2)) is acetic acid in the ethylene-vinyl acetate copolymer. This means that the saponification degree of the vinyl residue is less than 97 mol%. The lower limit of the saponification degree is not particularly limited, but is usually 40 mol% or more. When the saponification degree is lower than 40 mol%, the thermal stability of the resulting resin composition at the time of melting tends to decrease. The saponification degree of (F2) is preferably 80 mol% or more.

  (F2) having such a composition preferably has an MFR measured in accordance with JIS-K6730 of 0.5 to 300 g / 10 min from the viewpoint of melt fluidity and strength of the resin composition containing the same. The thing of 8-250g / 10min is more preferable.

The component (F1) ethylene-vinyl alcohol copolymer and the component (F2) ethylene-vinyl acetate copolymer partially saponified product (hereinafter collectively referred to as the component (F)) are both as required. Other monomers (compounds) may be copolymerized in a small amount. Examples of copolymerizable monomers include propylene, isobutene, α-octene, α-dodecene, α-olefins such as α-octadecene; unsaturated carboxylic acids, salts thereof, partial alkyl esters, fully alkyl esters, and acid anhydrides. Acrylonitrile; acrylamide; unsaturated sulfonic acid or a salt thereof. The proportion of these optional monomer residues in the component (F) molecule is usually about 10 mol% or less, preferably about 5 mol% or less.
<Conductivity improvement aid>
The thermoplastic resin composition of the present invention may further contain a conductivity improving aid (component (F)) as necessary. Examples thereof include a conductivity improving aid (component (F)), specifically nigrosine (component (F1)), semi-aromatic polyamide resin (component (F2)), novolak phenol resin, lithium halide and the like. Of these, nigrosine (F1) and semi-aromatic polyamide resin (F2) are more preferable from the viewpoint of the balance between rigidity and impact resistance.

  Here, nigrosine (F1), which is an example of the conductivity improving aid (F), refers to COLOR INDEX and C.I. I. SOLVENT BLACK5 and C.I. I. A black azine condensation mixture of triphenazine oxazine and a phenazine azine compound as described in SOLVENT BLACK7. Examples of commercially available nigrosine include Nubian Black EP-3, Nubian Black PA-9800, Nubian Black PA0800 (all manufactured by Orient Chemical Industry Co., Ltd.). Among these, Nubian Black EP-3 is preferable because the effect of improving conductivity is particularly large.

  The content of nigrosine (F1) as the conductivity improving aid (F) is preferably selected in the range of 0.05 to 30 parts by weight with respect to 100 parts by weight of the component (A). If the blending amount of nigrosine (F1) is less than 0.05 parts by weight, the effect of improving the conductivity is small, and if the blending amount is more than 30 parts by weight, the thermal stability and heat resistance of the final resin composition are lowered, and the melt flow There is a possibility that it may cause deterioration of property and releasability. A more preferable blending amount of nigrosine (F1) is 0.1 to 20 parts by weight.

  Moreover, as semi-aromatic polyamide resin (F2) as conductivity improving aid (F), aliphatic dibasic acids and aromatic diamines, or aromatic dibasic acids and aliphatic diamines are used as raw materials. Polyamide resin obtained by polycondensation of Specifically, the raw material aliphatic dibasic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadioic acid, hexadecadioic acid, hexadecenedioic acid, eico Examples include sandioic acid, eicosadienedioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Examples of aromatic diamines include meta-xylene diamine and para-xylene diamine. Aromatic dibasic acids include terephthalic acid, isophthalic acid, and phthalic acid. Examples of the aliphatic diamines include hexamethylene diamine tetramethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4 (or 2,4,4) -trimethylhexamethylene diamine, bis- (4 , 4'aminocyclohexyl) methane.

  Among these semi-aromatic polyamide resins, polyamide resins containing terephthalic acid and / or isophthalic acid and hexamethylenediamine as main components, that is, polyamide 6T, polyamide 6I, or 6I / 6T copolymerized polyamide, etc., and metaxylenediamine And / or a polyamide resin mainly composed of para-xylenediamine and adipic acid is particularly preferable because it has a large effect of improving the appearance of the molded product in addition to the conductivity promoting effect.

