JP2009275213A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition superior in compression permanent set characteristic and oil resistance property in a high temperature region, superior in softness and moldability, specially having no bloom-out. <P>SOLUTION: The thermoplastic elastomer composition comprises 100 pts.mass of an ethylene-α-olefin-non-conjugate copolymer rubber (a), 20-250 pts.mass of crystalline polypropylene (b), 2-30 pts.mass of a non-halogenic phenol resin cross-linking agent (c), 0.1-6 pts.mass of tin chloride (d), and 2-50 pts.mass of at least one kind of inorganic filler (e) selected from the group consisting of talc and clay. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition, and more specifically, it is excellent in compression set characteristics and oil resistance in a high temperature region, in addition to excellent flexibility and moldability, and in particular, there is no bloom-out (powder blowing). The present invention relates to a plastic elastomer composition.

  In recent years, thermoplastic elastomers, which are soft materials with rubber elasticity and do not require a vulcanization process, can be molded and processed like thermoplastic resins, and can be recycled. Automotive parts, home appliance parts, wire coating materials, medical Widely used in fields such as parts, footwear and sundries.

  Among thermoplastic elastomers, polystyrene-based thermoplastic elastomers such as styrene-butadiene block copolymer (SBS) and styrene-isoprene block copolymer (SIS), which are block copolymers of aromatic vinyl compound-conjugated diene compound, are The thermoplastic elastomer composition which is rich in flexibility, has a good rubber elasticity at room temperature, and is excellent in processability, is widely used as a substitute for vulcanized rubber.

  In addition, an elastomer composition obtained by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene in these elastomers is further improved as an elastomer having improved heat aging resistance (thermal stability) and weather resistance. Widely used.

  However, thermoplastic elastomer compositions using these block copolymers and hydrogenated block copolymers still have rubber-like properties such as oil resistance, heat / pressure deformation rate (compression set) and rubber at high temperatures. There is a problem in elasticity, and as a means for improving this point, a crosslinked product obtained by crosslinking a composition containing a hydrogenated derivative of the block copolymer has been proposed (see, for example, Patent Documents 1 to 5). .

  However, the crosslinked composition of the hydrogenated block copolymer disclosed in the above patent document has a problem that the compression set is still insufficient at a high temperature, particularly at 100 ° C. or more, and the mechanical strength tends to decrease. At present, the performance level required for vulcanized rubber applications has not been reached. In extrusion molding, since the melt tension at a high temperature is low, shape retention is deteriorated, and in injection molding, there are many problems on the molding surface such as a longer molding cycle (molding time).

  In addition, thermoplastic elastomer compositions obtained by dynamically crosslinking olefin resins and olefin copolymer rubbers are excellent in flexibility, heat aging resistance, weather resistance, mechanical properties, and the like (for example, patents). Reference 6-9). However, in these compositions, the compression set at a high temperature does not reach the performance level required for conventional vulcanized rubber applications.

In addition, in the field of vulcanized rubber, blooming out of a crosslinking accelerator has been a problem (for example, see Patent Document 10). Also in the field of thermoplastic elastomers, it has been known that low molecular weight organic additives such as antioxidants and lubricants bloom out depending on the compounding system (for example, see Patent Document 11).
In addition, the presence of bloom-out in calcium carbonate and silica in a thermoplastic elastomer by dynamic crosslinking using a phenol crosslinking agent based on EPDM has been a potential problem. However, it has been said that it is extremely difficult to solve the bloom-out while maintaining the mechanical properties and moldability required by the user.

JP 59-6236 A JP-A 63-57662 JP 58-133202 A JP 59-131613 A Japanese Patent Laid-Open No. Sho 61-218650 JP 62-62847 A JP-A 64-24839 JP-A-3-234744 JP-A-2-255733 Japanese Patent Laid-Open No. 11-80460 JP-A-5-287133

  An object of the present invention is to provide a thermoplastic elastomer composition which is excellent in compression set characteristics and oil resistance in a high temperature region, is excellent in flexibility and moldability, and particularly has no bloom out.

The present invention is as follows.
1. (A) 100 parts by mass of ethylene / α-olefin / non-conjugated diene copolymer rubber;
(B) 20 to 250 parts by mass of crystalline polypropylene,
(C) 2-30 parts by mass of a non-halogen phenol resin crosslinking agent,
(D) 0.1-6 parts by mass of tin chloride, and (e) at least one inorganic filler selected from the group consisting of talc and clay, 2-50 parts by mass of a thermoplastic elastomer composition, .

  2. 2. The thermoplastic elastomer composition as described in 1 above, wherein the mass ratio of the component (d) and the component (e) is 1.0 / 0.8 to 30 as the former / the latter.

  3. 3. The thermoplastic elastomer composition as described in 1 or 2 above, wherein the component (e) has an average particle size of 10 μm or less.

