JP6952445B2 - Polyolefin-based resin composition and automobile interior / exterior material using it - Google Patents

Description

The present invention relates to a polyolefin-based resin composition (hereinafter, also simply referred to as “resin composition”) and an automobile interior / exterior material using the same, and more specifically, it is colored with a black pigment, particularly a colorant containing carbon black. The present invention relates to a polyolefin-based resin composition capable of providing an automobile interior / exterior material having excellent heat resistance by using a specific hindered amine compound and a specific phosphorus-based antioxidant in combination with the polyolefin-based resin composition.

Polyolefin-based resins are lightweight, inexpensive, and have excellent physical properties such as mechanical properties, and can be imparted with even more excellent physical properties by being compatible with other resins. For example, by melt-kneading a polyolefin resin with rubber or an elastomer, impact resistance and workability can be improved. Due to these excellent properties, polyolefin resins are widely used in various fields.

In the automobile field, interior materials such as ceiling materials, sun visors, headrests, armrests, footrests, luggage floor covers, instrument panels, console box lids, center consoles, partition boards, door trims, airbag doors, various pillars, etc. Polyethylene-based resins are used in exterior materials such as weather strips, bumpers, and side mirror covers.

In the interior and exterior materials of automobiles, polyolefin resins and thermoplastic elastomers are blended in order to increase the impact strength. In addition, a filler is added to increase the rigidity of the resin composition.

Since automobiles are exposed to strong sunlight at high temperatures when parked outdoors, the interior and exterior materials are required to have a high degree of weather resistance and to suppress discoloration.

So far, it has been proposed to use various ultraviolet absorbers and light stabilizers for the polyolefin resin for the purpose of imparting weather resistance to the polyolefin resin. For example, Patent Document 1 describes an alkylbenzoate compound and 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10 in a polyolefin-based thermoplastic elastomer composition. An automobile interior material containing −tetraoxa-3,9-diphosphaspiro [5.5] undecane is disclosed.

Further, Patent Document 2 discloses a glass fiber reinforced thermoplastic resin composition containing an alkylbenzoate compound and a hindered amine compound. Further, Patent Document 3 discloses an olefin-based elastic resin composition in which a hindered amine compound and a benzoate compound are blended with a polyolefin-based resin and an olefin-based rubber. Furthermore, Patent Document 4 discloses a resin composition in which a monovalent hindered amine compound, a multivalent hindered amine compound and a benzoate compound are blended with a polyolefin resin.

All of these conventional polyolefin-based resin compositions are excellent in weather resistance, but the effect of blending a colorant, particularly when blending carbon black, has not been sufficiently investigated. Carbon black is used in various molded products because it is inexpensive and exhibits a strong color. However, it has been pointed out that when carbon black is added, the weather resistance is further improved due to the light shielding effect, but the heat resistance is lowered. Was there.

It is conceivable to increase the amount of the antioxidant in order to improve the heat resistance, but it is uneconomical to add a large amount of the antioxidant, and when the antioxidant bleeds out from the molded product and spoils the appearance of the molded product. There was also.

As a technique for improving the heat resistance of the polyolefin resin composition containing carbon black, for example, in Patent Document 5, the ethylene / α-olefin / non-conjugated diene copolymer composition is referred to as sulfur. A heat-resistant and anti-vibration rubber composition containing carbon black has been proposed, but the heat resistance is still unsatisfactory.

Japanese Unexamined Patent Publication No. 11-310667 Japanese Unexamined Patent Publication No. 2001-329178 JP-A-2009-144108 Japanese Unexamined Patent Publication No. 2005-054105 Japanese Unexamined Patent Publication No. 6-001891

As described above, various techniques for improving weather resistance have been proposed for polyolefin-based resin compositions, but the heat resistance when a colorant such as carbon black is blended has not yet been satisfactory.
Therefore, an object of the present invention is to improve the heat resistance of a polyolefin-based resin composition containing a colorant such as carbon black.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by blending a specific hindered amine compound and a specific phosphorus-based antioxidant with a polyolefin resin, and have found that the present invention can be solved. Has been completed.

（式（１）中、Ｒ^１１〜Ｒ^１４は、各々独立して、水素原子またはメチル基を表す。）

（式（２）中、Ｒ^２およびＲ^３は、各々独立して、炭素原子数１〜４０のアルキル基または炭素原子数６〜４０のアリール基を表し、アルキル基およびアリール基の水素原子は、炭素原子数１〜８のアルキル基で置換されていてもよい。） That is, the polyolefin-based resin composition of the present invention contains a polyolefin-based resin (A), a thermoplastic elastomer (B) (excluding the polyolefin-based resin (A)), and a filler (C).
The hindered amine light stabilizer (D) 0 represented by the following general formula (1) with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). Contains 0.01 to 5 parts by mass, 0.01 to 5 parts by mass of the phosphorus-based antioxidant (E) represented by the following general formula (2), and 0.01 to 10 parts by mass of the colorant (F). ,
The colorant (F) is characterized by containing carbon black.

(In formula (1), R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or a methyl group.)

(In the formula (2), R ² and R ³ each independently represent an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms, and the hydrogen atom of the alkyl group and the aryl group is , May be substituted with an alkyl group having 1 to 8 carbon atoms.)

Further, in the resin composition of the present invention, the thermoplastic elastomer (B) is contained in 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). It is preferably contained in an amount of 5 to 35 parts by mass.