The blending amount of the semi-aromatic polyamide resin (F2) as the conductivity improving aid (F) is preferably selected in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the component (A). When the blending amount of the semi-aromatic polyamide resin (F2) is less than 1 part by weight, the effect of improving conductivity is small. When the blending amount is more than 50 parts by weight, the heat resistance of the final resin composition is lowered and the melt fluidity is lowered. In some cases, it may cause a decrease in releasability during molding. A more preferable blending amount of the semi-aromatic polyamide resin (F2) is 1 to 20 parts by weight.
<Thermoplastic resin composition>
Component (A): polyamide resin, component (B): hydrogenated block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b in the thermoplastic resin composition of the present invention And / or ethylene-α-olefin copolymer, component (C): a hydrogenated product of a block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b. Modified hydrogenated block copolymer obtained by adding 0.3 to 2.5 parts by weight of a saturated acid and / or a derivative thereof to 100 parts by weight of the block polymer, and component (D): average particle diameter of 8 μm or less Each of the plate-like and / or needle-like inorganic fillers has the above-mentioned components as the weight ratio (A) / ((B) + (C) of the component (A) and the components (B) and (C). ) Is 90 / 10-60 / 40, The weight ratio (B) / (C) of component (B) to component (C) is 10/90 to 90/10, and the amount of component (D) is component (A), (B), (C ) In a ratio of 5 to 60 parts by weight with respect to a total of 100 parts by weight.

  A thermoplastic resin composition when (A) exceeds 90 parts by weight and (B) + (C) is less than 10 parts by weight in a total of 100 parts by weight of components (A), (B), and (C). On the contrary, when (A) is less than 60 parts by weight and (B) + (C) is more than 40 parts by weight, the appearance and fluidity of the thermoplastic resin composition are deteriorated, and dimensional stability. Also decreases.

  In 100 parts by weight of the total of components (B) and (C), when (B) is less than 10 parts by weight, the dimensional stability is poor, and when (C) is less than 10 parts by weight, the impact resistance is poor. Therefore, it is essential that the components (B) and (C) are used in a weight ratio of 10/90 to 90/10, more preferably the components (B) and (C) are 50/50 by weight. It is in the range of ~ 90/10.

  Next, with regard to component (D), if it is less than 5 parts by weight relative to 100 parts by weight of the total of components (A), (B), and (C), the dimensional stability and rigidity (flexural modulus) of the thermoplastic resin composition If the component (D) exceeds 60 parts by weight, the fluidity, appearance, and impact resistance deteriorate, which is not preferable.

  Component (F) used in the thermoplastic resin composition of the present invention: ethylene-vinyl alcohol copolymer and / or partially saponified ethylene-vinyl acetate copolymer, the content of component (A), component (B ), 0.5 to 20 parts by weight relative to 100 parts by weight of the total amount of component (C) and component (D). When the blending amount of component (F) is less than 0.5 parts by weight, the effect of improving the coating adhesion of the molded product obtained from the polyamide resin composition according to the present invention is small, and when it exceeds 20 parts by weight, the polyamide resin The reaction with (A) and the modified hydrogenated block copolymer (C) proceeds, the fluidity at the time of melting of the final resin composition decreases, and the thermal stability at the time of melting also deteriorates. The preferred amount of component (F) is 1 to 15 parts by weight, more preferably 2 to 10 parts by weight.

  Further, when the thermoplastic resin composition of the present invention contains component (E): conductive carbon black and / or hollow carbon fibril, the content of component (F) is the components (A), (B), It is 0.5-20 weight part with respect to a total of 100 weight part of (C), (D), and (E).

  Next, when component (E): conductive carbon black and / or hollow carbon fibril is further blended to impart conductivity, the content of component (E) with respect to 100 parts by weight of component (A) is 1-15. Parts by weight. If the content of the component (E) is less than 1 part by weight, the effect of improving the conductivity of the thermoplastic resin composition is low, and if it exceeds 15 parts by weight, the fluidity and impact resistance are lowered, which is not preferable.

  In order to further improve the conductivity, it is preferable to mix nigrosine or semi-aromatic polyamide as the conductivity improving aid (G). In addition, these components described as conductivity improvement auxiliary agent (G) also have the effect of improving the external appearance of the molded article obtained by making it contain in a composition.