  4). 4. The thermoplastic elastomer composition as described in any one of 1 to 3 above, wherein the component (a) is synthesized by a solution polymerization method.

  5). 5. The thermoplastic elastomer composition as described in 4 above, wherein the component (a) is synthesized by a metallocene catalyst.

  6). 6. The thermoplastic elastomer composition as described in any one of 1 to 5 above, wherein the crystallinity of the component (a) is 9 to 14%.

  7. The molded object formed by shape | molding the thermoplastic elastomer composition in any one of said 1-6.

According to the present invention, by specifying the types and blending amounts of the components (a) to (e), the compression set characteristics and oil resistance in the high temperature region are excellent, and the flexibility and moldability are particularly excellent. A thermoplastic elastomer composition free of bloom out is provided.
Bloom out is a phenomenon in which a component or derivative thereof contained in a composition floats on the surface of a molded product, exhibiting a so-called powder blowing state. The molded product has poor appearance, scratch resistance and wear resistance, Adverse effects such as deterioration of adhesion during color molding.

  Hereinafter, the components of the thermoplastic elastomer composition of the present invention, the production of the thermoplastic elastomer composition, and the uses of the thermoplastic elastomer composition will be described in detail.

1. Component (a) of thermoplastic elastomer composition: ethylene / α-olefin / non-conjugated diene copolymer rubber Component (a) used in the present invention is an ethylene / α-olefin / non-conjugated diene copolymer rubber. It is. The ethylene / α-olefin / nonconjugated diene copolymer rubber is obtained by polymerizing ethylene, an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene and the like and a nonconjugated diene compound. It is a copolymer. Among α-olefins, propylene is particularly preferable from the viewpoint of crosslinkability by a crosslinking agent and suppression of bloom-out.

  Examples of the non-conjugated dienes include 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4 -Hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, 5-isopropylidene-2-norbornene, 5 -Vinyl-norbornene, dicyclooctadiene, methylene norbornene and the like can be mentioned. Among them, 5-ethylidene-2-norbornene is particularly preferable from the viewpoint of crosslinkability with a crosslinking agent and the suppression of bloom-out.

  Specific examples of the component (a) include ethylene / propylene / nonconjugated diene copolymer rubber, ethylene / 1-butene / nonconjugated diene copolymer rubber, and the like. Among these, ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) is preferable from the viewpoint of crosslinkability by a crosslinking agent and the suppression of bloom-out.

  As the component (a) in the present invention, a component synthesized using a Ziegler catalyst or a metallocene catalyst is used. A Ziegler catalyst is a polymerization catalyst comprising a titanium compound or vanadium compound and an organoaluminum compound, and a metallocene catalyst is a highly active polymerization comprising a cyclopentadienyl derivative of a transition metal such as titanium or zirconium and a promoter. It is a catalyst. The metallocene-based catalyst is excellent in controllability of the molecular weight distribution, viscosity and non-conjugated diene compound content of the obtained polymer, and there is little fluctuation in performance between lots of the obtained polymer and within the lot. Therefore, it is preferable to use the component (a) prepared using a metallocene-based catalyst because there is no bloom-out, the smoothness of the surface of the molded product is improved, and there are few spots and smears.

  The range of the ethylene content of the component (a) is preferably 40 to 80% by mass, more preferably 50 to 75% by mass. Particularly in the above range, the balance between the manufacturability of the resulting composition, compression set at high temperature, and tensile strength is good. Moreover, 0.5-8 mass% is preferable, and, as for the range of content of a nonconjugated diene compound, More preferably, it is 2-6 mass%. By setting the content range of the non-conjugated diene compound to the above range, the compression set characteristics of the obtained composition can be further enhanced.

Moreover, 10-180 are preferable and, as for Mooney viscosity ML1 _{+ 4} (125 degreeC) of (a) component, 20-150 are more preferable. When the Mooney viscosity ML _{1 + 4} (125 ° C.) of the component (a) is less than 10, the compression set characteristic of the thermoplastic elastomer composition is lowered. If it exceeds 180, the moldability deteriorates. Further, by setting the Mooney viscosity ML _{1 + 4} (125 ° C.) of the component (a) within the specific range, the oil resistance and compression set characteristics can be further improved.

  In general, as a process for producing ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), a solution polymerization method mainly using an aliphatic hydrocarbon as a solvent is employed. A slurry polymerization method is also employed. In addition, a gas phase polymerization method in which various inert materials (for example, carbon black) are used as a dispersant in the monomer gas to promote a polymerization reaction has been industrialized. The synthesis by the solution polymerization method, unlike the gas phase polymerization method, is excellent in suppressing bloom-out because the polymer does not contain carbon black or the like. Furthermore, when a metallocene catalyst is used, the effect of suppressing bloom out is further improved. On the other hand, the synthesis by the gas phase polymerization method can synthesize a polymer having a higher molecular weight than the solution polymerization method or the slurry polymerization method. As a result, the Mooney viscosity can be increased, which is effective for oil resistance and compression set.

