JP6472205B2 - Low fogging thermoplastic elastomer composition and molded article thereof - Google Patents

Description

  The present invention relates to an olefinic thermoplastic elastomer composition, and more particularly to an olefinic thermoplastic elastomer composition having excellent fogging resistance (low wetting) and a molded article thereof.

  Olefin-based thermoplastic elastomers are lightweight and easy to recycle, and do not generate toxic gases during incineration, so they are energy-saving, resource-saving, and more recently, from the viewpoint of protecting the global environment, automotive parts and industrial machine parts. Applications are expanding to electrical / electronic parts and building materials.

  It is known that a mineral oil softener is added to the thermoplastic elastomer for the purpose of increasing flexibility and rubber elasticity.

  However, when an olefinic thermoplastic elastomer compounded with a mineral oil softener is used for automobile interior materials, etc., there is a problem that a fogging phenomenon (a phenomenon in which the glass becomes cloudy) occurs when used for a long time. Improvement was desired.

  As an olefinic thermoplastic elastomer composition excellent in fogging resistance, Patent Document 1 discloses that a crystalline polyolefin, an olefinic copolymer rubber, and an evaporation loss at 200 ° C. under normal pressure for 1 hour are 0.4 weight. %, And an olefinic thermoplastic elastomer composition comprising a paraffinic mineral oil softener having a kinematic viscosity at 40 ° C. of 50 to 250 cSt is disclosed.

Patent Document 2 describes that the kinematic viscosity at 40 ° C. of a refined mineral oil used as a mixture with a synthetic oil in an olefinic thermoplastic elastomer composition is preferably 400 mm ² / s or less (400 cSt or less). In the examples, refined mineral oil having a kinematic viscosity at 40 ° C. of 99 mm ² / s (99 cSt) is used.

  Although the volatile content in the mineral oil varies depending on the degree of purification, generally, the lower the viscosity of the mineral oil, the lower the molecular weight component, and thus the volatile content tends to increase.

Therefore, in the composition described in Patent Document 1, a mineral oil having a kinematic viscosity at 40 ° C. of 50 cSt or more is used. Patent Document 2 describes that the kinematic viscosity of mineral oil at 40 ° C. is preferably 400 mm ² / s or less (400 cSt or less), but the refined mineral oil used in the examples at 40 ° C. A mineral oil having a kinematic viscosity of 99 mm ² / s (99 cSt) and a kinematic viscosity at 40 ° C. of less than 50 cSt is not specifically used.

  Depending on the use of the elastomer, the compound may be required to have high fluidity. In that case, the plasticizer (softener) to be blended is preferably one having a low viscosity. However, when such a plasticizer is used, fogging easily occurs.

  On the other hand, GTL (Gas to Liquid) technology is a technology for producing a liquid oil or wax by polymerizing natural gas, and the oil obtained by this method is called a Fischer-Tropsch derived base oil. It is abbreviated as “GTL”.

  As a thermoplastic composition containing GTL, Patent Document 3 describes a thermoplastic polyolefin composition containing a thermoplastic polyolefin, a plasticizer having no functional group, and a nucleating agent, and does not have the functional group. Although GTL is described as a specific example of the plasticizer (Claims 1 and 48), GTL was blended in a composition containing an ethylene / α-olefin / non-conjugated polyene copolymer such as EPDM and an olefin resin. No specific example is described.

Patent Document 4 discloses a structure including a first member made of EPDM and a second member made of TPE attached to the first member, wherein at least the first member has a poly-α having specific physical properties. Although a structure containing a modifier selected from olefin, GTL and the like is described (claims 1, 5, 8 and 9), the specific examples of the modifier used in the examples are as follows. poly α-olefins (PAO) in a Spectra Shin ^TM (SpectraSyn ^TM) 100; is only (ExxonMobil Chemical Co. kinematic viscosity at kinematic viscosity 100 cSt, 40 ° C. at 100 ℃ 1240cSt), examples using GTL is specifically disclosed It has not been.