  In the case of a thermoplastic resin composition that contains component (E) and imparts conductivity, component saponified product of component (F): ethylene-vinyl alcohol copolymer and / or ethylene-vinyl acetate copolymer The content of is 0.5 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A), (B), (C), (D) and (E). When the blending amount of the component (F) is less than 0.5 parts by weight, the adhesion improving effect is small, and when it is more than 20 parts by weight, the fluidity is lowered and the thermal stability at the time of melting is deteriorated. Also in the case of the composition containing the component (E), the preferable amount of the component (F) is 1 to 15 parts by weight, and more preferably 2 to 10 parts by weight.

  The production of the thermoplastic resin composition of the present invention is preferably a melt mixing method, and a typical method of melt mixing includes a method using a melt kneader that is generally put to practical use for thermoplastic resins. Examples of the melt kneader include a uniaxial or multiaxial kneading extruder, a roll, and a Banbury mixer.

  When using the kneading extruder, preferably, the components (A), (B) and (C) are premixed, and charged in the upstream portion of the kneading extruder, reacted in a molten state, and continued. Then, the component (D) is introduced into the middle part of the kneading extruder to be mixed with the molten reactant, and if necessary, the conductive agent component (E) is introduced from the downstream part to be mixed with the melt. There is a method of forming pellets of a plastic resin composition.

  Alternatively, the components (A), (B), and (C) are mixed in advance, and charged into a kneading extruder and reacted in a molten state to obtain pellets. Next, the component (D) is charged into the pellet and the kneading extruder, mixed with the molten reactants of the components (A) to (C), and the component (E) is charged from the downstream portion as necessary. The method of mixing with a molten reaction material and making the pellet of a thermoplastic resin composition is mentioned.

  As another method, a master batch is prepared by mixing a part or all of the molten reactant of component (A) and component (E) in advance, and this master batch and components (A) to (C) Are mixed and charged into a kneading extruder, reacted in a molten state, and subsequently component (D) is charged in the middle portion of the kneading extruder to mix with the molten reactant to form a pellet of a thermoplastic resin composition. Alternatively, this master batch and components (A) to (C) are mixed, put into a kneading extruder and reacted in a molten state to obtain pellets, and then the pelletized material and component (D) are kneaded. A method of charging into an extruder and mixing with the molten reactants of components (A) to (C) to form pellets of a thermoplastic resin composition can be mentioned.

  By particularly subjecting the component (A), the component (B) and the component (C) to a melt reaction in advance, the component (D) is blended and melt-mixed in the melt reaction product, and particularly excellent impact resistance and dimensions. This is preferable because a resin composition excellent in stability (linear expansion coefficient), rigidity, and appearance can be obtained.

  The thermoplastic resin composition of the present invention can contain other various resin additives in addition to the above components. Examples of various resin additives include heat stabilizers, antioxidants, weather resistance improvers, nucleating agents, foaming agents, flame retardants, impact resistance improvers, lubricants, plasticizers, fluidity improvers, dyes and pigments. , Organic fillers, reinforcing agents, dispersants and the like. Including a liquid crystal polymer is effective in improving rigidity, heat resistance, dimensional accuracy, and the like.

  The method for producing a molded product from the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally employed for thermoplastic resins, that is, an injection molding method, a hollow molding method, an extrusion molding method, A sheet molding method, a thermoforming method, a rotational molding method, a lamination molding method, a press molding method, or the like can be employed.

  The thermoplastic resin composition of the present invention can be used in a wide range of fields as a raw material for producing electrical equipment parts, electronic equipment parts, automobile parts and the like, and is particularly useful as a raw material for producing automobile exterior parts.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these ranges. In the following examples and comparative examples, the blending amount means parts by weight.

