Technical field
[0001]The present invention relates to an olefinic thermoplastic elastomer composition and use thereof.
BACKGROUND
[0002]Olefinic thermoplastic elastomers, recycling lightweight is easy, also because it does not generate toxic gases during incineration, energy conservation, resource conservation, more recently, from the viewpoint of global environmental protection, especially of vulcanized rubber substitute auto parts, industrial machinery parts, electric and electronic parts, are widely used in building materials such as goods. As an example of such automobile parts include glass run channel.
[0003]
　Glass run channel is a sealing material provided between the window glass and the window frame (guide member), the sliding of the glass is required, the conventional are those rich in silicone additive .
[0004]
　However, in the manufacturing process of the glass run channel, the extruded linear sealing member is inserted into the mold of the corner portion, it is carried out adhesion of the molding and the straight portion of the corner portion by injection molding.
[0005]
　Patent Document 1, glass run channel body adhered glass sliding layer is high density polyethylene, although the configuration including the non-polar elastomers and lubricants (silicone masterbatch) is described, reference is made to adhesion of the corner portion It has not been.
[0006]
　Patent Document 2, the glass run channel comprising a composition containing silylated polyolefin thermoplastic elastomer has excellent adhesion and abrasion resistance of the substrate layer and the skin layer is described.
CITATION
Patent Document
[0007]
Patent Document 1: JP-A-10-193985 discloses (in particular Example 8)
Patent Document 2: JP 2015-189088 JP
Summary of the Invention
Problems that the Invention is to Solve
[0008]
　The present inventors have studied the adhesion of the corner portion of the molded product obtained from the olefinic thermoplastic elastomer composition comprising a silicone-based additive, the formulation containing a large amount of silicone additive, a problem in the adhesion of the corner portion it was found that may occur. Further, when formulating a number of silicone-based additive, it was found that low-temperature impact strength deteriorates.
[0009]
　An object of the present invention is to provide an olefinic thermoplastic elastomer composition capable of producing a molded article of glass run channel and the like having both adhesion and sliding of the corner portion of the obtained molded article.
Means for Solving the Problems
[0010]
　The gist of the present invention is as follows.
(1) Ethylene-alpha-olefin-non-conjugated polyene copolymer (A) and 5 to 30 parts by weight, a density of 0.90 g / cm 3 or more, 0.92 g / cm 3 or less is crystalline olefin resin ( B) 20 to 40 parts by weight, density 0.94 g / cm 3 or more, 0.97 g / cm 3 and high-density polyethylene (C) 20 to 40 parts by weight or less, ethylene and carbon atoms 3 12 ethylene · alpha-olefin copolymer (D) 5 ~ 12 parts by weight consisting of alpha-olefin, a silicone compound (E) 5 ~ 9 parts by weight of a thermoplastic elastomer composition comprising (however, (a), (B ), (C), and total 100 parts by mass of (D) and (E)).
(2) The thermoplastic elastomer composition according to the silicone compound (E) comprises a silicone oil and high molecular weight silicones (1).
(3) an ethylene-alpha-olefin copolymer (D) is a thermoplastic elastomer composition according to the comprising one or more selected from ethylene octene rubber and ethylene-butene rubber (1) or (2).
(4) the (1) to (3) Thermoplastic elastomer automotive glass run channel formed with the composition according to any one of.
The invention's effect
[0011]
　According to the thermoplastic elastomer composition of the present invention, to achieve both adhesion and sliding of the corner portion of the molded article obtained, and it is possible to produce shaped bodies such as glass run channel excellent in low-temperature impact strength .
　High density polyethylene, and ethylene-octene rubber, it can also maintain the sliding characteristics by blending an ethylene-based resin of the ethylene-alpha-olefin copolymer such as ethylene-butene rubber is the inability to predict those skilled in the art.
DESCRIPTION OF THE INVENTION
[0012]
　The following specifically describes the thermoplastic elastomer composition of the present invention.
[0013]
　The thermoplastic elastomer composition of the present invention, the ethylene-alpha-olefin-non-conjugated polyene copolymer (A), crystalline olefin resin (B), high-density polyethylene (C), the ethylene-alpha-olefin copolymer contains (D) and the silicone compound (E).
[0014]
Ethylene-alpha-olefin-non-conjugated polyene copolymer (A)]
　ethylene used in the present invention alpha-olefin-non-conjugated polyene copolymer (A), and ethylene, other than ethylene alpha-olefin, preferably and α- olefin having 3 to 20 carbon atoms, non-conjugated polyene, a copolymer preferably comprising a non-conjugated diene.
[0015]
　The copolymer (A) is "polymer production process (Co. Kogyo Chosakai, issued p.309 ~ 330)" or JP-A-9-71617 discloses according to the applicant of the application, JP-A 9-71618 JP, Hei 9-208615, JP-a No. 10-67823, JP-a No. 10-67824, JP-a No. 10-110054, JP-WO2009 / 081792 pamphlet, such as those described in WO2009 / 081794 pamphlet it can be produced by a conventionally known method such as that.