Further, in the resin composition of the present invention, it is preferable that the polyolefin-based resin (A) is an olefin block copolymer.

The automobile interior / exterior material of the present invention is characterized in that the polyolefin-based resin composition is used.

According to the present invention, it has become possible to realize a polyolefin-based resin composition capable of producing an automobile interior / exterior material having excellent heat resistance even if it contains a colorant such as carbon black.

Hereinafter, embodiments of the present invention will be described in detail.
The polyolefin-based resin composition of the present invention contains a polyolefin-based resin (A), a thermoplastic elastomer (B), and a filler (C) as essential components.

[Polyolefin-based resin (A)]
First, the polyolefin-based resin (A) used in the present invention will be described.
The polyolefin-based resin (A) used in the present invention can be used without particular limitation as long as it is a polyolefin. Specifically, polypropylene, isotactic polypropylene, syndiotactic polypropylene, and hemiisotac. Chick polypropylene, stereoblock polypropylene, cycloolefin polymer, polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylbutene, poly-3-methyl-1-pentene, poly-4 Examples thereof include homopolymers or copolymers of α-olefins such as −methyl-1-pentene and ethylene-propylene copolymers.

In the present invention, it is said that the effect of the present invention is remarkable by using an olefin block copolymer in which polyethylene, ethylene / α-olefin copolymer, ethylene / cyclic olefin copolymer, polypropylene and the like are covalently linked. It is preferable because it becomes.

The polyolefin resin (A) has three-dimensional regularity, specific gravity, type of polymerization catalyst, presence / absence or degree of removal of polymerization catalyst, degree of crystallization, polymerization conditions such as temperature and pressure, type of crystal, and small angle scattering of X-rays. Measured lamella crystal size, crystal aspect ratio, solubility in aromatic or aliphatic solvents, solution viscosity, melt viscosity, average molecular weight, degree of molecular weight distribution, number of peaks in molecular weight distribution, copolymer In the case of, the resin composition of the present invention may be different regardless of the resin selected, although the manifestation of the effect of the present invention may differ depending on the conditions such as block or random, and the compounding ratio of each monomer. Applicable to things.

[Thermoplastic elastomer (B)]
Next, the thermoplastic elastomer (B) will be described.
The thermoplastic elastomer (B) in the present invention means a polymer material that can be plasticized (fluidized) at a high temperature and processed like a plastic, and exhibits the properties of a rubber elastic body (elastomer) at a normal temperature. do.

The thermoplastic elastomer (B) is composed of a hard segment (plastic component) and a soft segment (elastic component), and in a single polymer, the hard segment and the soft segment are chemically bonded to form a block copolymer. Examples thereof include a blended structure called "sea island dispersion" or "polymer alloy" in which a mold and a hard segment and a soft segment are physically mixed.

(Block polymer type thermoplastic elastomer)
In the case of block polymer type thermoplastic elastomers, as hard segments, ethylene, propylene, 1-butadiene, 1-pentene, 3-methyl-1-butane, 1-hexene, 1-decene, 3-methyl-1-pentene, Α-olefins with 3 to 10 carbon atoms such as 4-methyl-1-pentene and 1-octene, styrene, butadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5- Non-conjugated diene having 5 to 15 carbon atoms such as dicyclooctadien, vinyl ester compound such as vinyl acetate, ethylenic unsaturated such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like Examples thereof include monomers such as carboxylic acid ester compounds, vinyl nitrile compounds such as acrylonitrile and methacrylonitrile.
These monomers may be used alone or in combination of two or more, or may be (co) polymerized.

Examples of the soft segment include polydiene such as ethylene propylene diene rubber, polybutadiene, and polyisoprene rubber. In the present invention, a copolymer of a polyolefin resin and ethylene propylene diene rubber is preferable.

(Blend type thermoplastic elastomer)
Examples of the blend-type thermoplastic elastomer suitable in the present invention include those containing an olefin resin as a hard segment and an olefin copolymer elastomer as a soft segment.

Examples of the olefin resin as a hard segment include low-density polyethylene, high-density polyethylene, linear high-density polyethylene, linear low-density polyethylene, branched low-density polyethylene, ethylene homopolymer, propylene homopolymer, or ethylene. And α-olefin copolymers, and examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1 Examples thereof include α-olefins having 3 to 10 carbon atoms such as octene and 1-butene. The olefin resin may be a single olefin resin or a combination of two or more kinds of olefin resins.

As the olefin-based copolymer elastomer as a soft segment, an elastomer which is a copolymer of ethylene and α-olefin is preferably used.

Further, in the case of the blend type thermoplastic elastomer, the soft segment may contain another elastomer together with the olefin copolymer elastomer as long as the effect of the present invention is not impaired. Examples of such other elastomers include styrene-based elastomers such as polybutadiene, hydrogenated polybutadiene, and hydrogenated polyisoprene, polyester-based elastomers such as vinyl chloride-based elastomers and polyethers, polyurethane-based elastomers, nylon-based elastomers, and natural rubbers. And other elastic elastomers can also be used.

The mass ratio of the hard segment and the soft segment in the blended thermoplastic elastomer can be appropriately set according to the desired purpose.