Patent Document 5 describes a composition in which a propylene / ethylene copolymer and polypropylene are blended with a modifier selected from polyalphaolefin having specific physical properties, GTL, and the like. is that used specifically in examples, Spectra Shin ^TM (SpectraSyn ^TM) 10 is a poly α-olefins (PAO) (ExxonMobil Chemical Co., Ltd .; kinematic viscosity at kinematic viscosity 10 cSt, 40 ° C. at 100 ℃ 66cSt), Spectra Shin ^{TM (SpectraSyn TM) 100 (ExxonMobil} Chemical Co., Ltd .; 100 kinematic viscosity at ° C. 100 cSt, 40 kinematic viscosity 1240cSt at ° C.), the parallax ^TM (Paralux ^TM) is a process oil 6001R (Chevron Texaco Corporation; kinematic at 100 ° C. Viscosity 13cSt at 40 ° C Viscosity 118CSt), a diisooctyl adipate Jay flex ^TM (JayFlex ^TM) DIOA is only an example of using the GTL is not specifically disclosed.

  Patent Document 6 includes an ethylene-propylene elastomer, a peroxide curing agent, and a non-functionalized plasticizer having a viscosity index of 120 or more, a kinematic viscosity at 100 ° C. of 20 cSt or more, and Mn of 1100 g / mol or more. And an elastomer composition that is substantially free of polyethylene in the composition and GTL as a specific example of the non-functionalized plasticizer (paragraph 0056).

  Patent Documents 3 to 6 do not mention any relationship between GTL and fogging resistance.

European Patent Application No. 1123946 International Publication No. 2007/060843 JP-T 2009-534499 (Claims 1 and 48) Special table 2008-545559 gazette Special table 2008-539306 gazette Special table 2010-516887 gazette

  An object of the present invention is to provide a thermoplastic elastomer composition that achieves both high fluidity of a compound and improvement of fogging resistance.

The gist of the present invention is as follows.
(1) Ethylene / α-olefin / non-conjugated polyene copolymer (A) 90 to 10 parts by weight, olefin-based resin (B) 10 to 90 parts by weight, and (A) and (B) total amount 100 parts by weight On the other hand, a mixture comprising 3 to 100 parts by weight of a softener (C) comprising a Fischer-Tropsch derived base oil and having a kinematic viscosity at 40 ° C. of less than 50 cSt is dynamically heat-treated in the presence of a crosslinking agent. The resulting thermoplastic elastomer composition.
(2) One or more types in which the olefin resin (B) is selected from homopolypropylene, random copolymers of α-olefins other than propylene and propylene, and block copolymers of α-olefins other than propylene and propylene The thermoplastic elastomer composition according to (1), which is a propylene-based polymer.
(3) The thermoplastic elastomer composition according to (1) or (2), wherein the crosslinking agent is an organic peroxide.
(4) The thermoplastic elastomer composition according to (1) or (2), wherein the crosslinking agent is a phenol resin.
(5) Any of the above (1) to (4), wherein the Fischer-Tropsch derived base oil is a hydrocarbon liquid derived from a liquid fuel production process, comprising hydroisomerized Fischer-Tropsch wax A thermoplastic elastomer composition according to claim 1.
(6) A molded product obtained by molding the thermoplastic elastomer composition according to any one of (1) to (5).
(7) The molded product according to (6), which is an automobile interior part.

  According to the present invention, there is provided a thermoplastic elastomer composition having both high fluidity of a compound and fogging resistance, wherein the softening agent has a low volatile content even when the viscosity is low, and the mechanical properties are equivalent to those of existing paraffin oil blended products. Can be provided.

FIG. 1 shows the measurement results of tensile properties.

  The thermoplastic elastomer composition of the present invention comprises an ethylene / α-olefin / non-conjugated polyene copolymer (A) 90 to 10 parts by weight, an olefin resin (B) 10 to 90 parts by weight, and (A) and (B In the presence of a crosslinking agent, a mixture comprising 3 to 100 parts by weight of a softener (C) comprising a Fischer-Tropsch derived base oil and a kinematic viscosity at 40 ° C. of less than 50 cSt with respect to a total amount of 100 parts by weight of It can be obtained by dynamic heat treatment.

[Ethylene / α-olefin / non-conjugated polyene copolymer (A)]
The ethylene / α-olefin / nonconjugated polyene copolymer (A) used in the present invention is ethylene, an α-olefin other than ethylene, preferably an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene, preferably Is a copolymer comprising a non-conjugated diene.

  The copolymer (A) can be produced by various known methods using a Ziegler-Natta type catalyst or a metallocene catalyst.