[0016]
　Ethylene-alpha-olefin-non-conjugated polyene copolymer used in the present invention as preferably olefin polymerization catalyst used in the preparation of (A), for example,
vanadium (V), zirconium (Zr), titanium (Ti) and transition metal compounds such as organic aluminum compounds known Ziegler catalyst consisting a (organoaluminum oxy compound);
metallocene compound of a transition metal selected from group 4 of the periodic table of the elements, the organoaluminum oxy-compound or the ionizing ionic known metallocene catalyst comprising a compound, for example a metallocene catalyst disclosed in JP-a-9-40586;
known metallocene catalyst comprising a specific transition metal compound, and a co-catalyst such as boron compounds, e.g., WO2009 / 072553 catalyst metallocene is described in pamphlet ;
And specific transition metal compounds, organometallic compounds, is described in the transition metal compound catalyst, for example, Japanese 2011-52231 JP react with an organoaluminum oxy-compound or the transition metal compound comprising a compound forming an ion pair and that the transition metal compound catalyst;
and the like. In particular the use of metallocene catalysts, the distribution of diene becomes uniform can introduce diene obtain high crosslinking efficiency be less, and particularly preferred because it can reduce the chlorine content of the catalyst-derived because of high catalytic activity.
[0017]
　Ethylene-alpha-olefin-non-conjugated polyene copolymer (A) used in the present invention, the structural units derived from ethylene, a total of 100 mole% of the structural unit of carbon atoms derived from the 3 ~ 20 alpha-olefin in the medium, the content of structural units derived from ethylene (Ea mol%) is usually 40 to 90 mol%, preferably 40 to 80 mol%, structural units the number of carbon atoms derived from the 3 ~ 20 alpha-olefin content is usually 60 to 10 mol%, preferably 60 to 20 mol%.
[0018]
　And the content of the structural units derived from ethylene, when the content of the structural unit the number of carbon atoms derived from the 3 ~ 20 alpha-olefin in the range, excellent mechanical properties, rubber elasticity, cold resistance and processability and it has the added advantage that the resulting thermoplastic elastomer composition. The content of structural units derived from ethylene 90 mol%, the content of the structural units having a carbon number derived from the 3 ~ 20 alpha-olefin is 10 mol% or more, the thermoplastic composition is flexible, rubber elasticity at low temperatures, excellent processability. The content of structural units derived from ethylene of 40 mol% or more, the content of the structural units having a carbon number derived from the 3 ~ 20 alpha-olefin is 60 mol% or less, the thermoplastic composition mechanical properties, excellent rubber elasticity at high temperature. The content of the ethylene structural unit of ethylene-alpha-olefin-non-conjugated polyene copolymer (A), and the content of the alpha-olefin structural unit 13 can be measured by C-NMR
[0019]
　The α- olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-Mechirudesen 1,11 Mechirudodesen - such as 1,12-ethyl tetradecene-1 and the like. Of these, propylene, 1-butene, 4-methylpentene-1,1-hexene, 1-octene are preferable, propylene is preferred. These α- olefins, alone or in combination of two or more are used.
[0020]
　As the non-conjugated polyene, specifically, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5 - dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene chain non-conjugated dienes; methyl tetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene , 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene , Cyclopentadiene, cyclic non-conjugated dienes such as norbornadiene; 2,3-isopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene such trienes such as 8-methyl-1,7-nonadiene and the like. Of these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene and 4-ethylidene-8-methyl-1,7-nonadiene preferred.
[0021]
　Ethylene-alpha-olefin-non-conjugated polyene copolymer (A) according to the present invention, 135 intrinsic viscosity measured in decalin ° C. [eta] is generally 0.6 ~ 6.5 dl / g, preferably 0 .8 ~ 6.0dl / g, and particularly preferably in the range of 0.9 ~ 5.5dl / g. When the intrinsic viscosity measured in a 135 ° C. decalin [eta] is in the range, it is excellent in terms of mechanical properties, rubber elasticity and processability balance excellent thermoplastic elastomer obtained.
[0022]
　It iodine value of the ethylene-alpha-olefin-non-conjugated polyene copolymer (A) according to the present invention is usually 2 ~ 50 g / 100 g, preferably 5 ~ 40 g / 100 g, more preferably 7 ~ 30 g / 100 g It is desirable Iodine value is below this range, reduces the cross-linking efficiency of thermoplastic elastomer, the rubber elasticity is lowered. Iodine value exceeds this range, crosslink density becomes too high to decrease elongation, there is a case where balance of physical properties may be deteriorated.
[0023]
　Ethylene-alpha-olefin-non-conjugated polyene copolymer (A) according to the present invention, the molecular weight distribution measured by GPC (Mw / Mn) is usually 1.5 to 50, preferably from 1.8 to 30 by weight, more preferably from 2.0 to 6. The molecular weight distribution becomes small content of low molecular weight components and below this range, processability is lowered. When the molecular weight distribution exceeds this range, the content of the low molecular weight component increases, fogging resistance is deteriorated.
[0024]
　Mooney viscosity [ML ethylene-alpha-olefin-nonconjugated polyene copolymer according to the present invention (A) 1 + 4 (100 ° C.)] is preferably 15 to 400. FIG. When Mooney viscosity is within this range, excellent processability balance between mechanical properties.
[0025]
[Crystalline olefin resin (B)]
　As the crystalline olefinic resin used in the present invention (B), preferably include peroxide-decomposition type olefin plastic.
[0026]
　The peroxide-decomposition type olefin plastic, mixed with peroxide, reducing the molecular weight by thermal decomposition by kneading under heating, refers to olefin plastic fluidity of the resin is increased, for example, isotactic polypropylene, a copolymer of propylene with a small amount of another α- olefin, such as propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene it can be mentioned copolymers.