Moreover, 9 to 14% is preferable and the crystallinity of the component (a) is more preferably 10 to 13%. If the degree of crystallinity is 9 to 14%, the effect of suppressing bloom out is further enhanced. If the degree of crystallinity is 10 to 13%, the bloom-out suppressing effect is further enhanced.
Here, the degree of crystallinity referred to in this specification is a value measured by DSC (differential scanning calorimetry), and is specifically measured by the following method.
(I) The sample is put in an aluminum pan with a known weight and dried under a pressure of about 10 Pa for 24 hours before sealing.
(Ii) Immediately after drying, the weight of the entire sample container is measured and sealed under pressure.
(Iii) A sample container is set in the sample holder of the DSC, and the temperature is increased to 230 ° C. at a temperature increase rate of 10 ° C./min.
(Iv) Maintain at 230 ° C. for 60 minutes to completely melt or relax the sample.
(V) Cool to 30 ° C. at the same rate (10 ° C./min) as the temperature rising rate.
(Vi) The degree of crystallinity is evaluated from the heat of crystallization (ΔHc) on the assumption that the completeness of crystals generated in the isothermal crystallization process is constant regardless of the crystal generation time.
(Vii) The degree of crystallinity is expressed as% of the crystallization heat (ΔHc) of component (a), where 100 is the heat of crystallization (ΔHc) of HDPE (HJ560: Nippon Polychem, specific gravity 0.964).

  Examples of commercially available products that can be used as the component (a) include Nordel IP 4725P, 4760P and 4770R (solution polymerization, trade name) and Nordel MG 46140, 47085, 47100 and 47130 (gas phase polymerization) manufactured by DuPont Dow Elastomer Japan. , Product name) and the like.

(B): Crystalline polypropylene The component (b) used in the present invention is crystalline polypropylene, and is used for the purpose of improving the oil resistance, adjusting the hardness, and improving the moldability of the thermoplastic elastomer composition.
Examples of the component (b) include a crystalline propylene homopolymer or a crystalline copolymer mainly composed of propylene. Examples of the copolymer include a block copolymer, a random copolymer, and a block / random copolymer. Examples of the component (b) include crystalline propylene polymers such as isotactic polypropylene, propylene / ethylene copolymer, propylene / butene-1 copolymer, propylene / ethylene / butene-1 terpolymer. Is mentioned.

The melting point by DSC of the component (b) is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, particularly preferably 150 ° C. or higher.
Here, the melting point by DSC is the peak top melting point obtained by a differential scanning calorimeter (DSC). Specifically, using DSC, a sample amount of 10 mg is taken, held at 190 ° C. for 5 minutes, and then −10 Crystallization is performed at a rate of temperature decrease of 10 ° C / min up to 10 ° C, held at -10 ° C for 5 minutes, and then measured to 200 ° C at a rate of temperature increase of 10 ° C / min.
(B) MFR (230 degreeC 21.18N load) of a component has preferable 0.1-850g / 10min, 0.2-300g / 10min is more preferable from the point of the balance of a physical property and a moldability, 0.5-20g / 10 min is more preferable.

  (B) The compounding quantity of a component is 20-250 mass parts with respect to 100 mass parts of (a) component, Preferably it is 30-210 mass parts. When the amount of component (b) exceeds the upper limit, compression set decreases, and when it is less than the lower limit, oil resistance, manufacturability and moldability decrease.

  Examples of commercially available products that can be used as the component (b) include Novatec BC8, BC08AHA, EA9, EC3HF, and EG7F (trade name) manufactured by Nippon Polychem Co., Ltd.

(C): Non-halogen phenol resin crosslinking agent The component (c) used in the present invention is a non-halogen phenol resin, and is a component that cross-links the component (a).

Examples of the non-halogen phenol resin include a condensation product of an alkyl-substituted phenol or an unsubstituted phenol with an aldehyde in an alkaline medium, preferably a condensate with formaldehyde. The substituted alkyl group in the alkyl-substituted phenol is preferably those having less than 20 carbon atoms, particularly dimethylolphenols substituted with a substituted alkyl group having 1 to 12 carbon atoms in the p-position. Moreover, the condensate of bifunctional phenol dialcohols is also preferable as a non-halogen phenol resin.
U.S. Pat. No. 4,311,628, U.S. Pat. Nos. 2,972,600 and 3,287,440 disclose a technique for crosslinking a thermoplastic vulcanized rubber with a phenol resin. Techniques can also be used in the present invention.