  Examples of the metallocene catalyst include transition metal compounds belonging to Group 4 of the periodic table (so-called metallocene compounds) containing a ligand having a cyclopentadienyl skeleton such as dimethylsilylene bis (2-methylindenyl) zirconium dichloride, methylalumoxane, and the like. It reacts with metallocene compounds such as organic aluminum oxy compounds, boron compounds such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, reactants of pentafluorophenol and organometallic compounds, or ion-exchange layered silicates. And known metallocene catalysts such as a catalyst comprising a cocatalyst that can be activated to a stable ionic state and an organoaluminum compound such as triethylaluminum used as necessary.

  The ethylene / α-olefin (molar ratio) in the copolymer (A) is usually 85/15 to 55/45, preferably 83/17 to 60/40.

  Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like can be mentioned.

  Specific examples of the non-conjugated diene include dicyclopentadiene, cyclooctadiene, methylene norbornene (eg, 5-methylene-2-norbornene), ethylidene norbornene (eg, 5-ethylidene-2-norbornene), methyltetrahydro Cyclic dienes such as indene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, norbornadiene; 1,4-hexadiene, 3-methyl-1 , 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl -1,6-octadiene, 6-ethyl-1,6-octadiene, 6 Propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7- Chains such as ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 7-methyl-1,6-octadiene State diene.

The Mooney viscosity ML _{1 + 4} (125 ° C.) of the copolymer (A) is usually from 10 to 200, preferably from 20 to 160, more preferably from 40 to 150, and the iodine value is usually from 3 to 25, preferably 5 ~ 25.

  The copolymer (A) can exist in all cross-linked states such as uncrosslinked, partially cross-linked, and fully cross-linked in the thermoplastic elastomer, but in the present invention, it exists in a completely or partially cross-linked state. It is necessary to be.

[Olefin resin (B)]
The olefin resin (B) used in the present invention is usually composed of a high molecular weight solid product obtained by polymerizing one or more monoolefins by a high pressure method or a low pressure method. Examples of such a resin include isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

  The suitable raw material olefin of the olefin-based resin (B) is preferably an α-olefin having 2 to 20 carbon atoms, specifically ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, Examples include octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. These olefins are used alone or in combination of two or more. The polymerization mode may be random type or block type as long as a resinous material is obtained. These olefin resins may be used alone or in combination of two or more.

  The olefin resin (B) used in the present invention is preferably a propylene polymer having a propylene content of 40 mol% or more, more preferably a propylene polymer having a propylene content of 50 mol% or more. .

  Among these olefin resins, propylene polymers, specifically, propylene homopolymers, propylene / ethylene block copolymers, propylene / ethylene random copolymers, propylene / ethylene / butene random copolymers, etc. Particularly preferred.

  In the olefin resin (B) used in the present invention, MFR (ASTM D1238-65T, 230 ° C., 2.16 kg) is usually 0.01 to 100 g / 10 minutes, particularly 0.05 to 50 g / 10 minutes. Preferably there is.

[Softener (C)]
The softener (C) used in the present invention comprises a Fischer-Tropsch derived base oil and is a softener having a kinematic viscosity at 40 ° C. of less than 50 cSt.

  In the present invention, the softening agent (C) is made of a Fischer-Tropsch derived base oil and is not particularly limited as long as the kinematic viscosity at 40 ° C. is less than 50 cSt.

Fischer-Tropsch derived base oils are known in the art. The term “Fischer-Tropsch derived” means that the base oil is or is derived from a synthetic product of the Fischer-Tropsch process. The term “Fischer-Tropsch derived base oil” is used in many patent documents such as Japanese Patent No. 4673342 and Japanese Patent No. 5546857.
Hereinafter, “Fischer-Tropsch derived base oil” is appropriately referred to as “GTL”.

  The GTL used in the present invention is required to have a kinematic viscosity at 40 ° C. of less than 50 cSt, and preferably 8 to 48 cSt, in order to achieve both high fluidity of the compound and fogging resistance. The kinematic viscosity is preferably 2 to 10 cSt, and more preferably 7 to 10 cSt.

  Since GTL used in the present invention has a narrow molecular weight distribution and a small amount of volatile matter, a product with less fogging than a normal process oil can be obtained when blended with a thermoplastic elastomer composition.