If necessary, the resin composition of the present invention may contain a peroxide, the polyolefin resin (A) or the thermoplastic elastomer (B) may be crosslinked by irradiation with energy rays, or the polyolefin. The based resin (A) or the thermoplastic elastomer (B) may be copolymerized with maleic acid or the like.

In the resin composition of the present invention, 5 to 35 parts by mass of the thermoplastic elastomer (B) is contained in 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). This is particularly preferable because the effect of the invention becomes remarkable. If the blending amount of the thermoplastic elastomer (B) is less than 5 parts by mass, the effect of the present invention may not be obtained, and if it exceeds 35 parts by mass, bloom of the additive may easily occur.

[Filler (C)]
Examples of the filler (C) used in the present invention include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, and glass powder. , Glass fiber, clay, dolomite, mica, silica, alumina, potassium titanate whisker, wallastenite, fibrous magnesium oxysulfate, hydrotalcite and the like. The presence / absence, particle size, and shape of the surface treatment of the filler (C) can be appropriately selected. In the present invention, the filler (C) preferably has an average particle size in the case of a spherical or flat plate shape, or an average fiber diameter of 5 μm or less in the case of a needle-like or fibrous material, and is particularly inexpensive. Talc is preferred.

The blending amount of the filler (C) is preferably 40 parts by mass or less in 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C), and 1 to 1 It is more preferably 30 parts by mass.

In addition to the polyolefin-based resin (A) and the thermoplastic elastomer (B), other resins can be blended in the resin composition of the present invention. Examples of other resins that can be used in the resin composition of the present invention include hydrocarbon resins, hydrogenated modified products of hydrocarbon resins (tacking agents), polyacetal resins, aliphatic polyketone resins (ketone resins), and the like. Polysulfone (for example, thermoplastic polysulfone, poly (ether sulfone), poly (4,4'-bisphenol ether sulfone), etc.), polyether ketone, poly (ether ether ketone), polyetherimide, polyarylate, thermoplastic polyurethane type Resins (eg, polymers obtained by reacting diisocyanate compounds such as tolylene diisocyanate with glycols and / or diamines, polyurethane elastomers which may have segments such as polytetramethylene glycol), thermoplastic polyimides, Examples thereof include polyoxybenzylene and epoxy resin.

When the above other resins are blended, the blending amount of the other resins is 30 parts by mass or less with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). Is preferable.

（式（１）中、Ｒ^１１〜Ｒ^１４は、各々独立して、水素原子またはメチル基を表す。） [Hindered amine compound (D)]
The specific structure of the hindered amine compound (D) used in the present invention is represented by the following general formula (1).

(In formula (1), R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or a methyl group.)

Specific examples of the hindered amine compound represented by the general formula (1) include trade names "ADEKA STAB LA-52", "ADEKA STAB LA-57", and "ADEKA STAB LA-502XP" manufactured by ADEKA CORPORATION.

In the resin composition of the present invention, the blending amount of the hindered amine compound (D) is 0.01 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). 5 parts by mass. If the blending amount of the hindered amine compound (D) is less than 0.01 parts by mass, sufficient weather resistance may not be exhibited, and if it exceeds 5 parts by mass, it may bleed out from the molded product. In the present invention, the preferable blending amount of the hindered amine compound (D) is 0.05 to 0.4 parts by mass.

（式（２）中、Ｒ^２およびＲ^３は、各々独立して、炭素原子数１〜４０のアルキル基または炭素原子数６〜４０のアリール基を表し、アルキル基およびアリール基の水素原子は、炭素原子数１〜８のアルキル基で置換されていてもよい。） [Phosphorus-based antioxidant (E)]
The phosphorus-based antioxidant (E) used in the present invention is represented by the following general formula (2).

(In the formula (2), R ² and R ³ each independently represent an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms, and the hydrogen atom of the alkyl group and the aryl group is , May be substituted with an alkyl group having 1 to 8 carbon atoms.)

Examples of the alkyl group having 1 to 40 carbon atoms include methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, and tert-amyl. , Cyclopentyl, 4-ethyl-2-methylheptyl, hexyl, 2-methylhexyl, 3-methylhexyl, cyclohexyl, 4-methylcyclohexyl, 2,4-dimethylhexyl, 1,2,4-trimethylcyclohexyl, heptyl, 2-Heptyl, 3-Heptyl, iso-Heptyl, tert-Heptyl, 1-octyl, iso-octyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, Examples thereof include octadecyl, icosyl, adamantyl, norbornyl and the like.

Examples of the aryl group having 6 to 40 carbon atoms include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl and 3-iso-propyl. Phenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butyl-phenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) ) Phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-Di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl, 2, 4-Di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'- Biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrosenyl and the like can be mentioned.

Specific examples of the phosphorus-based antioxidant (E) represented by the general formula (2) are 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4. 8,10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9- Diphosphaspiro [5.5] undecane and the like can be mentioned.

In the resin composition of the present invention, the blending amount of the phosphorus-based antioxidant (E) represented by the general formula (2) is the polyolefin-based resin (A), the thermoplastic elastomer (B) and the filler (C). The total amount is 0.01 to 5 parts by mass, preferably 0.05 to 0.4 parts by mass with respect to 100 parts by mass. If the blending amount of the phosphorus-based antioxidant (E) is less than 0.01 parts by mass, the effect of the present invention may not be obtained, and if it exceeds 5 parts by mass, the effect according to the added amount cannot be obtained. It is economical and may bleed out of molded products.