In obtaining each resin composition of Examples and Comparative Examples, the following raw materials were prepared.
1. Ingredient (A): Polyamide resin nylon-6: manufactured by Mitsubishi Engineering Plastics, product name-Novamid 1010J, relative viscosity 2.5 when measured at 23 ° C. 98% concentrated sulfuric acid 1% by weight, terminal carboxyl group Content / terminal amino group content ratio 2.6 (hereinafter abbreviated as PA6-1)
2. Component (B): hydrogenated block copolymer, ethylene-α-olefin copolymer styrene-ethylene / butylene-styrene copolymer (SEBS): manufactured by Kraton Polymer Co., Ltd., product name-Clayton G1652, styrene content 29% by weight, number average molecular weight 49,000 (hereinafter abbreviated as SEBS)
Ethylene-butene copolymer: manufactured by Mitsui Petrochemical Co., Ltd., product name: TAFMER A-4085, ASTM-D1238, temperature = 230 ° C., load = 2.16 kg, MFR 6.7 g / 10 minutes , Abbreviated as EBR)
3. Component (C): Modified hydrogenated block copolymer [Preparation of modified hydrogenated block copolymer]
SEBS (100 parts by weight), maleic anhydride (2.5 parts by weight) and radical generator (0.5 part by weight) are weighed in a bottle and mixed uniformly with a Henschel mixer. Manufactured, TEX-30XCT, screw diameter 30 mm, L / D = 42, barrel number 12), and subjected to a melt reaction at a cylinder temperature of 230 ° C. and a screw rotation speed of 300 rpm to give a modified hydrogenated block copolymer C-1 Obtained. As maleic anhydride, maleic anhydride manufactured by Mitsubishi Chemical Corporation is used, and as a radical generator, 1,3-bis (2-t-butylperoxyisopropyl) benzene (made by Kayaku Akzo) is used. , Product name-Parka Dox 14, half-life temperature 121 hours at 10 hours).

The modified hydrogenated block copolymer thus obtained was heated and dried under reduced pressure, and the amount of maleic anhydride added was determined by titration with sodium methylate. As a result, the amount of maleic anhydride added was 1.2 wt%. there were.
4). Ingredient (D): Inorganic filler magnesium silicate (talc): manufactured by Matsumura Sangyo Co., Ltd., product name—High filler # 5000PJ, average particle size 1.8 μm, average aspect ratio 6 plate crystal product (hereinafter abbreviated as D-1) )
Calcium silicate (Wollastonite): manufactured by Kawatetsu Mining Co., Ltd., product name -PH450, average particle diameter 3.8 μm, length 19 μm, average aspect ratio 7 needle crystal (hereinafter abbreviated as D-2)
Calcium silicate for comparison (Wollastonite): manufactured by Kawatetsu Mining Co., Ltd., product name -KH15, average particle size 9.6 μm, length 83 μm, average aspect ratio 10 needle crystal product (hereinafter abbreviated as D-3)
Glass fiber for comparative example: Asahi Fiber Glass Co., Ltd., product name-JA FT516, diameter 10 μm, length 3 mm fibrous product (hereinafter abbreviated as D-4)
5. Component (E): Conductive carbon black, hollow carbon fibril conductive carbon black: manufactured by Lion, product name-Ketjen black EC600JD, BET method surface area 1270 m ² / g, DBP oil absorption 495 ml / 100 g (hereinafter abbreviated as CB) )
6). Component (F): Ethylene / vinyl alcohol resin (F-1) EVOH G156A: Ethylene / vinyl alcohol resin (manufactured by Kuraray Co., Ltd., trade name: Eval G156A, ethylene copolymerization ratio is 47 mol%), and the density is 1.12, MFR (JIS-K6730, temperature = 190 ° C., load = 2.16 kg) is 6 g / 10 min.
(F-2) EVOH C109: ethylene vinyl alcohol resin (manufactured by Kuraray Co., Ltd., trade name: Eval C109, copolymerization ratio of ethylene is 35 mol%), with a density of 1.17 g / cm ³ , MFR (( The same condition measurement as in F-1) is 8 g / 10 min.
(F-3) EVOH H6960: Saponified ethylene / vinyl acetate copolymer (trade name: Mersen H6960, manufactured by Tosoh Corporation) having a density of 0.99 g / cm ³ and the same as MFR ((F-1) (Measured under conditions) is 40 g / 10 min, melting point is 113 ° C., vinyl acetate content is 4.2% by weight, and saponification degree is 90%.
7). Component (G): conductivity improving aid (G-1) nigrosine EP-3: nigrosine (black azine dye, manufactured by Orient Chemical Co., Ltd., trade name: Nubian Black EP-3).
(G-2) X21F07: Semi-aromatic polyamide resin (copolymerized polyamide resin of 6I / 6T, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Novamid X21F07).
8). Others (H-1) YD5013: Bisphenol type epoxy compound (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YD5013).
(H-2) AC5120: ethylene / acrylic acid copolymer (manufactured by Honeywell, trade name: AC wax 5120, acrylic acid content is 9.2% by weight).
[Preparation of test piece]
The thermoplastic resin composition is injection-molded using an injection molding machine (Toshiba IS150) under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and an ASTM test piece, 100 mmφ × 3 mmt disk-shaped molded product and coating film A 100 × 100 mm × 3 mmt square molded product was prepared for adhesion evaluation.
[Evaluation method]
(1) Fluidity (MFR)
According to JIS K7210, MFR (unit: g / 10 minutes) was measured under conditions of a temperature of 280 ° C. and a load of 5 kg.
(2) Flexural modulus The flexural modulus (unit: MPa) was measured according to ASTM D790.
(3) Impact resistance (surface impact)
Using a high-rate impact tester (manufactured by Shimadzu Corp.), a 100 mmφ disk sheet (thickness 3 mmt) was subjected to a punch impact test with a punch diameter of 1/2 inch, a support diameter of 3 inches, and a punching speed of 1 m / s. The greater the breaking energy (unit: J), the better the impact resistance.
(4) Dimensional stability (linear expansion coefficient)
The linear expansion coefficient (unit: K ⁻¹ ) was measured according to ASTM D696. However, the measurement temperature range was 23 to 80 ° C.
(5) Appearance Observe the appearance of the surface of the disk-shaped molded product visually, evaluate whether there are appearance defects such as mold release defects and silver streaks. Was evaluated as ○.
(6) Volume resistivity ASTM 2 dumbbell test piece (thickness 3 mm) parallel part was cut at both ends so as to be 50 mm in length, and silver paste was applied to the both end faces resulting from the cutting and dried at room temperature. Later, the resistance value (RL: unit Ω) between the both end faces was measured with a tester, and the volume resistivity R (unit: Ωcm) was calculated from the following equation.