[0027]
　Examples of the peroxide-decomposition type olefin plastic include homopolymers or copolymers of α- olefin having 2 to 20 carbon atoms.
[0028]
　The said α- olefins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1 - pentene, 1-octene, and the like.
[0029]
　Examples Specific examples of (b) peroxide decomposition type olefin plastics, such as (co) polymers are exemplified below.
(1) a propylene homopolymer
(2) propylene and random copolymers with other α- olefin 10 mol% or less
(3) propylene and a block copolymer of the following other α- olefin 30 mole%
( 4) 1-butene homopolymer
(5) 1-butene random copolymer with other α- olefin 10 mol% or less
(6) 4-methyl-1-pentene homopolymer
(7) 4-methyl 1-pentene random copolymer of the following other α- olefin 20 mol%
[0030]
　Crystalline olefin resin (B) used in the present invention, 230 ° C., a melt flow rate measured under a load 2.16kg (MFR: ISO1133,230 ℃, load 2.16 kg) is usually 5 ~ 150 g / 10 min , preferably in the range of 30 ~ 100 g / 10 min.
[0031]
　The density is usually 0.90 g / cm 3 or more and 0.92 g / cm 3 or less, preferably 0.91 g / cm 3 or more, 0.92 g / cm 3 or less. Here, the density is the density measured by pycnometer method (JIS K7112 B method).
[0032]
　The crystalline olefin resin used in the present invention (B), alpha-olefin and a copolymer of a small amount, for example 10 mole% or less of other polymerizable monomers, such as ethylene-vinyl acetate copolymer, ethylene · acrylic acid copolymer, may be used ethylene-methacrylic acid copolymers.
[0033]
　The crystalline olefin resin used in the present invention (B), polypropylene is particularly preferred.
[0034]
　Examples of commercial products of the polyolefin resin used in the present invention, for example, Prime Polypro (Co., Ltd. Prime Polymer), Mirason (KK Prime Polymer), Suntec (manufactured by Asahi Kasei Chemicals), Novatec (Japan Polypropylene ( Ltd.)), Sumitomo Noblen (manufactured by Sumitomo chemical Co.), Evolue (KK Prime polymer), HI-ZEX (KK Prime polymer), polymethylpentene resin (TPX) (manufactured by Mitsui chemicals Co., Ltd. ), and the like.
[0035]
　Crystalline olefin resin (B) used in the present invention, the ethylene-alpha-olefin-non-conjugated polyene copolymer with (A), may be present in completely or partially crosslinked thermoplastic elastomer.
[0036]
　Such complete or of partially crosslinked thermoplastic elastomer, the partially crosslinked thermoplastic elastomer, for example,
(1) (a) peroxide-crosslinkable olefin copolymer rubber, (b) peroxide-decomposition type olefin plastic ( mixture consisting of a crystalline olefin resin (B)), or (a a) a peroxide-crosslinkable olefin copolymer rubber, (b) peroxide-decomposition type olefin plastic (crystalline olefin resin (B) and), (c) a peroxide non-crosslinked rubber-like material and / or (d) a mixture comprising a mineral oil-based softening agent, obtained by dynamically heat-treated in the presence of an organic peroxide, partially crosslinked thermally thermoplastic elastomer,
(2) (a) and the peroxide-crosslinkable olefin copolymer rubber, (b) peroxide decomposition type olefin A system of plastic (crystalline olefin resin (B)), (c) a peroxide non-crosslinked rubber-like material and / or (d) a mixture comprising a mineral oil-based softening agent, dynamically in the presence of an organic peroxide the rubber composition is crosslinked obtained by heat treatment, (e) a crystalline olefinic resin (B) allowed the uniformly mixed, partially crosslinked thermoplastic elastomers, and the like.
[0037]
　Mixed with said (c) peroxide non-crosslinked rubber-like material, for example polyisobutylene, butyl rubber, atactic polypropylene, propylene content as such at least 50 mol% propylene · alpha-olefin copolymer rubber, a peroxide was not crosslinked be kneaded under heating, the flowability refers to gum hydrocarbon does not decrease.
[0038]
　Wherein A of (d) a mineral oil softening agent, when rolling ordinary rubber, weakening the intermolecular action force of the rubber, as well as to facilitate processing, or aid carbon black, a dispersion such as white carbon, or flexibility and allowed reducing the hardness of vulcanized rubber, elastic in petroleum fractions having a high boiling point which are used for the purpose of increasing the paraffinic, naphthenic, are distinguished in the aromatic system, or the like. Mineral oil softening agents such as paraffinic process oils, naphthenic process oils and the like.
[0039]
　In the thermoplastic elastomer, (b) peroxide-decomposition type olefin plastic (a) a peroxide-crosslinkable olefin copolymer mass compounding ratio of the rubber ((b) / (a)) is usually 90/10 3 to 10 / 90, preferably in the range of 70 / 30-15 / 85.
[0040]
　Further, as the rubber, when used in combination other rubber and ethylene-alpha-olefin-non-conjugated polyene copolymer (A), other rubber, the total amount of the peroxide-decomposition type olefin plastic and rubber 100 relative to the weight parts, usually 40 parts by weight or less, preferably in a proportion of 5 to 20 parts by weight.
