JP2002256158A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which maintains heat resistance, light resistance, mar resistance and the like at a good level and, simultaneously, excels in anti-fogging properties. SOLUTION: The thermoplastic elastomer composition comprises (A) 100 pts.wt. (A1) olefinic thermoplastic elastomer and/or (A2) styrenic thermoplastic elastomer, (B) 0.05-0.7 pt.wt. antioxidant, (C) 0.01-0.5 pt.wt. light stabilizer, (D) 0.01-0.5 pt.wt. lubricant, and (E) 0.01-5 pts.wt. metal chloride and/or metal aluminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic elastomer composition. More specifically, the present invention relates to an olefin-based thermoplastic elastomer composition and / or a styrene-based thermoplastic elastomer composition having good heat resistance, light resistance, scratch resistance, and excellent fogging resistance. is there.

[0002]

2. Description of the Related Art In recent years, olefin-based thermoplastic elastomer compositions and / or styrene-based thermoplastic elastomers have been widely used for automotive interior parts such as instrument panels and airbag covers. Here, the olefin-based thermoplastic elastomer composition and / or styrene-based thermoplastic elastomer used for automobile interior parts is required to have excellent general properties such as heat resistance, light resistance, and scratch resistance, as well as excellent fogging resistance. Is done. Here, fogging refers to a phenomenon in which various additives contained in the resin composition volatilize and adhere to the window glass, thereby causing inconvenience such as deterioration of visibility. From the viewpoint that heat resistance, light resistance, scratch resistance, etc. are maintained at a satisfactory high level, and from the viewpoint of excellent fogging resistance, an olefin-based thermoplastic elastomer composition and / or a styrene-based thermoplastic according to a conventional technique is used. Elastomer compositions have not been fully satisfactory.

[0003]

Under such circumstances,
An object of the present invention is to provide an olefin-based thermoplastic elastomer composition and / or a styrene-based thermoplastic elastomer which maintain heat resistance, light resistance, scratch resistance and the like at a satisfactory level and have excellent fogging resistance. It is in providing a composition.

[0004]

That is, the present invention comprises the following components (A) to (E), and the content of the component (B) is 0 per 100 parts by weight of the content of the component (A). .05-
0.7 parts by weight, and the content of the component (C) is 0.01 to
0.5 part by weight, and the content of the component (D) is 0.01 to
0.5 part by weight, and the content of the component (E) is 0.01 to
It relates to a thermoplastic elastomer composition of 5 parts by weight. (A): (A1) olefin-based thermoplastic elastomer and / or (A2) styrene-based thermoplastic elastomer (B): antioxidant (C): light stabilizer (D): lubricant (E): metal chloride and / or Or aluminate

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention comprises (A1)
Olefinic thermoplastic elastomer and / or (A2)
It is a styrene-based thermoplastic elastomer.

(A1) As the olefin-based thermoplastic elastomer, compound TPO ("TPO" means olefin-based thermoplastic elastomer), reactor TPO, or a mixture thereof may be used. The reactor TPO is also called a polymerization reactor TPO, and is an olefin-based thermoplastic elastomer in which a rubber component as a soft part is dispersed in a matrix resin as a hard part during polymerization.

Among (A1) olefin-based thermoplastic elastomers, those containing (a) 10-65% by weight of a polypropylene-based resin and (b) 90-35% by weight of an olefin-based rubber are moldability and flexibility. It is preferable from the viewpoint of mechanical strength. However, the total amount of (a) and (b) is 100
% By weight.

(A) The polypropylene resin is a crystalline polymer containing a repeating unit derived from propylene. (A) Among polypropylene resins, (a1) homopolypropylene, (a)
2) Propylene-ethylene random copolymer, (a3)
A propylene-ethylene block copolymer is preferred, and these may be used alone or in combination of two or more. Here, (a1) is a propylene homopolymer.
(A2) is a copolymer in which propylene and ethylene are randomly polymerized. (A3) is composed of a first segment and a second segment. The first segment is a homopropylene portion of propylene homopolymerization, and the second segment is a block copolymer of a propylene-ethylene random copolymer portion. As the first segment (a3), a propylene-ethylene random copolymer having a different ethylene content from the second segment may be used.