Examples of preferred non-halogen phenolic resins are defined by general formula (I). Preferably Q is selected from the divalent groups —CH ₂ — and —CH ₂ —O—CH ₂ —, n is 0 or a positive integer from 1 to 20, and R has less than 20 carbon atoms. Organic group. Even more preferably, R is an organic group having 1 to 12 carbon atoms in the p-position.

  Examples of the above-mentioned non-halogen-based phenolic resins include Taquilol 201 and 202 (trade name) manufactured by Taoka Chemical Co., Ltd., PR-4507 (trade name) manufactured by Gunei Chemical Industry Co., Ltd., and manufactured by Hoechst. Vulcaresat 510E, 532E, Vulcaresen E, 105E, 130E, Vulcaresol 315E (trade name), Amberol ST 137X (trade name) manufactured by Rohm & Haas, Sumitomo Durez Co., Ltd. Sumitrite Resin PR-22193 (trade name) Anchor Chem. Symform-C-100, C-1001 (trade name) manufactured by the company, Tamanol 531 (trade name) manufactured by Arakawa Chemical Industries, Ltd., and Chemichemistry Chem. Specifieddy SP1045, SP1055, SP1056, SP1059 (trade name), U.S.A. C. CRR-0803 (trade name) manufactured by C company, CRM-0803 (trade name) manufactured by Showa Union Synthesis Co., Ltd., Vulkadur A (trade name) manufactured by Bayer, and the like are mentioned. Product name) can be preferably used.

  Of these, the following p-octylphenol formaldehyde resin (mass average molecular weight Mw = 2,500 to 4,000) is particularly preferred as the component (c). The said resin can also utilize what is marketed as said Tackirol 201,202 (brand name).

  (C) The compounding quantity of a component is 2-30 mass parts with respect to 100 mass parts of (a) component, Preferably it is 3-15 mass parts. When the compounding amount of the component (c) exceeds 30 parts by mass, the fluidity of the thermoplastic elastomer composition is remarkably reduced, making it difficult to produce and mold. On the other hand, if it is less than 2 parts by mass, the compression set characteristics and oil resistance of the thermoplastic elastomer composition deteriorate.

(D): Tin chloride The component (d) used in the present invention is tin chloride (SnCl ₂ ), and is used for more effectively improving the function of the crosslinking agent of the component (c). Further, by combining the component (d) with the component (c) and the component (e) described below, the compression set characteristics and oil resistance in the high temperature region can be expressed well, and the bloom-out An inhibitory effect is manifested.

(D) A component is mix | blended in the range of 0.1-6 mass parts with respect to 100 mass parts of (a) component, and 0.5-3 mass parts is preferable. When the blending amount of the component (d) exceeds 6 parts by mass, the crosslinking does not occur uniformly, the fluidity of the resulting thermoplastic elastomer composition is lowered and the production / molding becomes difficult, and the bending whitening property and the bending fatigue resistance are improved. Getting worse. In addition, the bloom-out suppressing effect is not exhibited.
When the blending amount of the component (d) is less than 0.1 parts by mass, the crosslinking reaction is not sufficient, the oil bleed resistance and the oil resistance are deteriorated, and the compression set is also deteriorated, which is not preferable.

In the present invention, by setting the quantitative relationship between the component (c) and the component (d) within a specific range, it is possible to suppress bloom-out while maintaining compression set characteristics, oil resistance, flexibility, and moldability. The effect can be further enhanced. That is, when the component (c) is 1, the (mass) and component (d) are preferably 0.05 to 1.2.
As the component (d), a commercially available product can be used.

(E): at least one inorganic filler selected from the group consisting of talc and clay The component (e) used in the present invention is at least one inorganic filler selected from the group consisting of talc and clay, and bloom. Contributes to the suppression of out. Inorganic fillers other than this component do not show the effect of suppressing bloom out (excluding (g) zinc oxide described below). A particularly preferred form of the present invention is a form in which no inorganic filler other than (e) component and (g) zinc oxide is used as the inorganic filler.
(E-1) Talc Talc is a kind of magnesium clay mineral, also called talc, and is generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O. Chemical composition, the SiO ₂ 58 to 66% 28 to 35% of MgO, comprising of H ₂ O to about 5%, as other minor _{components, Fe 2 O 3, Al 2} O 3, CaO, Na 2 O, K It is a substance containing ₂ O, TiO ₂ , P ₂ O ₅ , SO ₃ or the like. The pH changes from 8 to 11 due to impurities, and the specific gravity is about 2.7. The crystal structure is a three-layer structure having SiO _{2 on the} surface, MgO having a hydroxyl group in the _second layer, and SiO ₂ in the third layer. Actually, these crystals overlap several times.
(E-2) Clay Clay is a viscosity mineral mainly composed of aluminum silicate, and the chemical composition is SiO ₂ or SiO 30-80%, Al ₂ O ₃ 0.5-50%, It is a substance containing 0.1 to 35% of MgO or MgO ₂ and containing Fe ₂ O ₃ , FeO, CaO, Na ₂ O, K ₂ O, TiO ₂ , moisture, etc. as other minor components.