  The GTL used in the present invention is a waxy carbonization synthesized in a Fischer-Tropsch process, which is part of a Gas-To-Liquids process from gas. It consists of a raw material oil or oil derived from hydrogen, and is a liquid having a viscosity equivalent to a lubricating oil.

  The waxy synthetic hydrocarbon is a gaseous carbon-containing compound such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylene, butyne, It is induced by one or more synthesis reaction, mixing, conversion reaction, and / or transfer reaction using a gaseous hydrogen-containing compound as a raw material.

  A preferred feed is “syngas” (syngas consisting essentially of carbon monoxide and hydrogen) produced from a suitable feed such as natural gas and / or coal.

  GTL feedstocks or oils include hydroisomerized synthetic waxes, hydroisomerized Fischer-Tropsch waxes (including waxy hydrocarbons and similar oxygen-containing compounds), or mixtures thereof. Modified waxes are included.

  Furthermore, the GTL feedstock or oil is composed of other hydroisomerized feedstock or feedstock oil.

  Particularly preferred GTL feedstocks or oils are composed mostly of hydroisomerized Fischer-Tropsch waxes and / or other hydrocarbon liquids obtained by other Fischer-Tropsch synthesis reactions.

  For the hydrocarbon synthesis reaction including the synthesis of wax hydrocarbons by the Fischer-Tropsch synthesis reaction, a known appropriate process such as a slurry method, a fixed bed method, or a fluidized bed of catalyst particles in a hydrocarbon liquid is used. It is done.

  The catalyst is a heterogeneous catalyst in which a Group VIII metal such as Fe, Ni, Co, Ru, and Re is supported on a suitable inorganic carrier, or a crystalline catalyst such as a zeolite catalyst.

  The process of producing a lube oil feedstock or feedstock from a waxy feedstock is characterized as a hydrodewaxing process. The hydrotreating step is generally not necessary in the case of Fischer-Tropsch wax, but can be carried out before the hydrodewaxing if desired. It is preferred that certain Fischer-Tropsch waxes remove oxygen-containing compounds and other Fischer-Tropsch waxes be treated with oxygen-containing compounds prior to the hydrodewaxing step.

  The hydrodewaxing process is generally carried out in the presence of hydrogen under the conditions of a catalyst or catalyst and high temperature and pressure. Catalysts are disclosed in, for example, heterogeneous catalysts such as Co, Mo, W, etc. supported on suitable oxide supports, or ZSM-23, ZSM-48, and other US Pat. No. 4,906,350, often It is a homogeneous catalyst such as a zeolite catalyst used in combination with a Group VIII metal such as Pd or Pt.

  This process is followed by a solvent and / or catalytic dewaxing step to reduce the pour point of the hydroisomerization reaction product. In the solvent dewaxing step, the waxy component is physically separated from the hydroisomerization reaction product.

  In the catalytic dewaxing step, a part of the hydroisomerization reaction product is converted into low boiling point hydrocarbons. In the catalyst dewaxing step, a shape-selective molecular sieve such as zeolite or silicoaluminophosphate is used in combination with a catalytic metal such as Pt, and in the presence of hydrogen by a fixed bed, fluidized bed, or slurry process, Performed under high temperature and high pressure conditions.

  Catalysts, processes and compositions useful for GTL feedstocks or oils, feedstocks or oils derived from Fischer-Tropsch hydrocarbons, and hydroisomerized feedstocks or oils are described, for example, in US Pat. 817,693, 4,542,122, 5,5456,74, 4,568,663, 4,6211,072, 4,663,305, 4,897, 178, 4,900,407, 4,921,594, 4,923,588, 4,937,399, 4,975,177, 5,059,299 5,158,671, 5,182,248, 5,200,382, 5,290,426, 5,516,740, 5,580,442, 5,885,438, No.5,9 5,416, 5,935,417, 5,965,475, 5,976,351, 5,977,425, 6,025,305, 6,080, 301, 6,090,989, 6,096,940, 6,103,099, 6,165,949, 6,190,532, 6,332,974 6,375,830, 6,383,366, 6,475,960, 6,620,312, 6,676,827; European Patents 324528, 532116 532118, 537815, 583836, 666894, 668342, 776959; WO 97/31693, 99/20720, 99/45085, 02/6471. No., No. 02/64711, No. 02/70627, No. 02/70629, No. 03/33320, and British Patent No. 1,350,257, No. 1,390,359, are disclosed in No. 1,429,494 and No. 1,440,230.