(A) Melt flow rate of polypropylene resin (hereinafter referred to as MFR) (JIS K-
7210, a load of 21.18 N, and a temperature of 230 ° C.) are preferably 0.1 mm from the viewpoint of further improving formability and mechanical strength.
1 to 150 g / 10 min, more preferably 0.5 g
１００100 g / 10 min. The higher the MFR, the better the moldability, while the lower the MFR, the better the mechanical strength.

(A) The polypropylene-based resin can be produced by using any polymerization catalyst of a Ziegler-based catalyst or a metallocene-based catalyst.

(B) The olefin rubber is an amorphous polymer obtained by randomly copolymerizing one or more olefin monomers. Among the (b) olefin rubbers, (b1) an ethylene-α-olefin copolymer rubber and (b2) an ethylene-α-olefin-nonconjugated diene copolymer rubber are preferable from the viewpoint of availability. May be used alone or in combination of two or more.

(B1) The ethylene-α-olefin copolymer rubber is a copolymer rubber obtained by randomly polymerizing ethylene and an α-olefin having 3 or more carbon atoms. The α-olefin has 3 to 8 carbon atoms from the viewpoint of availability.
Are preferable, and propylene, 1-butene, 1-hexene and 1-octene are more preferable. The content of the repeating unit (α-olefin unit) derived from α-olefin in (b1) is preferably from 10 to 60% by weight from the viewpoint of further increasing mechanical strength and flexibility. The higher the content of the α-olefin unit, the more excellent the flexibility, while the smaller the content of the α-olefin unit, the better the mechanical strength.

(B2) The ethylene-α-olefin-non-conjugated diene copolymer rubber is a copolymer rubber obtained by randomly polymerizing ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated diene. As the α-olefin, from the viewpoint of availability, α-olefins having 3 to 8 carbon atoms are preferable, and propylene is more preferable. The content of the α-olefin unit in (b2) is preferably from 10 to 60% by weight from the viewpoint of further increasing mechanical strength and flexibility. The higher the content of the α-olefin unit, the more excellent the flexibility, while the smaller the content of the α-olefin unit, the better the mechanical strength. As the non-conjugated diene, a non-conjugated diene having 4 to 30 carbon atoms is preferable from the viewpoint of availability, for example, 1,4-hexadiene,
6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-
Chain non-conjugated dienes such as 1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-
Cyclic non-conjugated dienes such as chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, 2
-Norbornadiene, 1,3,7-octatriene,
Trienes such as 1,4,9-decatriene are mentioned, among which dicyclopentadiene and 5-ethylidene-
2-norbornene is preferred.

(B) The Mooney viscosity at 121 ° C. (ML _{1 + 4} 121 ° C.) of the olefin rubber is preferably from 5 to 350, more preferably from 10 to 300, from the viewpoint of further improving moldability and mechanical strength. is there. The higher the Mooney viscosity, the better the mechanical strength, while the lower the Mooney viscosity, the better the moldability.

(B) The olefin rubber may be an oil-extended rubber. The content of extender oil when using oil-extended rubber is
Normally 20 to 20 per 100 parts by weight of rubber excluding extension oil
0 parts by weight. Extending oils are mineral oil based softeners and the like. The mineral oil-based softeners include paraffin-based, naphthene-based and aroma-based softeners, and paraffin-based softeners are preferred. When the oil-extended rubber is used as the olefin rubber (b), the Mooney viscosity described above is the Mooney viscosity of the oil-extended rubber.

(B) The olefin rubber can be produced using any polymerization catalyst such as a Ziegler catalyst, a vanadium catalyst or a metallocene catalyst.

The proportions of (a) the polypropylene resin and (b) the olefin rubber are (a) 10 to 65% by weight and (b) 90 to 35% by weight from the viewpoint of further improving moldability and flexibility. And more preferably (a) 15
-60% by weight and (b) 85-40% by weight. However, the total weight of (a) and (b) is 100% by weight. The higher the amount of (a), the better the moldability.
The less is, the better the flexibility.