[Colorant (F)]
As the colorant (F) used in the resin composition of the present invention, various conventionally known pigments can be used and are not particularly limited. For example, black pigments, white pigments, yellow pigments, orange pigments, red pigments, purple pigments, blue pigments, green pigments, brown pigments and the like can be mentioned. These pigments may be used as powders, or may be used by adjusting a slurry dispersed in a solvent or varnish.
In particular, when the polyolefin-based resin composition of the present invention is used as an automobile material, it is preferable to contain a black pigment as a colorant (F), and a black pigment and a white pigment may be blended and used as gray.

Examples of the black pigment include oxides such as magnetite-type triiron tetroxide, copper, chromium, zinc or a composite oxide of copper / zinc, carbon black, lamp black, charcoal black, bone charcoal, graphite, mars black, and pigment. Black 12, Cobalt Black, Manganese Black, Chrome Green Black Hematite, Mineral Black, Slate Black, Copper Chrome Black, Titanium Antimony Gray, Titanium Vanadium Antimony Gray, Cobalt Nickel Gray, Manganese Ferrite Black, Iron Cobalt Chrome Black, Copper Chrome Black, Examples thereof include iron cobalt black, chrome iron nickel black, pigment black 31, pigment black 32, pigment black 33, and pigment black 34.
In the present invention, carbon black is preferably used among the black pigments because black can be strongly displayed and is inexpensive.

Examples of the white pigment include titanium oxide, zinc oxide, zinc sulfide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate and the like.

The blending amount of the colorant (F) in the resin composition of the present invention is 0.01 to 10 with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). It is by mass, preferably 0.1 to 5 parts by mass. If the blending amount of the colorant (F) is less than 0.01 parts by mass, uneven coloring may occur, and if it exceeds 10 parts by mass, the physical properties of the molded product may deteriorate.

In the resin composition of the present invention, the hindered amine compound (D), the phosphorus-based antioxidant (E) and the colorant (F) are compared with the polyolefin-based resin (A), the thermoplastic elastomer (B) and the filler (C). The method of blending the above is not particularly limited, and can be carried out by a conventionally known method. For example, the powder or pellet of the polyolefin resin (A) and the components (B), (C), (D), (E), and (F) may be mixed in a dry blend, and (D), ( After pre-blending a part of the components E) and (F), it may be dry-blended with the remaining components. After the dry blend, for example, it may be mixed using a mill roll, a Banbury mixer, a super mixer or the like, and kneaded using a single-screw or twin-screw extruder or the like. This mixing and kneading is usually performed at a temperature of about 120 to 250 ° C. Further, a method of adding any of the components (D), (E), and (F) at the polymerization stage of the polyolefin resin may be used.

Further, it is mixed with a granulating aid such as binder, wax, solvent, silica, etc. in a desired ratio in advance, and then granulated to obtain a one-pack composite additive, and this one-pack composite additive is added to the polyolefin resin. To prepare a masterbatch containing a high concentration of any of the components (D), (E), and (F), and add this masterbatch to the components (A), (B), and (C). A method or the like can also be adopted.

The resin composition of the present invention may contain a known resin additive, if necessary, as long as the effects of the present invention are not impaired. Such known resin additives are, for example, different from those represented by the above general formula (1), hindered amine compounds, phenolic antioxidants, and those represented by the above general formula (2). Phosphorus-based antioxidants, thioether-based antioxidants, UV absorbers, nucleating agents, flame retardants, flame retardants, lubricants, metal soaps, heavy metal deactivators, antistatic agents, cross-linking agents, cross-linking aids, Examples include softeners and hydrotalcites.

Examples of the hindered amine compound different from the one represented by the above general formula (1) include 2,2,6,6-tetramethyl-4-piperidyl stearate and 1,2,2,6,6-pentamethyl-. 4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6) −Tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butane tetracarboxylate, bis (1,2,2,6) 6-Pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl- 2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate weight Condensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis ( 2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2] 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-Tetrakiss [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) ) -S-Triazine-6-yl] Aminoundecane, 1,6,11-Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl)) Amino) -s-triazine-6-yl] aminoundecane, bis {4 -(1-octyloxy-2,2,6,6-tetramethyl) piperidyl} decandionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidine) carbonate, Examples thereof include the former trade name TINUVIN NOR 371 manufactured by BASF.

When a hindered amine compound different from the one represented by the general formula (1) is used, the blending amount thereof is 100 parts by mass in total of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). On the other hand, the total amount of the hindered amine compound represented by the general formula (1) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrene phenol, and 2,2'-methylenebis (4). -Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert-) Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3) , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2'-Oxamide-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3- (3', 5'-di-tert-butyl) -4'-Hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl , 2,5-Di-tert-amylhydroquinone, a polymer of hinderedphenol (trade name AO.OH.98, manufactured by Adecapalmarol), 2,2'-methylenebis [6- (1-methylcyclohexyl)) -P-cresol], 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5) -Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4 8,10-Tetra-tert-butylbenz [d, f] [1,3,2] -dioxaphosphobin, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy Reaction product of -2 (3H) -benzofuranone and o-xylene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2-ylamino ) Phenol, DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4'-hydroxy-3'-tert-) Butyl-phenyl) butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,3) 5-Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-) tert-Butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) ) Butyric acid] glycol ester, 4,4'-butylidenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 2,2'- Ethilidenbis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl -6- (2-Hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate , 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tet Lakis [methylene-3- (3', 5'-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl) -5-Methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8, 10-Tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionic acid amide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, myristyl-3- (3,5-di-tert-butyl) 3- (3,5-Dialkyl-4-hydroxyphenyl) propion such as -4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, etc. Examples include acid derivatives.