[0041]
　The thermoplastic elastomer preferably used in the present invention, the crystalline polypropylene, consists of ethylene-alpha-olefin-non-conjugated diene copolymer, present in a state where they are partially crosslinked in the thermoplastic elastomer, and mass compounding ratio of the crystalline polypropylene and the rubber (crystalline polypropylene / rubber) is an olefin-based thermoplastic elastomer in the range of 70 / 30-10 / 90.
[0042]
　More specific examples of the olefin thermoplastic elastomer preferably used in the present invention, the rubber comprising an ethylene-propylene-diene copolymer (a-1) 30 ~ 90 parts by weight with crystalline polypropylene (b-1) 70-10 parts by weight [total amount of the components (a-1) and (b-1) is a 100 parts by weight] and the rubber (a-1) other than the rubber (c) and / or mineral oil type a mixture of a softener (d) 5 ~ 150 parts by weight, obtained by dynamically heat-treated in the presence of an organic peroxide, said rubber (a-1) can be mentioned partially crosslinked thermoplastic elastomer It is.
[0043]
　Examples of the organic peroxides, specifically, dicumyl peroxide, di -tert- butyl peroxide, 2,5-dimethyl-2,5-di - (tert-butylperoxy) hexane, 2,5-dimethyl-2, 5-di - (tert- butylperoxy) hexyne-3,1,3-bis (tert- butylperoxy-isopropyl) benzene, 1,1-bis (tert- butylperoxy) -3,3,5-trimethylcyclohexane, n - butyl-4,4-bis (tert- butylperoxy) valerate, benzoyl peroxide, p- chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert- butyl peroxybenzoate, tert- butylperoxy isopropyl carbonate, diacetyl peroxide Lauroyl peroxide, etc. tert- butyl cumyl peroxide.
[0044]
　Of these, odor, in terms of scorch stability, 2,5-dimethyl-2,5-di - (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di - (tert-butyl peroxy) hexyne 3,1,3-bis (tert- butylperoxy-isopropyl) benzene, 1,1-bis (tert- butylperoxy) -3,3,5-trimethylcyclohexane, n- butyl-4,4-bis (tert- butylperoxy) valerate are preferred, 1,3-bis (tert- butylperoxy-isopropyl) benzene is most preferred.
[0045]
　Organic peroxides, based on the total amount of 100 parts by mass of the crystalline polyolefin and rubber, generally 0.01 to 5 parts by weight, preferably used in a ratio of 0.05 to 3 parts by weight.
[0046]
　Upon crosslinking treatment by the organic peroxide, sulfur, p- quinone dioxime, p, p'-dibenzoyl quinone dioxime, N- methyl -N, 4-di-nitroso aniline, nitroso benzene, diphenyl guanidine, trimethylol propane, N , N'-m-phenylene maleimide, divinylbenzene, triallyl cyanurate, crosslinking aids such as triallyl isocyanurate or ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, it can be blended polyfunctional methacrylate monomers such as allyl methacrylate, vinyl butyrate, and polyfunctional vinyl monomers such as vinyl stearate.
[0047]
　The use of compounds as described above, uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferable. Divinyl benzene, easy to handle, said has good compatibility with the crystalline polyolefin and the rubber which is a main component of the crosslinked treated and has a function of solubilizing the organic peroxide, organic peroxide dispersant to act as, a homogeneous crosslinking effect by heat treatment, balanced thermoplastic elastomer balance between fluidity and physical properties is obtained.
[0048]
　Wherein the crosslinking aid or the polyfunctional vinyl monomer such as, with respect to said object to be crosslinked treated whole 100 parts by weight, used in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight It is preferred. When the amount of the crosslinking assistant or polyfunctional vinyl monomer is more than 5 parts by mass, when the amount of the organic peroxide is large, the crosslinking reaction proceeds too rapidly, thermoplastic elastomer obtained is flowable inferior, whereas, if the amount of the organic peroxide is small, crosslinking auxiliary and polyfunctional vinyl monomer, remains as unreacted monomer in the thermoplastic elastomer, thermoplastic elastomer, thermally during processing molding changes in the physical properties or caused by history. Therefore, crosslinking auxiliary and polyfunctional vinyl monomer should not be excessively blended.
[0049]
　It said "dynamically heat treating" refers to kneading in a molten state the components as described above.
[0050]
　The kneading apparatus, conventionally known kneading apparatus, for example, open type mixing roll, non-open type Banbury mixer, extruder, kneader, continuous mixer or the like is used. Of these, non-open type kneading apparatus is preferable, kneading, a nitrogen gas, is preferably carried out in an atmosphere of an inert gas such as carbon dioxide.
[0051]
　The kneading temperature is generally 0.99 ~ 280 ° C., preferably 170 ~ 250 ° C., the kneading time is usually 0.5 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is, 10 ~ 50,000sec as shear rate -1 , preferably 100 ~ 20,000Sec -1 is determined in the range of.
[0052]
　Incidentally, fully crosslinked thermoplastic elastomer, the (1) can be prepared by varying the thermoplastic amount of the organic peroxide according to the process for the preparation of elastomers, conditions such as kneading time (2) .
[0053]
[High-density polyethylene (C)]
　high-density polyethylene used in the present invention (C) is a component for achieving both adhesion and sliding properties, density is generally 0.940 ~ 0.970 g / cm 3 , preferably ～ 0.965 g 0.945 / Cm 3 is. Here, the density is the density measured by pycnometer method (JIS K7112 B method).