As the component (A), a composition obtained by adding a crosslinking agent and a crosslinking aid to (a) a polypropylene resin and (b) an olefin rubber and dynamically heat-treating the composition may be used. As crosslinking agents, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne 3,1,3-bis (T-butylperoxyisopropyl) benzene, 1,
1-di (t-butylperoxy) 3,5,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t
Organized oxides such as -butylperoxybenzoyl) hexine-3 and dicumyl peroxide can be used. Of these, 2,5-dimethyl-2,5- (t-butylperoxy) hexane is preferred.

Examples of the crosslinking assistant include N, N'-m-phenylenebismaleimide, toluylenebismaleimide, p-quinonedioxime, nitrobenzene, diphenylguanazine, trimethylolpropane, divinylbenzene, ethylene glycol dimethacrylate, and polyethylene glycol. Examples thereof include dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. Among them, N, N'-m-phenylenebismaleimide and trimethylolpropane are preferable.

The (A2) of the present invention is a styrene-based thermoplastic elastomer. Among them, (a) 10-65% by weight of a polypropylene-based resin, and (c) at least a polymer block comprising at least two styrenes, From the viewpoints of moldability, flexibility and mechanical strength, those containing 90 to 35% by weight of a hydrogenated product of a block copolymer composed of a polymer block composed of one conjugated diene compound are preferred. However, the total weight of (a) and (c) is 100% by weight. As the conjugated diene compound (c), butadiene and isoprene are preferred. The ratio (weight ratio) of the styrene unit / conjugated diene compound unit (c) is preferably from 10/90 to 50/50 from the viewpoint of further increasing mechanical strength and flexibility.
A larger amount of styrene units (less conjugated diene compound) has better mechanical strength, while a smaller number of styrene units (more conjugated diene compound) has better flexibility.

The ratio of the hydrogenated product of the block copolymer consisting of (a) a polypropylene resin, (c) a polymer block comprising at least two styrenes and at least one polymer block comprising a conjugated diene compound is as follows: , Moldability,
From the viewpoint of enhancing flexibility, (a) 10 to 65% by weight,
(c) 90 to 35% by weight is preferred, more preferably
(a) 20 to 50% by weight, and (c) 80 to 50% by weight.
However, the total weight of (a) and (c) is 100% by weight.
More (a) is more excellent in moldability, while less (a) is more flexible. The details of (a) the polypropylene-based resin are as described above.

The component (B) antioxidant of the present invention is for preventing or reducing thermal deterioration or oxidative deterioration of the thermoplastic elastomer composition, and includes a phenolic antioxidant and an amine antioxidant. They are classified into primary antioxidants and secondary antioxidants such as sulfur-based antioxidants and phosphorus-based antioxidants, and these may be used alone or in combination of two or more.

Specific examples of the primary antioxidant include triethylene glycol-bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4
-Hydroxy-3,5-di-t-butylanilino)-
1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, N, N'-hexamethylenebis (3,
5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
-Isocyanurate, 2,4-bis [(octylthio)
Methyl] -o-cresol, isooctyl-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 3,9-bis [2- [3- (3-t-butyl-4
-Hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-
Phenolic antioxidants such as tetraoxaspiro [5,5] undecane, butylhydroxytoluene, 2,6-di-t-butyl-p-cresol, phenyl-α-naphthylamine, phenyl-β-naphthylamine, N, N '
Diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine,
N-phenylene-N′-isopropyl-p-phenylenediamine, aldol-α-naphthylamine, 2,2
4-trimethyl-1,2-dihydroquinone polymer,
Examples include amine antioxidants such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone.

Specific examples of the secondary antioxidant include thiobis (β-naphthol) and thiobis (N-phenyl-β-
Naphthylamine), 2-mercaptobenzothiazole,
2-merbutobenzimidazole, dodecyl mercaptan, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate,
Sulfur antioxidants such as dilauryl thiodipropionate and distearyl thiodipropionate, tetrakis (2,4-di-t-butylphenol) -4,4′-biphenylenediphosphonite, distearyl pentaerythritol di Phosphite, cyclic neopentanetetraylbis (octadecylphosphite),
Trisnonylphenyl phosphite, bis (2,4-
And phosphorus-based antioxidants such as di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl phosphite).