  Particularly preferred processes are disclosed in EP-A-464546 and 464547. Processes using Fischer-Tropsch wax feed are described in US Pat. Nos. 4,594,172, 4,943,672, 6,046,940, 6,103,099, 6, 332,974, 6,375,830, and 6,475,960.

  Preferred GTL-derived liquids are available from suppliers such as Chevron, ConcoPhillips, ExxonMobil, Sasol, SasolChevron, Shell, Statoil and Syntroleum.

  As used herein, “hydroisomerization” is a catalytic process in which normal paraffins and / or slightly branched isoparaffins are converted to more branched isoparaffins by transfer (also known as isodewaxing). “Wax” is a hydrocarbon-like substance mainly composed of paraffin molecules, mostly normal paraffin, having a melting point of 0 ° C. or higher and solid at or near room temperature.

  The GTL used for the softener (C) usually has a viscosity index higher than 95, preferably higher than 100.

  The softening agent (C) may be oil extended to the ethylene / α-olefin / non-conjugated polyene copolymer (A) or may be added later without oil extension.

  The blending amount of the softening agent (C) is 3 with respect to 100 parts by weight of the total amount of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the olefin resin (B) together with the oil fraction. -100 parts by weight, preferably 5-80 parts by weight.

[Softener (D)]
In this invention, you may use softeners (D) other than a softener (C) in the range which does not impair the effect of this invention.

  Specifically, process oil, lubricant oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, petroleum softener such as petroleum jelly, coal tar softener such as coal tar and coal tar pitch, castor oil, Fat oil softeners such as linseed oil, rapeseed oil, soybean oil, coconut oil, waxes such as tall oil, sub (factis), beeswax, carnauba wax, lanolin, ricinoleic acid, palmitic acid, stearic acid, barium stearate Fatty acids and fatty acid salts such as calcium stearate and zinc laurate, naphthenic acid, pine oil, rosin or derivatives thereof, terpene resin, petroleum resin, coumarone indene resin, synthetic polymer substances such as atactic polypropylene, dioctyl phthalate, dioctyl Adipate, dioctyl Ester softeners such Baketo, microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, end modified polyisoprene, water 添末 end modified polyisoprene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils. Among these, petroleum softeners, particularly process oils are preferably used.

  The blending amount of the softening agent (D) is usually 50 parts by weight or less, preferably 40 parts by weight or less with respect to 100 parts by weight of the softening agent (C) together with the oil fraction.

[Thermoplastic elastomer composition]
In the thermoplastic elastomer composition of the present invention, the blending amount of the olefin resin (B) is 100 parts by weight of the total amount of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the olefin resin (B). On the other hand, it is 10 to 90 parts by weight, preferably 10 to 70 parts by weight.

  In the thermoplastic elastomer composition of the present invention, as the rubber component, in addition to the ethylene / α-olefin / non-conjugated polyene copolymer (A), other rubbers may be used in combination. The other rubber is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the α-olefin / non-conjugated polyene copolymer (A).

  Examples of other rubbers include diene rubbers such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), natural rubber (NR), and butyl rubber (IIR), SEBS, and polyisobutylene.

  The thermoplastic elastomer composition of the present invention includes components other than the ethylene / α-olefin / non-conjugated polyene copolymer (A), the olefin resin (B) and the softener (C), such as a heat stabilizer, a charge Additives such as an inhibitor, a weather resistance stabilizer, an anti-aging agent, a filler, a colorant, and a lubricant can be blended as necessary within the range not impairing the object of the present invention.

  As one of the preferable embodiments, with respect to 100 parts by weight of the elastomer composition of the present invention, other than the ethylene / α-olefin / non-conjugated polyene copolymer (A), the olefin resin (B) and the softener (C). Examples of the component include 30 parts by weight or less, but the present invention is not limited thereto.

  The thermoplastic elastomer composition of the present invention comprises an ethylene / α-olefin / non-conjugated polyene copolymer (A), an olefinic resin (B), a softening agent (C), and additives that are blended as necessary. A thermoplastic elastomer composition obtained by dynamically heat-treating a mixture containing the mixture in the presence of a crosslinking agent, preferably an organic peroxide or a phenol resin.