Further, from the viewpoint of the bloom-out suppressing effect and the mechanical properties of the composition, the average particle size of the component (e) is preferably 10 μm or less, and more preferably 10 μm to 0.4 μm. More specifically, the average (volume basis) particle size of (e-1) talc is more preferably 10 μm to 1 μm (laser diffraction method, measuring instrument: MT3000 manufactured by Nikkiso Co., Ltd.), (e− 2) The average particle size of the clay is more preferably 5 μm to 0.4 μm (microscan analyzer method, measuring instrument: microscan analyzer, Quantachrome Corp).
In addition, the average particle diameter of (e-1) talc is a value measured by a laser diffraction method. Moreover, the average particle diameter of (e-2) clay is a value measured by a microscan analyzer method.

(E) The compounding quantity of a component is 2-50 mass parts with respect to 100 mass parts of (a) component, and 5-30 mass parts is preferable. If it exceeds 50 parts by mass, the extrusion moldability and the injection moldability are remarkably deteriorated, the manufacturability is deteriorated and the mechanical properties are lowered. In addition, bloom out occurs. If it is less than 2 parts by mass, the bloom-out suppressing effect does not appear.
As talc and clay, commercially available products can be used.

  In the present invention, by setting the quantitative relationship between the component (d) and the component (e) within a specific range, it is possible to suppress bloom-out while maintaining compression set characteristics, oil resistance, flexibility and formability. The effect can be further enhanced. That is, when the component (d) is 1, the mass (mass) and the component (e) are preferably in the range of 0.8 to 30, and more preferably in the range of 3 to 14.

(F): Non-aromatic rubber softener (optional component)
In the thermoplastic elastomer composition of the present invention, optional components other than the components (a) to (e) can be added. For example, (f) a non-aromatic rubber softener can be used for the purpose of imparting flexibility and improving moldability of a thermoplastic elastomer composition.

  Examples of the component (f) include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms. Specific examples include butane, pentane, hexane, heptane, octane, and nonane. , Decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosan, docosan, tricosan, tetracosan, pentacosan, hexacosan, heptacosan, octacosan, nonacosan, triacontan, entriacontan, dotriacontan, N-paraffins (linear saturated hydrocarbons) such as pentatriacontane, hexacontane, heptacontane, isobutane, isopentane, neopentane, isohexane, isopentane, neohexane, 2 3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2, 2,3-trimethylbutane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2,2 , 3-trimethylpentane, isooctane, 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, isononane, 2-methylnonane, isodecane, isoundecane, isododecane, isotridecane, Isotetradecane, isopentadecane, isooctadecane, isonanodecane, Soeikosan, 4-ethyl-5-isoparaffins methyl octane (branched saturated hydrocarbons) and can include derivatives of these saturated hydrocarbons. These non-aromatic rubber softeners are preferably used in a mixture and are liquid at room temperature.

  Commercially available non-aromatic rubber softeners that are liquid at room temperature include NA Solvent (isoparaffinic hydrocarbon oil, trade name) manufactured by Nippon Oil & Fats, PW-90 (n) of Idemitsu Kosan Co., Ltd. -Paraffinic process oil (trade name), IP-solvent 2835 (synthetic isoparaffinic hydrocarbon, 99.8% by mass or more isoparaffin, trade name) manufactured by Idemitsu Petrochemical Co., Ltd., manufactured by Sanko Chemical Industry Co., Ltd. And neothiozole (n-paraffinic process oil, trade name).

  Moreover, a small amount of unsaturated hydrocarbons and derivatives thereof may coexist in the component (f). Unsaturated hydrocarbons include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2 -Ethylene hydrocarbons such as butene, 1-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, acetylene, methylacetylene, 1-butyne, 2- Examples thereof include acetylene hydrocarbons such as butyne, 1-pentyne, 1-hexyne, 1-octyne, 1-nonine and 1-decyne.

  (F) As for the compounding quantity of a component, 10-300 mass parts is preferable with respect to 100 mass parts of (a) component, More preferably, it is 50-200 mass parts. When the blending amount of the component (f) exceeds 300 parts by mass, bleeding tends to occur on the surface of the molded body made of the composition obtained, and mechanical properties and compression set properties are deteriorated.