When the phenolic antioxidant is blended, the blending amount is 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). It is preferably 0.01 to 0.5 parts by mass, more preferably 0.01 to 0.5 parts by mass.

Examples of phosphorus-based antioxidants different from those represented by the above general formula (2) include triphenylphosphite, diisooctylphosphite, heptaxitriphosphite, triisodecylphosphite, and diphenylisooctylphos. Fight, Diisooctylphenylphosphite, Diphenyltridecylphosphite, Triisooctylphosphite, Trilaurylphosphite, Diphenylphosphite, Tris (dipropylene glycol) phosphite, Dioleylhydrogenphosphite, Trilauryltrithiophos Fight, bis (tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbis (nonylphenyl) phosphite, poly (dipropylene glycol) phenylphosphite, tetra Phenyldipropyl glycol diphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, Tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) Monophenylphosphite, alkyl (C10) bisphenol A phosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, tetra ( Tridecyl) Isopropyridene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (tridecyl) 2-Methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phos Phenyl-10-oxide, (1-methyl-1-propanol-3-ylidene) tris (2-1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecylphosphite, 2,2'-Methylenebis (4,6-te) rt-Butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -octadecylphosphite, 2,2'-ethylidenebis (4,6-di-tert) -Butylphenyl) fluorophosphite, 4,4'-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyl) Dibenzo [d, f] [1,3,2] dioxaphosfepin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa -3,9-Diphosphespiro [5,5] undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4 ′ -Isopropyridene diphenol C12-15 alcohol phosphite, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol can be mentioned.

When a phosphorus-based antioxidant different from that represented by the above general formula (2) is blended, the blending amount thereof is the total of the polyolefin-based resin (A), the thermoplastic elastomer (B) and the filler (C). The total amount of the phosphorus-based antioxidant represented by the general formula (2) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass.

Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl. ) Sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, disstearyl-3,3'-thiodipropio Nate, lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), distearyl-disulfide and the like.

When the thioether-based antioxidant is blended, the blending amount is 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). It is preferably 0.01 to 0.5 parts by mass, more preferably 0.01 to 0.5 parts by mass.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-Hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5) -Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5) -Dicmylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole Polyethylene glycol ester of, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert -Butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl)) -5-tert-Butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5 -(2-Methacryloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert -Butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4 -(3-Methacryloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypro) Pill) Phenyl] 2- (2-Hydroxyphenyl) benzotriazoles such as benzotriazole; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2-( 2-Hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-Dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl) 2- (2-Hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as -4-hexyloxyphenyl) -1,3,5-triazine; phenylsalicylate, resorcinol monobenzoate, 2, 4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-) tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,3) Phenylates such as 5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2'-ethoxyoxanilide, 2- Substituted oxanilides such as ethoxy-4'-dodecyloxanilide; cyano such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Acrylates; various metal salts or metal chelates, particularly nickel, chromium salts, chelates and the like. For example, a benzotriazole compound, a triazine compound, a benzophenone compound, a benzoate compound, a cyanoacrylate compound, a salicylate compound, an oxanilide compound, and other ultraviolet absorbers can be mentioned.

When the ultraviolet absorber is blended, the blending amount is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). More preferably, 0.01 to 0.5 parts by mass.

Examples of the nucleating agent include carboxylic acid metals such as sodium benzoate, 4-tert-butyl benzoate aluminum salt, sodium adipate and disodium dicyclo [2.2.1] heptane-2,3-dicarboxylate. Salt, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-di) Phosphate metal salts such as -tert-butylphenyl) phosphate, dibenzylene sorbitol, bis (methylbenzylene) sorbitol, bis (3,4-dimethylbenzylene) sorbitol, bis (p-ethylbenzylene) sorbitol, and bis (dimethyl) Benzene) Polyhydric alcohol derivatives such as sorbitol, N, N', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', N" -tricyclohexyl-1,3 , 5-Benzene tricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide, amide compounds such as 1,3,5-tri (2,2-dimethylpropanamide) benzene and the like can be mentioned.

When the nucleating agent is blended, the blending amount is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). More preferably, 0.01 to 0.5 parts by mass.

Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinolbis (diphenyl phosphate), (1-methylethylidene). -4,1-Phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, ADEKA Co., Ltd. trade name Adecastab FP-500, ADEKA Co., Ltd. trade name Adecastab FP-600 , Aromatic phosphate ester such as ADEKA Co., Ltd. trade name Adecastab FP-800, phosphonic acid ester such as divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, diphenyl Methyl phosphinate, phosphinic acid esters such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicredylphosphazene, melamine phosphate Phenyl-based flame retardants such as melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compound and red phosphorus, magnesium hydroxide, hydroxide. Metal hydroxides such as aluminum, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2- Dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tri) Bromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, and bromine-based difficulties such as brominated styrene. Fuels and the like can be mentioned. These flame retardants are preferably used in combination with a drip inhibitor such as fluororesin and a flame retardant aid such as polyhydric alcohol and hydrotalcite.