R = RL × AL / L
(In the formula, AL means the cross-sectional area (unit: cm ² ) of the test piece, and L means the length (unit: cm) of the test piece.)
(7) Paint film adhesion (%)
A square plate-shaped test piece having a size of 100 mm × 100 mm and a thickness of 3 mm is prepared. First, an acrylic / urethane paint (OP-Z-NY, manufactured by Origin Electric Co., Ltd.) is applied to the surface of the test piece. And baked at a temperature of 80 ° C. for 60 minutes. Next, 100 squares of slits having a 1 mm width on one side were formed on the painted film surface after baking. A cellophane tape was attached to the surface of the coating film, and when this cellophane tape was peeled off, it was visually observed whether the coating film surface was peeled off together. The coating film surface was not peeled off by the cellophane tape, and was represented by the residual rate (%) of the mass remaining on the surface of the test piece. The larger this value, the better the coating film adhesion.
[Methods for producing compositions of Examples and Comparative Examples]
[Examples 1 to 5]
First, components (A), (B), and (C) are mixed with a tumbler mixer, and a twin-screw extruder (manufactured by Nippon Steel Works, TEX-30XCT, L / D = 42, barrel number 12) is used. The mixture was charged from the barrel 1 and melt-kneaded under conditions of a cylinder temperature of 230 ° C. and a screw rotation speed of 400 rpm to obtain pellets.

Next, component (D) was blended in this melt-kneaded product, mixed with a tumbler mixer, and melt-kneaded under the same conditions to obtain pellets composed of components (A), (B), (C), and (D).

Next, the pellets of component (F) were mixed with the tumbler mixer into the pellets composed of components (A), (B), (C), and (D), and molding and evaluation were performed using this dry blend. . The results are shown in Table 1.
[Example 6]
The components (A), (B), and (C) were produced by the same method as in Example 1 except that the component (E) was side-fed from the barrel 5 when melt-kneading. The results are shown in Table 1.
[Examples 7 and 8 ]
The components (A), (B), and (C) were produced by the same method as in Example 6 except that the component (G) was blended at the same time when the components were mixed with a tumbler mixer. The results are shown in Table 1.
[Comparative Example 1]
Manufactured in the same manner as in Example 1 except that the component (F) was not blended. The results are shown in Table 1.
[Comparative Example 2]
When component (D) was blended, component (H) was blended at the same time, and the component was manufactured in the same manner as in Example 1 except that component (F) was not blended. The results are shown in Table 1.
[Comparative Examples 3 and 4]
When the component (D) was blended, the component (H) was blended at the same time, and the component (F) was produced in the same manner as in Example 6 except that the component (F) was not blended. The results are shown in Table 1.