  Specific examples of the organic peroxide used as the crosslinking agent include 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-butylperoxyisopropyl) 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-butylperoxybenzoate, tert-butylperoxyisopropyl Carbonate, diaceti Peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.

  Among these, in terms of odor and 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-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (Tert-Butylperoxy) valerate is preferred, and 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 1,3-bis (tert-butylperoxyisopropyl) benzene are most preferred.

  In this invention, an organic peroxide is 0.05-3 weight part normally with respect to 100 weight part of total amounts of an olefin resin (B), all the rubber components, and a softening agent (C), Preferably it is 0.00. It is used at a ratio of 1 to 1 part by weight.

  In the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane , N, N'-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate, or ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate Polyfunctional methacrylate monomers such as these; polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

  By using such a compound, a uniform and mild crosslinking reaction can be expected.

  Compounds such as the above-mentioned crosslinking aid or polyfunctional vinyl monomer improve the fluidity of the resulting thermoplastic elastomer and prevent changes in physical properties due to thermal history during processing and molding. In this respect, it is preferably used in a proportion of 0.1 to 2 parts by weight, particularly 0.3 to 1 part by weight, based on 100 parts by weight of the entire cross-linked product.

  The phenolic resin used as a crosslinking agent is also called a phenolic curative and refers to a vulcanizing agent containing a phenolic curing resin, preferably US Pat. No. 4,311,628. Examples thereof include a phenolic curative system composed of a phenolic curing resin and a cure activator disclosed in the specification.

Basic components of the systems are substituted phenol in an alkaline medium (e.g., halogen substituted phenol, C ₁ -C ₂ alkyl substituted phenol) or unsubstituted phenol with an aldehyde, or preferably by condensation with formaldehyde, or bifunctional phenol dialcohols (preferably, the para position is C ₅ -C ₁₀ dimethylol phenols substituted with an alkyl group) a phenolic curing resin made by condensation of. Particularly suitable are halogenated alkyl-substituted phenolic curable resins prepared by halogenation of alkyl-substituted phenolic curable resins. A phenolic vulcanizing agent system consisting of a methylolphenol curable resin, a halogen donor and a metal compound can be particularly recommended, and details thereof are described in US Pat. Nos. 3,287,440 and 3,709,840. Non-halogenated phenolic curable resins are used simultaneously with the halogen donor, preferably with a hydrogen halide scavenger. Usually, halogenated phenolic curable resins, preferably brominated phenolic curable resins containing 2 to 10% by weight of bromine, do not require a halogen donor, for example, iron oxide, titanium oxide, oxidized Used simultaneously with hydrogen halide scavengers such as magnesium, magnesium silicate, silicon dioxide and preferably metal oxides such as zinc oxide. Although the presence of such a scavenger promotes the crosslinking action of the phenolic curable resin, it is desirable to share a halogen donor and zinc oxide in the case of a rubber that is not easily vulcanized with the phenolic curable resin. The preparation of halogenated phenolic curable resins and their use in vulcanizing systems using zinc oxide are described in U.S. Pat. Nos. 2,972,600 and 3,093,613, the disclosures of which are described in U.S. Pat. Incorporated herein by reference together with the disclosure of US Pat. Nos. 3,287,440 and 3,709,840. Examples of suitable halogen donors include stannous chloride, ferric chloride, or halogen donating heavys such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). Coalesce is mentioned. As used herein, the term “activator” refers to any substance that substantially increases the crosslinking efficiency of the phenolic curable resin, and includes metal oxides and halogen donors, which are used alone. Or used in combination. For more details on phenolic vulcanizing systems, see “Vulcanization and Vulcanizing Agents” (W. Hoffman, Palmerton Publishing Company). Suitable phenolic curable resins and brominated phenolic curable resins are commercially available, for example such resins from Schenectady Chemicals, Inc. under the trade designations “SP-1045”, “CRJ-352”, “ It can be purchased as “SP-1055” and “SP-1056”. Similar functionally equivalent phenolic curable resins can also be obtained from other suppliers.

  The phenol resin is a suitable vulcanizing agent from the viewpoint of preventing fogging because it hardly generates decomposition products.

  The phenolic resin is used in an amount sufficient to achieve essentially complete vulcanization of the rubber.

  The phenol resin is used in an amount of phenolic curable resin with respect to 100 parts by weight of the total amount of the olefin resin (B), all rubber components, and softener (C), usually 0.5 to 10 weights. Parts, preferably 0.5 to 5 parts by weight, more preferably 1 to 5 parts by weight.