When the flame retardant is blended, the blending amount is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). ~ 30 parts by mass is more preferable.

The lubricant is added for the purpose of imparting slipperiness to the surface of the molded product and enhancing the scratch-preventing effect. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as bechenic acid amide and stearic acid amide. One of these may be used alone, or two or more thereof may be used in combination.

When the lubricant is blended, the blending amount is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). 1 to 0.5 parts by mass is more preferable.

The metal soap represents a metal salt of an aliphatic carboxylic acid, and the aliphatic carboxylic acid may have a hydroxyl group, a cycloalkyl group, or a branch. Specifically, acetic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, enanthic acid, pelargonic acid, capric acid, neodecic acid, undecic acid, lauric acid, tridecic acid, myristic acid, Pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadesilic acid, arachidic acid, behenic acid, lignoseric acid, cellotic acid, montanic acid, melicic acid, touhaku acid, linderic acid, tsuzuic acid, palmitreic acid, myristoleic acid, Petroseric acid, oleic acid, ellaic acid, bacenoic acid, linoleic acid, linoelydic acid, γ-linolenic acid, linolenic acid, ricinolic acid, naphthenic acid, avietic acid, hydroxyacetic acid, lactic acid, β-hydroxypropionic acid, 2-methyl Examples thereof include metal salts such as −β-hydroxypropionic acid, α-hydroxybutyric acid, β-hydroxybutyric acid, γ-hydroxybutyric acid, monomethylolpropionic acid, dimethylolpropionic acid, and 12-hydroxystearic acid.
Among these, those having an aliphatic group having 12 to 22 carbon atoms are preferable, and myristic acid, stearic acid, 12-hydroxystearic acid and the like are particularly preferable.

Examples of the metal of the metal salt of the aliphatic carboxylic acid include alkali metal, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium and hafnium. Among these, alkali metals such as sodium, lithium and potassium are particularly preferably used.

When the metal soap is blended, the blending amount is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). 0.01 to 5 parts by mass is more preferable.

Examples of heavy metal inactivating agents include salicylamide-1,2,4-triazole-3-yl, bissalicylic acid hydrazide, dodecane dioil bis (2- (2-hydroxybenzoyl) hydrazide), and bis (3-( 3,5-di-t-butyl-4-hydroxyphenyl) propionic acid) hydrazide and the like can be mentioned.

When the heavy metal inactivating agent is blended, the blending amount thereof is 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). Is preferable, and 0.01 to 5 parts by mass is more preferable. stomach.

Examples of the cross-linking agent include 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3,1 , 3-Bis (tert-butylperoxyisopropyl) benzene, 1,1-di (tert-butylperoxy) 3,5,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (peroxybenzoyl) ) Organic peroxides such as hexane-3 and dicumylperoxide can be mentioned. In addition, the organic peroxide can be mixed with a diluent and used as a liquid or powdery substance. Examples of the diluent include oils, organic solvents, inorganic fillers (silica, talc, etc.) and the like.

When the cross-linking agent is blended, the blending amount is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). 0.1 to 5 parts by mass is more preferable.

Examples of the cross-linking aid include those used mainly for increasing the degree of cross-linking of the cross-linking type thermoplastic elastomer, and those having a plurality of double bonds in the molecule are preferable. Specifically, tetraethylthiuram disulfide (TETD), tetramethylthiuram disulfide (TMTD), N, N'-m-phenylene bismaleimide, toluylene bismaleimide, P-quinonedioxime, nitrobenzene, diphenylguanidine, divinylbenzene, Examples thereof include ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropantrimethacrylate, and allyl methacrylate. These cross-linking aids may be used alone or in combination of two or more.

When the cross-linking aid is blended, the blending amount is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). More preferably, 1 to 10 parts by mass.

Examples of the softener include process oils, aliphatic cyclic saturated hydrocarbon resins and the like.

When the softener is blended, the blending amount is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). ~ 30 parts by mass is more preferable.

Hydrotalcites are complex salt compounds consisting of magnesium, aluminum, hydroxyl groups, carbonic acid groups and arbitrary crystalline water known as natural products or synthetic products, and magnesium or a part of aluminum is part of other materials such as alkali metal and zinc. Examples thereof include those substituted with a metal and those substituted with a hydroxyl group and a carbonic acid group with another anionic group. Specifically, for example, the hydrotalcite metal represented by the following general formula (3) is replaced with an alkali metal, and the Al-Li-based hydrotalcites include the following general formula (4). The compound represented by is also used.

（式中、ｘ１およびｘ２は各々下記式で表される条件を満たす数を表し、ｐは０または正の数を表す。０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０である。）

（式中、Ａq−は、ｑ価のアニオンを表し、ｐは０または正の数を表す。）
また、上記ハイドロタルサイトにおける炭酸アニオンは、一部を他のアニオンで置換したものでもよい。

(In the formula, x1 and x2 each represent a number satisfying the conditions represented by the following formula, and p represents 0 or a positive number. 0 ≦ x2 / x1 <10,2 ≦ x1 + x2 ≦ 20.)

(In the equation, Aq− represents a q-valent anion and p represents 0 or a positive number.)
Further, the carbonate anion in the above hydrotalcite may be partially replaced with another anion.

Hydrotalcites may be obtained by dehydrating crystalline water, and are higher fatty acids such as stearic acid, higher fatty acid metal salts such as oleic acid alkali metal salt, and organic sulfonic acid metals such as dodecylbenzene sulfonic acid alkali metal salt. It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester, a wax or the like.