[0054]
　The high-density polyethylene (C), for example, ethylene homopolymer or ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, ethylene-4-methyl-1-pentene, ethylene and ethylene-1-octene - made of α- olefin copolymer can be used. The polymerization catalyst used for the polymerization of these polymers, for example, a known Ziegler, multi-site catalyst such as Philips system, zirconocene, titanocene, hafnocene (collectively, metallocene) Kaminsky catalyst such as, post-metallocene catalyst It includes highly active single-site catalyst such as.
[0055]
　The melting point of the high-density polyethylene (C), from the viewpoint of adhesiveness, is usually 110 ~ 0.99 ° C., preferably 115 ~ 0.99 ° C., more preferably 120 ~ 140 ° C.. Here the melting point using a differential scanning calorimeter (DSC), a sample of about 10mg heating rate 10 ° C. / temperature was increased from -40 ℃ to 200 ° C. in minutes, after holding for 1 minute at 200 ° C., the cooling rate It was cooled at 10 ° C. / min to -40 ° C., is again, to 200 ° C. at a heating rate of 10 ° C. / min was determined from the measured thermogram when the temperature was raised crystal melting peak temperature (Tm).
[0056]
　The melt flow rate of the high-density polyethylene (C) (MFR), from the viewpoint of sliding property improving, preferably 0.01 ~ 25 g / 10 min, more preferably 0.01 to 15. Here, MFR is a value measured in accordance with ASTM D1238, the measurement conditions were 190 ° C., a 2.16kg load.
[0057]
Ethylene-alpha-olefin copolymer (D)]
　ethylene used in the present invention alpha-olefin copolymer (D) is a component for increasing the low-temperature impact strength of a molded article to be obtained, in amorphous There, and a melt flow rate (MFR), from the viewpoint of sliding property improving, preferably 0.05 ~ 15 g / 10 min, more preferably 0.05 to 10. Here, MFR is a value measured in accordance with ASTM D1238, the measurement conditions were 230 ° C., a 2.16kg load.
[0058]
　The melt flow rate of the ethylene · alpha-olefin copolymer (D), when the polymerization of ethylene and alpha-olefin which is a raw material, be adjusted to be within a desired range by adjusting the degree of polymerization as appropriate it is possible.
[0059]
　The ethylene · alpha-olefin copolymer (D) has a density of 0.85 ~ 0.92 g / cm 3 is preferably used what is. It is possible to increase the tensile breaking elongation and impact resistance of the molded article obtained by the density in such a range. The density in the present invention means a JIS K 7112 "Density measurement method of specific gravity of plastics" measured values in conformity with. To adjust the specific gravity within the range of above may be appropriately adjusting the ratio of the raw material monomer used in the polymerization of ethylene · alpha-olefin copolymer (D).
[0060]
　The ethylene-alpha-olefin copolymer (D), such as ethylene-octene rubber, ethylene-butene rubber.
[0061]
　As a method for producing the ethylene · alpha-olefin copolymer (D), a known polymerization method using a catalyst for olefin polymerization is used. Ethylene-alpha-olefin copolymer (D), for example, Ziegler-Natta catalysts, with complex-based catalyst such as a metallocene complex and non-metallocene complex, solution polymerization, slurry polymerization, high pressure ionic polymerization method, a vapor phase polymerization, addition, bulk polymerization method using a radical initiator is preferably produced by a solution polymerization method. Among these methods of polymerizing monomers using a Ziegler-Natta catalyst or complex catalyst, or the use of a process for polymerizing monomers in the presence of a metallocene catalyst particularly preferred.
[0062]
Silicone compound (E)]
　The silicone compound used in the present invention (E) is mainly added for sliding resistance reduction.
[0063]
　As the silicone compound used in the present invention, for example, silicone oil, high molecular weight silicones (silicone gum), although silicone powder and the like, (E-1) silicone oil, preferably a kinematic viscosity 5000 mm 2 / s less than the silicone oil and (E-2) is preferably used in combination with a high molecular weight silicone (silicone gums).
[0064]
　(E-1) mass mixing ratio of the silicone oil and (E-2) high molecular weight silicones (silicone gums) ((E-1) / (E-2)) is usually 90 / 10-10 / 90, preferably is in the range of 75 / 25-25 / 75.
[0065]
　Examples of the silicone oil, dimethyl silicone oil, phenylmethyl silicone oil, alkyl silicone oil, fluorosilicone oil, tetramethyl tetraphenyl trisiloxane, modified silicone oil, and the like.
[0066]
　The high molecular weight silicones (silicone gum), usually, the weight average molecular weight used 100,000 or more. The weight average molecular weight of the silicone gum is preferably 100,000 to 800,000, more preferably 450,000 to 650,000. As the high molecular weight silicones (silicone gum), those of non-crosslinkable are preferred.
[0067]
　The weight average molecular weight, for example, can be measured under the following conditions of GPC (gel permeation chromatography).