(G): Zinc oxide (optional component)
Moreover, (g) zinc oxide can also be mix | blended with the thermoplastic elastomer composition of this invention for the purpose of further improving the bloomout suppression effect. (G) As for the compounding quantity of a component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, and it is still more preferable that it is 0.5-10 mass parts. Within this range, the bloom-out suppressing effect is further enhanced and the mechanical characteristics are also improved. If it exceeds 20 parts by mass, the mechanical properties deteriorate.
As the component (g), a commercially available product can be used.

Other ingredients:
In the thermoplastic elastomer composition of the present invention, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a crystal nucleating agent, an antiblocking agent, and an improvement in sealing properties are further added within the range not impairing the object of the present invention. Agents, mold release agents such as stearic acid and silicone oil, lubricants such as polyethylene wax, colorants, pigments, foaming agents, flame retardants and the like can be blended.

2. Production of Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention is produced by melt-kneading the components (a) to (e) and, if necessary, adding other components simultaneously or in any order. be able to. Preferably, it is a production method in which the above components (a) to (e) and other components as necessary are simultaneously added and melt-kneaded.

  The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be performed continuously by using an appropriate L / D twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the temperature of the melt-kneading is preferably 160 to 240 ° C., and it is preferable to take a kneading time of 5 to 20 minutes in order to sufficiently advance the crosslinking.

3. Applications The thermoplastic elastomer composition of the present invention is excellent in compression set characteristics and oil resistance in a high temperature region, and is excellent in flexibility and moldability, and particularly has no bloom out. It can be used for the following applications that are molded by a method, an injection molding method, a thermoforming method, an elastic-welding method, a compression molding method, or the like.

  Specific applications include automotive gaskets, lighting gaskets, 3D exchange blow clean air ducts, fulro seal hinge covers, belly pans (Robotek extrusion gaskets), cup holders, side brake grips, shift knob covers, seat adjustment knobs, IP skins. , Flapper door seal, wire harness grommet, rack and pinion boot, suspension cover boot (strut cover boot), glass guide, inner belt line seal, roof guide, trunk lid seal, molded quarter window gasket, corner molding, glass encap push (Robotech Extrusion), Food Seal, Glass Encapsulation ( Out molding), glass run channels, secondary seals, and the like. Industrial parts include curtain wall gaskets for high-rise buildings, window frame seals, adhesion to metals / reinforcing fibers, parking deck seals, expansion joints, expansion joints for earthquake countermeasures, residential window door seals (for example, coextrusion), Housing door seal, handrail skin, walking mat (sheet), foot rubber, washing machine drain hose (two-color molding with PP, etc.), washing machine lid seal, air conditioner motor mount, drain pipe seal (two-color molding with PP) Etc.), riser tubes, (PVC etc.) pipe joint packings, caster wheels, printer rolls, duct hoses, wires & cables, syringe shrimp gaskets and the like. Furthermore, as daily necessities / parts, speaker surround, hairbrush grip, razor grip, cosmetic grip / foot, toothbrush grip, daily necessities brush grip, broom tip, kitchenware grip, measuring spoon grip, branch cutting scissor grip, glass heat-resistant container lid Garden grips, scissor grips, stapler grips, computer mice, golf bag parts, wall-coated iron grips, chainsaw grips, screwdriver grips, hammer grips, electric drill grips, grinder grips, alarm clocks, etc.

In addition, vehicle parts such as weather seals, brake parts such as cups, coupling discs and diaphragm cups, and covers, boots such as constant speed joints and rack transmission joints, tubes, sealing gaskets, hydraulic or pneumatic Actuating device parts, O-rings, pistons, valves, valve seats, valve guides and other elastic polymer-based parts, or elastic polymers combined with other materials such as metal / plastic combination materials, transmission belts, etc. It is done.
Among the above, various products included in the category of skin materials that are visible by touching or being exposed to human hands, in particular, skin materials for automobiles (interior / exterior members), are preferable for use in the present invention.

  EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, the manufacturing method of the test piece used by the Example and the comparative example, the evaluation method, and a raw material are as follows.

  Each component was put into a pressure kneader type mixer having a capacity of 3 L at a component ratio (parts by mass) shown in Tables 1 to 6, melt kneaded at a kneading temperature of 180 ° C., and a kneading time of 10 to 30 minutes, and pelletized. Next, test pieces were prepared from the obtained pellets by press molding, extrusion molding, and injection molding, and subjected to respective tests.