Component (B) of the thermoplastic elastomer composition
Is from 0.05 to 100 parts by weight of the component (A).
0.7 parts by weight is preferred, and more preferably 0.1 to 0.1 part by weight.
6 parts by weight. If the content of the component (B) is too small, the heat resistance may be poor, whereas if it is too large, the fogging resistance may be poor.

The component (C) light stabilizer of the present invention is for preventing and reducing light deterioration of the thermoplastic elastomer composition, and is classified into a hindered amine light stabilizer and an ultraviolet absorber. Alternatively, two or more kinds may be used in combination.

Specific examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4
-Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] −2,2,6
6-tetramethyl-4-piperidyl- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5
-Di-t-butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-
4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-succinate
2,2,6,6-tetramethylpiperidine polycondensate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, phenyl-4-piperidinyl carbonate and the like.

Specific examples of the ultraviolet absorber include 2-
(2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-
(Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl ) Hydroxybenzo such as benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, and 2,2'-methylenebis (4-t-octyl-6-benzotriazolyl) phenol Triazole UV absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-
Examples include hydroxybenzophenone-based ultraviolet absorbers such as 4-octoxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).

Component (C) of the thermoplastic elastomer composition
Is 0.01 to 100 parts by weight of the component (A).
0.5 parts by weight is preferred, and more preferably 0.05 to
0.4 parts by weight. If the content of the component (C) is too small, the light resistance may be poor. On the other hand, if the content is too large, the fogging resistance may be poor.

The component (D) of the present invention is a lubricant, which imparts lubricity to the surface of the molded product and improves scratch resistance. Preferred specific examples include unsaturated fatty acid amides such as erucic acid amide and oleic acid amide, and saturated fatty acid amides such as behenic acid amide and stearic acid amide. The content of the component (D) in the thermoplastic elastomer composition is preferably from 0.01 to 0.5 part by weight, more preferably from 0.05 to 0.4 part by weight, based on 100 parts by weight of the component (A). . If the content of the component (D) is too small, the scratch resistance may be poor. On the other hand, if the content is too large, the fogging resistance may be poor.

The component (E) of the present invention is at least one selected from the group consisting of metal chlorides and aluminates. Examples of the metal chloride include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, iron chloride, and zinc chloride. Examples of the metal aluminate include lithium aluminate, sodium aluminate, and aluminate. Potassium, magnesium aluminate, calcium aluminate and the like can be mentioned.
These compounds may be used alone or in combination of two or more. Among these compounds, iron chloride and sodium aluminate are preferred from the viewpoints of fogging resistance, heat resistance and light resistance.

Component (E) of the thermoplastic elastomer composition
Is 0.04 parts by weight based on 100 parts by weight of the component (A).
It is preferably 1 to 5 parts by weight, more preferably 0.05 to 2 parts by weight.
Parts by weight. If the content of the component (E) is too small, the fogging resistance may be poor. On the other hand, if the content is too large, the heat resistance, light resistance and scratch resistance of the resin may be poor.

The thermoplastic elastomer composition of the present invention comprises:
An antistatic agent may be added as another additive. As the antistatic agent, amide-based cations, polyhydric alcohol derivatives, stearic acid esters, glycerin fatty acid esters, polyethylene glycol fatty acid esters, stearic acid monoglyceride, fatty acid monoglyceride and the like are used. The amount of the antistatic agent to be added is preferably 0.01 to 0.5 part by weight, more preferably 0.05 to 0.4 part by weight, per 100 parts by weight of component (A). If the amount is too small, the antistatic property may be poor, while if it is too large, the fogging resistance may be poor.

Further, the thermoplastic elastomer composition of the present invention comprises talc, hydrotalcite, calcium carbonate,
Inorganic fillers such as calcined kaolin; neutralizing agents such as calcium oxide, magnesium oxide and zinc oxide; flame retardants such as aluminum hydroxide, magnesium hydroxide and antimony oxide; silicone oils; pigments; Etc. may be added.