[0068]
[Measurement conditions for the gel permeation chromatography (GPC)]
Equipment: manufactured by Tosoh Corporation HLC-8120
Column: Polymer Laboratories Ltd. PL 10u Mixed B (7.5mm I.D × 30cm × 2)
Detector: differential refractometer rate detector (RI / internal)
solvent: toluene (special grade)
temperature: 40 ° C.
flow rate: 1.0 mL / min
injection volume: 110 [mu] L
concentration: 0.1 wt%
calibration samples: monodisperse polystyrene
calibration method: polystyrene conversion
[0069]
　Incidentally, GPC measurement of the high molecular weight silicone in the masterbatch (silicone gum) in advance in the master batch, for example by performing the following process, after separating the polypropylene with high molecular weight silicones (silicone gums), the obtained polymer weight it can be carried out by measuring the silicone (silicone gums).
[0070]
[Separation between high molecular weight silicones (silicone gums) and polypropylene]
　First, a sample (master batch) and 0.05g weighed, 0.1 g / L BHT (dibutylhydroxytoluene) was added to the addition of xylene 10 mL, 125 ° C. in stirred 60 min to dissolve the masterbatch. After the master batch was visually confirmed that it has completely dissolved, the solution was allowed to stand for about 3 hours at room temperature, to precipitate a crystalline polypropylene in the liquid. The crystals were precipitated solution to suction filtration using a product of Sumitomo Electric Industries, Ltd. Fluoropore FP-100 (1μm), and washed with xylene 3 mL, CXS (xylene solubles, high molecular weight silicones (silicone gums)) and CXIS (xylene No soluble portion is separated into polypropylene). After it was solidified preliminary drying by nitrogen blow of room temperature CXS, vacuum dried at 60 ° C.. Vacuum drying is carried out until no weight loss. Performing GPC measurement using a CXS content after vacuum drying.
[0071]
　The high molecular weight silicones (silicone gums), such as manufactured by Dow Corning Toray Co., Ltd. BY27-001, Dow Corning Toray Silicone Co., Ltd. CF-9150, manufactured by Shin-Etsu Silicone X-21-3043, manufactured by Shin-Etsu Silicone Co., it can be used X-22-2101.
[0072]
[Thermoplastic elastomer composition]
　The thermoplastic elastomer composition of the present invention, the ethylene-alpha-olefin-non-conjugated polyene copolymer (A) and 5 to 30 parts by weight, crystalline olefin resin (B) 20 ~ 40 including a mass portion, a high-density polyethylene (C) 20 ~ 40 parts by weight, the ethylene · alpha-olefin copolymer (D) and 5 to 12 parts by weight, a silicone compound (E) 5 ~ 9 parts by weight (however , (a), (B) , (C), (D) and the sum of (E) and 100 parts by weight). Components in the ratio of said (A), (B), (C), by blending (D) and (E), is both the adhesion and sliding of the corner portion of the molded article obtained, and, it is possible to produce a shaped body such as excellent glass run channels in the low temperature impact strength.
[0073]
　If the amount of the ethylene-alpha-olefin-non-conjugated polyene copolymer (A) is less than the above lower limit, flexibility crease occurs without the other hand, if it exceeds the upper limit, sliding properties deteriorate . When the amount of the crystalline olefin resin (B) is less than the above lower limit, the moldability is deteriorated, while when it exceeds the upper limit, flexibility crease occurs without. When the amount of high-density polyethylene (C) is less than the above lower limit, the sliding resistance is deteriorated, while when it exceeds the upper limit, it creases occur hard. If the amount of the ethylene · alpha-olefin copolymer (D) is less than the above lower limit, the elongation decreases, and low-temperature characteristics are deteriorated, while when it exceeds the upper limit, softened slidability deteriorates . If the amount of the silicone compound (E) is less than the above lower limit, the sliding resistance is deteriorated, while when it exceeds the upper limit, with the adhesive of the corner portion of the molded article to be obtained is lowered, also the low-temperature impact strength Getting worse.
[0074]
　The thermoplastic elastomer composition of the present invention, the ethylene-alpha-olefin-non-conjugated polyene copolymer in which at least part of which is crosslinked (A), crystalline olefin resin (B), high-density polyethylene (C), ethylene · alpha-olefin copolymer (D) and the silicone compound (E), if necessary, a rubber softener (e.g., the above (d) a mineral oil softening agent) after a further melt kneading the other components, it can be produced by employing the method of granulation or pulverization.
[0075]
　The thermoplastic elastomer composition of the present invention, from the viewpoint of sliding property and low-temperature properties and flexibility, the ethylene-alpha-olefin-nonconjugated polyene copolymer uncrosslinked (A), crystalline olefin resin (B ) and an organic peroxide, if necessary, the mixture dynamically heat treated to contain other components, partially or completely crosslinked ethylene-alpha-olefin-non-conjugated polyene copolymer (a) after creating the thermoplastic elastomer containing, as the rest of the crystalline olefin resin (B), high-density polyethylene (C), an ethylene · alpha-olefin copolymer (D) and the silicone compound (E), needs Correspondingly, after the melt-kneading other components it is preferably produced by a method of granulation or pulverization.
[0076]
　As the kneading apparatus, a mixing roll and an intensive mixer (e.g., Banbury mixer, kneader), it can be used a uniaxial or biaxial extruder or the like, a non-open type apparatus is preferred.
[0077]
[Use of the thermoplastic elastomer composition]
　The thermoplastic elastomer composition of the present invention, various known molding method, specifically, for example, extrusion molding, press molding, injection molding, calender molding, hollow molding building various the molding method may be a thermoplastic elastomer molding. Further, the molded like sheets obtained in the molding method thereof capable of secondary processing by the thermal molding.