Evaluation method (1) Specific gravity:
In accordance with JIS K 7112, measurement was performed using a 1 mm thick press sheet as a test piece.
(2) Hardness:
In accordance with JIS K 7215, a 6.3 mm thick press sheet was used as a test piece, and the durometer hardness was measured using type A.
(3) Tensile strength, 100% modulus, elongation:
In accordance with JIS K 6301, a 1 mm thick press sheet was punched into a No. 3 dumbbell as a test piece and used. The tensile speed was 500 mm / min.
(4) Compression set:
In accordance with JIS K 6262, a 6.3 mm thick press sheet was used as a test piece. The measurement was performed at 120 ° C. for 22 hours under the condition of 25% deformation.
(5) Volume swelling rate (%) (Evaluation of oil resistance):
In accordance with JIS K 6258, a 2 mm thick press sheet was used as a test piece. The volume swelling rate after immersion in IRM # 903 was measured at 120 ° C. for 72 hours.
(6) Manufacturability:
Manufacturability in the pellet manufacturing process was evaluated according to the following criteria.
○: A kneaded product can be formed and discharged without contamination of the kneading tank.
X: A kneaded mixture cannot be formed and / or the kneading tank is significantly contaminated.
(7) Extrudability (appearance evaluation):
A flat plate having a width of 50 mm and a thickness of 0.5 mm was extruded at 200 to 220 ° C. with a 40 mm extruder, the surface appearance and shape of the molded product were observed, and evaluated according to the following criteria.
○: The mirror surface property of the molded product surface is good, the shape is stable, and no flaws are generated.
X: The molded article surface has at least one of the following problems: poor specularity, generation of a pattern, inadequate edges, conspicuous spots, and occurrence of scouring.
(8) Injection moldability (appearance evaluation):
With a 120t injection molding machine, the mold temperature is set to 30 ° C., a 130 mm × 130 mm × 2 mm sheet is injection molded at 200 to 220 ° C., and the appearance of the molded product is visually observed to check for the occurrence of flow marks, sink marks, and blisters. Evaluation was made according to the following criteria.
◯: The surface of the molded product has good specularity, and no flaws are generated.
X: A pattern due to peeling of a flow mark or material occurs on the surface of the molded product. Or noticeably.
(9) Bloom out (appearance, scratch resistance):
The mold temperature was set to 30 ° C. with a 120-ton injection molding machine, a 130 mm × 130 mm × 2 mm sheet was injection molded at 200 to 220 ° C., and the sheet surface after standing for 30 days at 23 ° C. was visually observed. evaluated.
A: There is no visible powder blowing on the surface. In addition, even if the surface is rubbed with a nail, no scraped material is generated.
◯: There is no powder spray visible on the surface, but some cloudiness is observed on the surface.
Δ: Cloudiness is observed on the surface, and scraped material is generated when the surface is rubbed with a nail.
X: There is powder powder that can be clearly seen, and scraped material is generated when the surface is rubbed with a nail.

Used raw material (a) component:
Nordel MG 47085 (manufactured by DuPont Dow Elastomer Japan): ethylene / propylene / ethylidene norbornene copolymer rubber (EPDM) synthesized by a gas phase polymerization method using a metallocene catalyst, specific gravity: 0.86, Mooney viscosity ML _{1 + 4} (125 ° C.): 80 (ASTM D-1646), ethylene content: 69.5%, ENB content: 4.5%, carbon black content: 30 phr
Nordel IP 4760P (manufactured by DuPont Dow Elastomer Japan): ethylene / propylene / ethylidene norbornene copolymer rubber (EPDM) synthesized by a solution polymerization method using a metallocene catalyst, specific gravity: 0.88, Mooney viscosity ML _{1 + 4} (125 ° C.): 60 (ASTM D-1646), ethylene content: 67%, ENB content: 4.9%, carbon black content: 0 phr, crystallinity by DSC: 10% by weight
Nordel IP 4770R (manufactured by DuPont Dow Elastomer Japan): ethylene / propylene / ethylidene norbornene copolymer rubber (EPDM) synthesized by solution polymerization method using metallocene catalyst, specific gravity: 0.88, Mooney viscosity ML _{1 + 4} (125 ° C.): 70 (ASTM D-1646), ethylene content: 70%, ENB content: 4.9%, carbon black content: 0 phr, crystallinity by DSC: 13% by weight
(B) Component:
Novatec BC8 (manufactured by Nippon Polychem Co., Ltd.): block copolymer of propylene and ethylene mainly composed of crystalline polypropylene, density: 0.902 g / cm ³ , MFR (230 ° C., 21.18 N load): 1. 8g / 10min, melting point 160 ° C
(C) Component:
Tackirol 201 (manufactured by Taoka Chemical Co., Ltd.): C ₈ alkylphenol formaldehyde resin, mass average molecular weight: 2,500 to 4,000
(D) Component:
Anhydrous stannous chloride (manufactured by Showa Kako Co., Ltd.)
(D) Comparative component:
Hypalon 40 (manufactured by DuPont Elastomer Co., Ltd.): chlorosulfonated polyethylene, density 1.18 g / cm ³ , chlorine content 30%, sulfur content 1.0%.
(E) Component:
(E-1):
RT-2 (manufactured by Katsumiyama Mining Co., Ltd.): talc, average (volume basis) particle size of 3 μm by laser diffraction method (MT3000 manufactured by Nikkiso Co., Ltd.)
(E-2):
No. 80 (manufactured by Shiroishi Calcium Co., Ltd.): dry classification clay, average particle diameter 0.65 μm by microscan analyzer method (measuring instrument: microscan analyzer, Quantachrome Corp)
(E) Comparative component:
Ns400 (manufactured by Nitto Flour Industry Co., Ltd.): Calcium carbonate, average particle size 1.7 μm
VN3 (manufactured by Tosoh Silica Co., Ltd.): silicon dioxide, bulk specific gravity 135 g / l, primary particle diameter 16 nm
CR-90 (manufactured by Ishihara Sangyo Co., Ltd.): Titanium dioxide, specific gravity 4, average particle size 0.25 μm
(F) Component:
PW-90 (Idemitsu Kosan Co., Ltd.): Paraffin oil (g) Ingredients:
2 types of zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd.)