The hydrotalcites may be natural products or synthetic products. Examples of the method for synthesizing such a compound include Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Square Root Guide No. 3-36839, and Japanese Patent Application Laid-Open No. 61-174270. , A known method described in Japanese Patent Application Laid-Open No. 5-179052 and the like. Further, the hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.

When hydrotalcites are blended, the blending amount is 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). Preferably, 0.05 to 3 parts by mass is more preferable.

Further, in the resin composition of the present invention, an anti-slip agent, an anti-blocking agent, an anti-fog agent, a foaming agent, a foaming aid, a vulcanizing agent, a vulcanization accelerator, and vulcanization, as long as the effects of the present invention are not impaired. Other ingredients such as auxiliaries, activators, hygroscopic agents, adhesives and mold release agents may be added. These components may be used alone or in combination of two or more.

The resin composition of the present invention can be molded using a known molding method. Specific examples include injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, calendar molding, slush molding, dip molding, foam molding, etc., but injection with less product loss. A molding method is preferably used.

The resin composition of the present invention has excellent heat resistance and is suitably used for interior and exterior materials of automobiles exposed to sunlight outdoors. However, polyolefin-based resin compositions such as daily necessities, miscellaneous goods, and toys are molded. The resin composition of the present invention can be used in the obtained general molded product.

The automobile interior / exterior material of the present invention uses the polyolefin-based resin composition of the present invention, whereby excellent heat resistance can be exhibited even when a coloring material such as carbon black is blended. It is a thing.

Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples and the like. The blending amount in the table below indicates the part by mass.

[Examples 1-1 to 3-3, Comparative examples 1-1 to 3-13]
70 parts by mass of the trade name "Novatec PP BC03B" (olefin block copolymer) manufactured by Nippon Polypropylene Co., Ltd. as the polyolefin resin (A), and 10 mass of the trade name "Engage 8100" of the Dow Chemical Company as the thermoplastic elastomer (B). Parts, 0.05 parts by mass of stearic acid, and the formulation shown in Tables 1 to 4 below with respect to 20 parts by mass of the trade name "Micron Ace P-4" manufactured by Nippon Tarku Co., Ltd. as the filler (C). Additives were compounded in amounts and mixed. After mixing, pellets were obtained by melt-kneading using a twin-screw extruder (trade name TEX-30α manufactured by Japan Steel Works, Ltd.) under the conditions of a melting temperature of 230 ° C. and a screw speed of 150 rpm.

[Reference Examples 1 and 2]
Additives were blended with 0.05 parts by mass of stearic acid and the blending amounts shown in Table 5 below with respect to 100 parts by mass of the trade name "Novatec PP BC03B" manufactured by Nippon Polypropylene Co., Ltd. and mixed. After mixing, pellets were obtained by melt-kneading using a twin-screw extruder (trade name TEX-30α manufactured by Japan Steel Works, Ltd.) under the conditions of a melting temperature of 230 ° C. and a screw speed of 150 rpm.

(Oven test)
Using the obtained pellets, injection molding was performed at an injection temperature of 230 ° C. using an injection molding machine (EC100-2A, 50t; manufactured by Toshiba Machine Co., Ltd.) to prepare a flat plate-shaped test piece of 25 mm × 50 mm × 2 mm. , Was allowed to stand in an oven at 150 ° C. After standing, the test piece was taken out every 50 hours, and the presence or absence of cracks was confirmed under microscopic observation. If there were no cracks, the test piece was immediately returned to the oven at 150 ° C., and if cracks were confirmed, the time elapsed in the oven test was recorded. These observation results are also shown in Tables 1 to 5 below.

（Ｄ）−１：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＬＡ−５０２ＸＰ」（主成分としてブタン−１，２，３，４−テトラカルボン酸テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジニルを５０質量％含有するマスターバッチ）
比較化合物１：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＬＡ−４０２ＡＦ」（主成分として、脂肪酸（Ｃ１２〜１４）−２，２，６，６−テトラメチル−４−ピペリジニルエステルを含有するマスターバッチ）
比較化合物２：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＬＡ−７０４」（主成分として、脂肪酸（Ｃ１４）−１，２，２，６，６−ペンタメチル−４−ピペリジニルエステルを含有するマスターバッチ）
（Ｅ）−１：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＰＥＰ−３６Ａ」（３，９−ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）−２，４，８，１０−テトラオキサ−３，９−ジホスファスピロ［５．５］ウンデカン）
比較化合物３：株式会社ＡＤＥＫＡ製 商品名「アデカスタブ２１１２」〔トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト）
（Ｆ）−１：カーボンブラック３５質量％含有マスターバッチ
ＡＯ−６０：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＡＯ−６０」〔ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナート］〕