[0078]
　Thermoplastic elastomer molded article of the present invention is not particularly limited its intended use, for example, automobile parts, civil engineering and building materials goods, electric and electronic parts, sanitary goods, a variety known applications such as films and sheets it is preferred.
[0079]
　According to the thermoplastic elastomer composition of the present invention, to achieve both adhesion and sliding of the corner portion of the molded article obtained, and, since it is possible to manufacture a molded article excellent in low-temperature impact strength, automotive is optimal for producing a molded product having a corner portion, such as a glass run channel.
[0080]
　This specification includes the contents as disclosed in the specification of Japanese Patent Application No. 2017-072019 which is a priority document of the present application.
Example
[0081]
　Hereinafter, the present invention is described with reference examples, the present invention is not limited to these examples.
[0082]
　Each physical property in the following were measured or evaluated by the following methods.
[0083]
[2-layer molding]
　The two layers forming was carried out in pellet comprising a thermoplastic elastomer composition prepared in Example (sliding material). Extruder substrate using the 50mm single-screw extruder (manufactured by Nippon steel Corporation) MILASTOMER A800B temperature conditions using (manufactured by Mitsui Chemicals, Inc.) C1 / C2 / C3 / C4 / C5 = 160/170 / extrusion was carried out at 180/190/200 ° C.. Also the sliding layer 30mm single screw extruder performs two layers forming the sliding layer under the conditions at (Ltd Research Laboratory of Plastics Technology) C1 / C2 / C3 = 200 /210/230 ℃, substrate / sliding It created the extruded sheet of Dozai = 1.8mmt / 0.2mmt.
[0084]
[Shore A hardness (instantaneous
　value) in compliance with JIS K6253, a press sheet having a thickness of 2mm to 2 ply was measured by Shore A hardness tester.
[0085]
[Tensile properties]
　using 50t press, were prepared from the thermoplastic elastomer composition: a (preparation conditions preheated 230 ° C., 8 min, pressure, 6 minutes) sheet sample (2mm thick) test samples, measuring temperature 25 ° C., subjected to tensile test at a tensile rate of 500 mm / min and 200 mm / min condition, tensile strength (TB) and tensile elongation at break (EB) were measured.
[0086]
[Melt flow rate
　(MFR) of] in compliance with ASTM D1238 230 ° C., was determined melt flow rate (MFR) measured at 10kg load.
[0087]
[Low brittle temperature
　(Btp)] was measured according to ASTM D746.
[0088]
[Dynamic friction coefficient]
　Place the glass plate with a load surface of 200g of the sample film, which was pulled in the direction parallel with the film surface at 0.3 m / min. Force required at that time (g) was measured, (in accordance with ASTM D 1894-63) The force of the divided by the weight of the glass plate was expressed by the coefficient of dynamic friction.
[0089]
Adhesive Strength]
　The pellets of the thermoplastic elastomer compositions obtained in Examples and Comparative Examples (sliding material) were fused tested in the following manner. First, a test piece was prepared by punching a JIS3 dumbbell specimen of extruded sheet having a thickness of 2 mm (sliding surface thickness 0.2 mm). Thereafter, the dumbbell test piece 2 is divided, it was inserted into the test piece mold 50 ° C. of 150ton injection molding machine (NSK Ltd. NEX140). Thereafter, MILASTOMER G800BS (olefinic thermoplastic elastomer, manufactured by Mitsui Chemicals, Inc.) was injected to prepare a dumbbell specimen. (Cylinder temperature nozzle front / middle portion / rear = 250 ℃ / 230 ℃ / 210 ℃) Thereafter, a tensile test at a tensile speed of 500 mm / min, was evaluated in adhesion (adhesive strength, adhesion elongation).
[0090]
[Film thickness of the residual ratio (1 after thousand times slides)
　evaluated the glass run slide abrasion tester (daily total intensity measurement, Ltd.) sliding layer using an extrusion sheets two layers formed by using said went. It was abrasion test using a glass wear child. The cycle speed and 3kgf load to the glass perform 10,000 sliding test as one cycle / second, was conducted slidability voted residual rate of scraping surface of the glass contacts.
[0091]
　Remaining rate = (initial film thickness - scraped film thickness) / (initial film thickness)
[0092]
　Example 1
(1) Ethylene-alpha-olefin-nonconjugated polyene copolymer production of a thermoplastic elastomer containing (A) (alpha)
　ethylene-alpha-olefin-nonconjugated polyene copolymer as (A) Mitsui EPT (TM) 3072EPM (manufactured by Mitsui Chemicals, Inc. ethylene-propylene-ENB copolymer) (catalog value: ethylene content 64 wt%, ENB content of 5.4 wt%; molar conversion value (ethylene and a total of 100 moles of propylene % and): ethylene content 75.8 mol%, propylene content 24.2 mol%; oil extension amount 40 parts by; 140 parts by weight of iodine value 11.5), polypropylene as the crystalline olefin resin (B) resin (trade name: Prime Polypro E-200GP, (Ltd.) manufactured by Prime polymer Co., homo, MFR (230 ℃, 21.2N) 2.0g / 10 , Density 0.90 g / cm 3 ) 40 parts by mass, divinylbenzene 0.3 as an organic peroxide (1,3-bis (tert- butylperoxy-isopropyl) benzene) and 0.3 part by weight, crosslinking aid as a crosslinking agent parts by weight of phenolic antioxidant as an antioxidant (trade name: Irganox 1010, manufactured by BASF Japan Ltd.) 0.20 parts by mass, a benzotriazole ultraviolet absorber (trade name: Tinuvin 326FL, BASF Japan Co., Ltd.) 0.20 parts by weight of a hindered amine (HALS) type weathering stabilizer (trade name: Sanol LS-770, manufactured by Sankyo Lifetech Co., Ltd.) 0.10 parts by weight, carbon black master batch (PE4993, Cabot Corporation Ltd.) 4.0 parts by mass, the softening agent (Diana process PW-100, paraffin O Le) thoroughly mixing the 60 parts by weight of a Henschel mixer, and extruding kneaded under the following conditions, to obtain a partially or fully crosslinked thermoplastic elastomer (alpha).