Examples 1-27 and Comparative Examples 1-24
The component ratio (parts by mass) and evaluation results of each example are shown in Tables 1 to 3, and the component ratio (parts by mass) and evaluation results of each comparative example are shown in Tables 4 to 6.

As is apparent from Tables 1 to 3, the thermoplastic elastomer composition of the present invention had good characteristics (Examples 1 to 27).
On the other hand, as shown in Tables 4 to 6, the compositions of Comparative Examples 1 and 2 in which the blending amount of the component (b) is less than the lower limit of the present invention are inferior in oil resistance, manufacturability and moldability, and the upper limit The compositions of Comparative Examples 3 to 4 exceeding the range are inferior in compression set characteristics. Moreover, the composition of Comparative Examples 5-6 whose compounding quantity of (c) component is less than the lower limit of this invention is inferior to a compression set characteristic and oil resistance, and is a composition of Comparative Examples 7-8 exceeding the upper limit. The product is inferior in manufacturability and moldability. Moreover, the composition of Comparative Examples 9-10 whose compounding quantity of (d) component is less than the lower limit of this invention is inferior to a compression set characteristic and oil resistance, and is a composition of Comparative Examples 11-12 exceeding the upper limit. The product is inferior in manufacturability, moldability, and blooming suppression effect. As the component (d), the compositions of Comparative Examples 13 to 14 using a component (chlorosulfonated polyethylene) that acts as a halogen donor other than tin chloride are inferior in moldability and bloom-out suppression effect. Moreover, the composition of Comparative Examples 15-16 in which the blending amount of the component (e) is less than the lower limit of the present invention is inferior in bloom-out suppressing effect, and the compositions of Comparative Examples 17-18 exceeding the upper limit are tensile. Properties, manufacturability, moldability, and blooming suppression effect are poor. The compositions of Comparative Examples 19 to 24 use inorganic fillers other than talc and clay as the component (e). These compositions were inferior in bloom-out suppression effect or inferior in manufacturability, and the desired effect was not obtained.

Examples 28-29
Composition of each component shown in Example 2 and Example 3 (as a skin material) and talc-reinforced polypropylene (100 parts by mass of polypropylene (Novatec BC8 (manufactured by Nippon Polychem Co., Ltd.)) as a base material (core material) : Block copolymer of propylene and ethylene mainly composed of crystalline polypropylene, density: 0.902 g / cm ³ , MFR (230 ° C., 21.18 N load): 1.8 g / 10 min, melting point 160 ° C.), A co-extrusion test was conducted with talc (melt-kneaded product with 20 parts by mass of RT-2 (manufactured by Katsumiyama Mining Co., Ltd.)).
The coextrusion molding conditions are as follows.
The thickness of the skin material was about 400 μm, the thickness of the core was about 2 mm, and co-extrusion was performed from two 40 mm single-screw extruders (dies 200 ° C., cylinders 160 to 200 ° C.).
When the bloom-out of the obtained laminate skin portion was evaluated in the same manner as in the above example (23 ° C. × 30 days), all were evaluated as ◎.

Claims (4)

(A) 100 parts by mass of ethylene / α-olefin / non-conjugated diene copolymer rubber;
(B) 20 to 250 parts by mass of crystalline polypropylene,
(C) 2-30 parts by mass of a non-halogen phenol resin crosslinking agent,
(D) 0.1-6 parts by mass of tin chloride, and (e) at least one inorganic filler selected from the group consisting of talc and clay, 2-50 parts by mass of a thermoplastic elastomer composition, .   2. The thermoplastic elastomer composition according to claim 1, wherein a mass ratio of the component (d) and the component (e) is 1.0 / 0.8 to 30 as the former / the latter.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the component (e) has an average particle size of 10 µm or less.   The molded object formed by shape | molding the thermoplastic elastomer composition in any one of Claims 1-3.