(D) -1: Product name "ADEKA STAB LA-502XP" manufactured by ADEKA Corporation (Tetrakis butane-1,2,3,4-tetracarboxylic acid as a main component (1,2,2,6,6-pentamethyl-4) -Masterbatch containing 50% by mass of piperidinyl)
Comparative Compound 1: ADEKA CORPORATION Product name "ADEKA STAB LA-402AF" (master batch containing fatty acid (C12-14) -2,2,6,6-tetramethyl-4-piperidinyl ester as the main component)
Comparative Compound 2: ADEKA CORPORATION Product name "ADEKA STUB LA-704" (master batch containing fatty acid (C14) -1,2,2,6,6-pentamethyl-4-piperidinyl ester as the main component)
(E) -1: Product name "ADEKA STAB PEP-36A" manufactured by ADEKA Corporation (3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa -3,9-Diphosphaspiro [5.5] undecane)
Comparative Compound 3: Made by ADEKA Corporation Product name "ADEKA STUB 2112" [Tris (2,4-di-tert-butylphenyl) phosphite)
(F) -1: Masterbatch AO-60 containing 35% by mass of carbon black: Made by ADEKA Corporation Product name "ADEKA STUB AO-60" [Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-) Hydroxyphenyl) Propionate]]]

ＡＯ−５０：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＡＯ−５０」〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオン酸ステアリル〕
ＡＯ−２０：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＡＯ−２０」〔１，３，５−トリス［［３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル］メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン

AO-50: Made by ADEKA Corporation Product name "ADEKA STUB AO-50" [3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate]
AO-20: Made by ADEKA Corporation Product name "ADEKA STUB AO-20" [1,3,5-Tris [[3,5-di-tert-butyl-4-hydroxyphenyl] methyl] -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -Trione

（Ｄ）−２：ブタン−１，２，３，４−テトラカルボン酸テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジニル
比較化合物４：１，２，２，６，６−ペンタメチル−４−ピペリジノールと炭素原子数１２〜１４の脂肪酸とのエステル化反応物
比較化合物５：１，２，２，６，６−ペンタメチル−４−ピペリジノールとステアリン酸のエステル化反応物
（Ｆ）−２：ダークグレー顔料マスターバッチ（顔料が、カーボンブラック／酸化チタン＝４／１（質量比）であり、顔料を２４質量％含有するマスターバッチ）

(D) -2: Butane-1,2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl comparative compound 4: 1,2,2,6,6- Esteration reaction product of pentamethyl-4-piperidinol and fatty acid having 12 to 14 carbon atoms Comparative compound 5: 1,2,2,6,6-Esteration reaction product of pentamethyl-4-piperidinol and stearic acid (F) -2: Dark gray pigment master batch (pigment is carbon black / titanium oxide = 4/1 (mass ratio), master batch containing 24% by mass of pigment)

ＡＯ−４１２Ｓ：株式会社ＡＤＥＫＡ製 商品名「アデカスタブＡＯ−４１２Ｓ」〔２，２’−ビス｛［３−（ドデシルチオ）−１−オキソプロポキシ］メチル｝プロパン−１，３−ジイル−ビス［３−（ドデシルチオ）プロピオネート］
ＤＳＴＤＰ：ジステアリルチオジプロピオネート

AO-412S: Made by ADEKA Corporation Product name "ADEKA STAB AO-412S"[2,2'-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diyl-bis [3- (Dodecilcio) Propionate]
DSTDP: Distearylthiodipropionate

From Comparative Examples 1-1 to 1-3 and Comparative Examples 3 to 4 to 3-7, when a compound different from the hindered amine compound (D) represented by the general formula (1) was used, the heat resistance was poor. It could be confirmed.

Further, also when a compound different from the phosphorus-based antioxidant (E) represented by the general formula (2) is used from Comparative Examples 1-4 to 1-5 and Comparative Examples 3-1 to 3-3. It was confirmed that the heat resistance was poor. Furthermore, from the comparison results of Comparative Example 3-8 and Comparative Example 3-10, and Comparative Example 3-9 and Comparative Example 3-11 to 13-13, even if a thioether-based antioxidant is added, the heat resistance is almost the same. It didn't improve.

Furthermore, from Reference Examples 1 and 2, the effect of the present invention could not be confirmed when the thermoplastic elastomer (B) and the filler (C) were not blended.

On the other hand, it was confirmed that the polyolefin-based resin composition of the present invention exhibited excellent heat resistance and was suitable for interior and exterior materials of automobiles. From Examples 2-1 to 2-3, the phenolic antioxidant did not affect the effect of the present invention.

Claims (4)

Contains a polyolefin resin (A), a thermoplastic elastomer (B) (excluding the polyolefin resin (A)) and a filler (C).
The hindered amine light stabilizer (D) 0 represented by the following general formula (1) with respect to 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). .01～5 parts by weight of a phosphorus antioxidant (E) 0.01 to 5 parts by weight of the following general formula (2), and, a colorant (F) 0.01 to 10 parts by weight ,
A polyolefin-based resin composition, wherein the colorant (F) contains carbon black.

(In formula (1), R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or a methyl group.)

(In the formula (2), R ² and R ³ each independently represent an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms, and the hydrogen atom of the alkyl group and the aryl group is , May be substituted with an alkyl group having 1 to 8 carbon atoms.) The first aspect of claim 1, wherein the thermoplastic elastomer (B) is contained in an amount of 5 to 35 parts by mass in 100 parts by mass of the total amount of the polyolefin resin (A), the thermoplastic elastomer (B) and the filler (C). Polyolefin resin composition of. The polyolefin-based resin composition according to claim 1 or 2, wherein the polyolefin-based resin (A) is an olefin block copolymer. An automobile interior / exterior material using the polyolefin-based resin composition according to any one of claims 1 to 3.