[0093]
(Kneading conditions)
Extruder: No. KTX-46, Kobe Steel Co., Ltd.
Cylinder temperature: C1 ~ C2 120 ℃, C3 ~ C4 140 ℃, C5 ~ C14 200 ℃
die temperature: 200 ° C.
Screw rotation speed: 400 rpm
extrusion rate : 80kg / h
[0094]
(2) Preparation of thermoplastic elastomer composition
　obtained by the process, to partially or fully crosslinked thermoplastic elastomer (alpha) 25 parts by mass, as a crystalline olefin resin (B), a propylene / ethylene random copolymer (crystalline resin) (trade name: Prime Polypro B241, (Ltd.) manufactured by Prime polymer Co., density: 0.91 g / cm 3 , MFR (temperature: 230 ° C., load: 21.2 N): 0. 5 g / 10 min, density 0.91 g / cm 3 ) 20 parts by weight and ultra high molecular weight polyethylene (trade name: Miperon XM-220, manufactured by Mitsui Chemicals, Inc., weight average molecular weight of 2,000,000, melting point 136 ° C., an average particle diameter of 30 [mu] m) 10 parts by mass, as a high-density polyethylene (C) (Corporation) manufactured by Prime polymer Co., Ltd. high-density polyethylene (trade name: Hizex 8200B, density = 0. 5 g / cm 3 , due to the ASTM D1238 MFR (190 ℃, 2.16kg load) 0.03 g / 10 min) 40 parts by weight, Dow Chemical Co. ethylene octene rubber of an ethylene-alpha-olefin copolymer (D) ( product name: engage EG8003, MFR (230 ℃, 2.16kg load) 2 g / 10 min, density 0.885 g / cm 3 ) 10 parts by mass, as the silicone compound (E), silicone masterbatch (trade name: BY27-001 , manufactured by Dow Corning Toray Co., Ltd., pellet prepared by dispersing the silicone gum in polypropylene, silicone gums content: 50 wt%) 10 parts by mass of silicone oil (trade name: SH200-3000CS, manufactured by Dow Corning Toray Co., Ltd.) after thorough mixing 4 parts by mass in a Henschel mixer, an extruder And the mixture was kneaded under the following conditions.
[0095]
　The properties of the obtained thermoplastic elastomer composition were evaluated. The results are shown in Table 1.
[0096]
(Kneading conditions)
Extruder: No. KTX-46, Kobe Steel Co., Ltd.
Cylinder temperature: C1 ~ C2 120 ℃, C3 ~ C4 140 ℃, C5 ~ C14 200 ℃
die temperature: 200 ° C.
Screw rotation speed: 400 rpm
extrusion rate : 80kg / h
[0097]
　Comparative Examples 1 to 5]
　In Example 1 (2), except that the blending ratio of each component were changed as described in Table 1, to prepare pellets of a thermoplastic elastomer composition in the same manner as in Example 1 .
[0098]
　Physical properties evaluated using the resulting pellet was carried out. The results are shown in Table 1.
[0099]
　In Comparative Example 3, a propylene · alpha-olefin copolymer as the crystalline olefin resin (B) (trade name: TAFMER XM-7070, manufactured by Mitsui Chemicals, Inc.) was used.
[0100]
[Table 1]

[0101]All publications cited herein shall be incorporated herein patents and patent applications as reference.

The scope of the claims

[Requested item 1]Ethylene-alpha-olefin-non-conjugated polyene copolymer (A) and 5 to 30 parts by weight, a density of 0.90 g / cm 3 or more, 0.92 g / cm 3 or less is crystalline olefin resin (B) 20 and to 40 parts by weight, density 0.94 g / cm 3 or more, 0.97 g / cm 3 and high-density polyethylene (C) 20 to 40 parts by weight or less, ethylene and carbon atoms 3 to 12 α- olefin ethylene · alpha-olefin copolymer consisting of (D) and 5 to 12 parts by weight, the silicone compound (E) 5 ~ 9 parts by weight of a thermoplastic elastomer composition comprising (however, (a), (B), ( C), and total 100 parts by mass of (D) and (E)).
[Requested item 2]
　Silicone compound (E) is a thermoplastic elastomer composition of claim 1 comprising a silicone oil and high molecular weight silicones.
[Requested item 3]
　Ethylene-alpha-olefin copolymer (D) according to claim 1 or 2 thermoplastic elastomer composition according comprises one or more selected from ethylene octene rubber and ethylene-butene rubber.
[Requested item 4]
　Thermoplastic elastomer automotive glass run channel formed with the composition according to any one of claims 1-3.