In order to obtain the thermoplastic elastomer composition of the present invention, the respective components may be melt-kneaded using, for example, a twin-screw extruder or a Banbury mixer.

The thermoplastic elastomer composition of the present invention comprises:
Taking advantage of the above-mentioned excellent features, it can be used for two-color molded products such as automobile airbag covers, console boxes, shift levers, door trims, and skin materials such as instrument panels, doors, and glass runs.

[0037]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Sumitomo Chemical Industries, Ltd. ethylene-propylene random copolymer Nobrene Z144A (hereinafter r-PP, MFR = 3
0 g / 10 min, ethylene content 3.4 wt%) 50 parts by weight and Sumitomo Chemical Co., Ltd. ethylene-propylene copolymer rubber Esplen 201 (hereinafter EPR-1, ML _{1 +} 412)
1 ° C. = 29, propylene content 53% by weight) 10 parts by weight and Sumitomo Chemical Co., Ltd. ethylene-propylene copolymer rubber Esplen 512P (hereinafter EPR-2, ML _{1 +} 41)
21 ° C. = 68, propylene content: 31% by weight) 40 parts by weight, Irganox 1010 (Ciba.
0.2 parts by weight of Specialty Chemicals Co., Ltd., 0.2 parts by weight of Sumisorb 300 (hereinafter, light-resistant agent-1, manufactured by Sumitomo Chemical Co., Ltd.) as a light-proofing agent, Sanol LS-770 (hereinafter, light-resistant agent-2, manufactured by Sankyo Co. ) 0.1 parts by weight, 0.1 part by weight of LA-52 (hereinafter referred to as Lightfastener-3, manufactured by Asahi Denka), 0.05 parts by weight of Denone SL-12 (manufactured by Marubishi Yuka) as a lubricant, iron chloride (III) 0.8 parts by weight of hexahydrate was kneaded at 200 ° C. using Labo Plastmill to obtain a thermoplastic elastomer composition. Then, press at 200 ° C, thickness 2mm
Sheet was obtained. The obtained sheet is 25 mm x 100 m
m and 100 ° C., 20 ° C. using the apparatus shown in FIG.
A fogging test was performed with Hr, and after the test, the haze of the glass plate was measured using a haze meter manufactured by Suga Test Instruments Co., Ltd.
A low haze value indicates good fogging properties. Table 1 shows the results.

Example 2 The procedure of Example 1 was repeated, except that 0.8 parts by weight of sodium aluminate was used instead of iron (III) chloride hexahydrate. Table 1 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated except that iron (III) chloride hexahydrate was not used. Table 1 shows the results.

[0040]

[Table 1]

[0041]

As described above, according to the present invention, it is possible to provide a thermoplastic elastomer composition which maintains heat resistance, light resistance, scratch resistance and the like at a satisfactory high level and has excellent fogging resistance. did it. The thermoplastic elastomer composition of the present invention has excellent flexibility and mechanical strength, and is a two-color molded article such as an airbag cover, a console box, a shift lever, and a door trim of an automobile, an instrument panel, a door, and a skin of a glass run. Used for materials.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an apparatus used for a fogging test.

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Claims (3)

[Claims] 1. The composition contains the following components (A) to (E), and the content of the component (B) is 0.05 to 0.7 parts by weight per 100 parts by weight of the content of the component (A). The content of the component (C) is 0.01 to 0.5 parts by weight, the content of the component (D) is 0.01 to 0.5 parts by weight, and the content of the component (E) is 0 to 0.5 parts by weight. 0.01 to 5 parts by weight of the thermoplastic elastomer composition. (A): (A1) olefin-based thermoplastic elastomer and / or (A2) styrene-based thermoplastic elastomer (B): antioxidant (C): light stabilizer (D): lubricant (E): metal chloride and / or Or metal aluminate 2. The thermoplastic elastomer composition according to claim 1, which is used for automotive interior parts. 3. The thermoplastic elastomer composition according to claim 2, wherein the automotive interior parts are used for airbag covers.