［実施例、比較例の品質評価結果］
上記手法により求められた組成物の評価結果は以下の通りであった。
［実施例１〜５と比較例１、２］
実施例１〜５は成分（Ｆ）を配合しなかった比較例１に比べ、剛性、耐衝撃性、寸法安定性、外観を保持したまま、更に塗装膜密着性にも優れている事が分かる。
［実施例６と比較例３、比較例４］
実施例６は、成分（Ｆ）の代わりに、成分（Ｈ）を配合した比較例３、４に比べ、外観に優れている事が分かる。

[Quality evaluation results of Examples and Comparative Examples]
The evaluation results of the composition obtained by the above method were as follows.
[Examples 1 to 5 and Comparative Examples 1 and 2]
It turns out that Examples 1-5 are excellent also in coating film adhesiveness, maintaining rigidity, impact resistance, dimensional stability, and external appearance compared with the comparative example 1 which did not mix | blend a component (F). .
[Example 6, Comparative Example 3, and Comparative Example 4]
It turns out that Example 6 is excellent in the external appearance compared with the comparative examples 3 and 4 which mix | blended the component (H) instead of the component (F).

In particular, for Comparative Example 3 blended with (H-1), the fluidity, impact resistance and conductivity are also excellent, and for Comparative Example 4 blended with (H-2), It can be seen that it is excellent in rigidity, dimensional stability, impact resistance, and coating film adhesion.
[Example 6 and Examples 7 and 8]
It can be seen that in Examples 7 and 8 in which the component (G) was blended with the composition of Example 6, the conductivity was further improved.

Since the thermoplastic resin composition of the present invention has an excellent balance of impact resistance, dimensional stability, and rigidity, and has an excellent appearance, it can be used in a wide range of fields such as electric / electronic parts, mechanical parts, and automobile parts. It is particularly useful as a material for automobile exterior parts. Moreover, since it is excellent in electroconductivity and coating film adhesiveness, the application of electrostatic coating in a large molded article is effective.

Claims (22)

Component (A): polyamide resin,
Component (B): Hydrogenated product of block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b and / or ethylene-α-olefin copolymer, component (C): The hydrogenated product of the block copolymer of the vinyl aromatic compound polymer block a and the conjugated diene compound polymer block b is mixed with an unsaturated acid and / or a derivative thereof per 100 parts by weight of the hydrogenated product of the block polymer. , 0.3 to 2.5 parts by weight of a modified hydrogenated block copolymer,
Component (D): Plate-like and / or needle-like inorganic filler having an average particle size of 8 μm or less, and
Component (F): In a composition comprising a partially saponified product of ethylene-vinyl alcohol copolymer and / or ethylene-vinyl acetate copolymer, each of the above components is divided into component (A) and component (B), The weight ratio (A) / ((B) + (C)) of (C) is 90 / 10-60 / 40, and the weight ratio (B) / (C) of component (B) to component (C) is 50/50 to 90/10, and
The amount of component (D) is 5 to 60 parts by weight with respect to a total of 100 parts by weight of components (A), (B), and (C), and the amount of component (F) is components (A), (B), ( For a total of 100 parts by weight of C) and (D),
A thermoplastic resin composition characterized by being blended at a ratio of 0.5 to 20 parts by weight.   As for the hydrogenated product of the block copolymer of component (B) and component (C), both of the vinyl aromatic compound polymer block a and the conjugated diene compound polymer block b are of the aba type. The thermoplastic resin composition according to claim 1, which has a triblock structure.   The thermoplastic resin composition according to claim 1 or 2, wherein component (C) is a modified hydrogenated block copolymer to which an unsaturated acid and / or a derivative thereof is added in the presence of a radical generator.   Component (A) has a relative viscosity of 2.1 to 3.5 measured at a temperature of 23 ° C., 98 wt% concentrated sulfuric acid at a concentration of 1 wt%, and the ratio of terminal carboxyl group content to terminal amino group content. The thermoplastic resin composition according to any one of claims 1 to 3, which is a polyamide resin having a terminal carboxyl group content / terminal amino group content of 0.8 to 4.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein the component (D) has an average particle size of 5 µm or less.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the component (D) is magnesium silicate and / or calcium silicate.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the average particle size of the component (D) is 3.5 µm or less.   Ingredients (A), (B), (C) and (D) are prepared by subjecting the components (A), (B) and (C) to a melt reaction in advance, and blending and kneading the component (D) with the melt reaction product. The thermoplastic resin composition according to any one of claims 1 to 7, which is obtained by dry blending the component (F) with a melt-kneaded product comprising:   The thermoplastic resin composition according to any one of claims 1 to 8, further comprising 0.05 to 30 parts by weight of component (G1): nigrosine based on 100 parts by weight of component (A). .   Furthermore, the thermoplastic resin as described in any one of Claims 1 thru | or 9 which mix | blends 1-30 weight part with respect to 100 weight part of component (A2): a semi-aromatic polyamide resin. Composition. Component (A): polyamide resin,
Component (B): hydrogenated block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b and / or ethylene-α-olefin copolymer,
Component (C): Hydrogenated product of block polymer with unsaturated acid and / or derivative thereof as hydrogenated product of block copolymer of vinyl aromatic compound polymer block a and conjugated diene compound polymer block b A modified hydrogenated block copolymer added to 0.3 to 2.5 parts by weight with respect to 100 parts by weight,
Component (D): Plate-like and / or needle-like inorganic filler having an average particle size of 8 μm or less,
Component (E): conductive carbon black and / or hollow carbon fibril, and
Component (F): In a composition comprising a partially saponified product of ethylene-vinyl alcohol copolymer and / or ethylene-vinyl acetate copolymer, each of the above components is divided into component (A) and component (B), The weight ratio (A) / ((B) + (C)) of (C) is 90 / 10-60 / 40, and the weight ratio (B) / (C) of component (B) to component (C) is 50/50 to 90/10, and
The amount of component (D) is 5 to 60 parts by weight based on 100 parts by weight of the total of components (A), (B) and (C), and the amount of component (E) is 100 parts by weight of component (A). 1 to 15 parts by weight, and the amount of component (F) is 0.5 to 20 parts by weight with respect to 100 parts by weight in total of components (A), (B), (C), (D) and (E) A thermoplastic resin composition characterized by being blended in a ratio.   As for the hydrogenated product of the block copolymer of component (B) and component (C), both of the vinyl aromatic compound polymer block a and the conjugated diene compound polymer block b are of the aba type. The thermoplastic resin composition according to claim 11, which has a triblock structure.   The thermoplastic resin composition according to claim 11 or 12, wherein the component (C) is a modified hydrogenated block copolymer to which an unsaturated acid and / or a derivative thereof is added in the presence of a radical generator.   Component (A) has a relative viscosity of 2.1 to 3.5 measured at a temperature of 23 ° C., 98% by weight of concentrated sulfuric acid at 1% by weight, and a ratio of terminal carboxyl group content to terminal amino group content ( The thermoplastic resin composition according to any one of claims 11 to 13, which is a polyamide resin having a terminal carboxyl group content / terminal amino group content of 0.8 to 4.   The thermoplastic resin composition according to any one of claims 11 to 14, wherein the average particle size of the component (D) is 5 µm or less.   The thermoplastic resin composition according to any one of claims 11 to 15, wherein the component (D) is magnesium silicate and / or calcium silicate.   The thermoplastic resin composition according to any one of claims 11 to 16, wherein the average particle size of the component (D) is 3.5 µm or less.   The thermoplastic resin composition according to any one of claims 11 to 16, wherein the component (E) is conductive carbon black having a dibutyl phthalate oil absorption of 200 ml / 100 g or more.   The component (A) and the component (E) are melt-kneaded in advance, and the component (D) is blended and kneaded into a melt reaction product obtained by adding (B) and (C) to the melt reaction. The thermoplastic resin composition according to any one of claims 11 to 18. The components (A), (B), and (C) are added in advance to cause a melt reaction, and the melt reaction product is blended with the component (D) and the component (E) and kneaded. The thermoplastic resin composition according to any one of claims 11 to 18, which is obtained by dry blending F) .   The thermoplastic resin composition according to any one of claims 11 to 20, further comprising 0.05 to 30 parts by weight of component (G1): nigrosine based on 100 parts by weight of component (A). .   The thermoplastic resin according to any one of claims 11 to 21, further comprising 1 to 30 parts by weight of component (G2): semi-aromatic polyamide resin based on 100 parts by weight of component (A). Composition.