  The term “dynamically heat-treating” refers to kneading each component as described above in a molten state.

  As the kneading apparatus, a conventionally known kneading apparatus, for example, an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer or the like is used. Among these, a non-open type kneading apparatus is preferable, and the kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The kneading is preferably performed at a temperature at which the half-life of the organic peroxide used is less than 1 minute. The kneading temperature is usually 150 to 280 ° C, preferably 170 to 240 ° C, and the kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. The applied shear force is determined as a shear rate within a range of 10 to 50,000 sec ⁻¹ , preferably 100 to 20,000 sec ⁻¹ .

  The thermoplastic elastomer composition of the present invention comprises an olefin resin (B), a rubber and a softening agent (C), and thus has excellent high-temperature fluidity and extrusion moldability. Therefore, compression molding, transfer molding, injection molding, It can shape | mold using the shaping | molding apparatus conventionally used in extrusion molding etc.

[Automobile interior parts]
The molded article of the present invention is obtained by molding the thermoplastic elastomer composition of the present invention, and is optimal for use as an automobile interior part.

The automobile interior part of the present invention is usually produced according to the following conventional method.
(1) Supply to a plastic processing machine such as an extrusion molding machine with a T-die or a calendar molding machine and mold it into a desired shape such as a sheet.
(2) Molding into a desired shape by injection molding.

  A surface layer made of at least one compound selected from polyurethane, saturated polyester, acrylic ester resin, polyvinyl chloride and isocyanate resin can be provided on the skin layer of the automobile interior part of the present invention.

  As the saturated polyester used for forming such a surface layer, polyethylene terephthalate, polybutylene terephthalate, and derivatives thereof are used. As the acrylic ester resin, polymethyl (meth) acrylate, polyisobutyl (meth) acrylate, poly-2-ethylhexyl (meth) acrylate, or the like is used. Furthermore, as the isocyanate resin, polyhexamethylene diisocyanate, polyisophorone diisocyanate, or the like is used.

  Such a surface layer is preferably 300 μm or less. A primer layer can be interposed between the skin layer and such a surface layer.

  Furthermore, the automobile interior part of the present invention can constitute a laminate with a polyolefin foam or a laminate with a polyolefin resin. Examples of the polyolefin used here include olefin-based resins used in the production of the olefin-based thermoplastic elastomer composition. In particular, polyethylene, polypropylene and the like are preferable.

  In such a laminate, for example, an olefinic thermoplastic elastomer composition is extruded using an extruder with a T-die, and the extruded thermoplastic elastomer composition in a molten state is laminated with a polyolefin foam sheet. It is manufactured by passing through a pair of rolls in a state or by sequential injection molding of a polyolefin resin and an olefinic thermoplastic elastomer.

  The automobile interior part of the present invention is mainly used as a skin layer for door trims, instrumental panels, ceilings, handles, console boxes, seats and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
In addition, the measuring method of the physical property performed about the softener used by the Example and the comparative example is as follows.

[density]
The measurement was carried out at 15 ° C. according to the method of ISO 12185.
[Color (Saybolt)]
Measured according to ASTM D156 method.
[Refractive index]
Measured at 20 ° C. according to ASTM D1218 method.
[Flash point]
It was measured according to the method of ISO 2592.
[Pour point]
Measured according to ISO 3016 method.
[Kinematic viscosity]
Measurements were taken at 40 ° C. and 100 ° C. according to the method of ISO 3104.
[Viscosity index]
It was measured according to the method of ISO 2909.
[5vol% distillation temperature]
It measured according to the method of JIS K2254.
[Aniline point]
Measured according to the method of ISO 2977.
[sulfur]
It was measured according to the method of ISO 14596.

  The measurement methods and evaluation methods of physical properties carried out below are as follows.

[MFR (g / 10 min)]
MFR was measured at 230 ° C. and a load of 10 kgf in accordance with JIS K6721.
[Shore A hardness]
Based on JIS K6253, it measured with the Shore A hardness meter using the press sheet of thickness 3mm.
[Tensile properties]
It measured according to the method of JISK6301.
M100: Stress at 100% elongation TB: Tensile strength EB: Tensile elongation at break [Compression set (CS)]
The prepared sheets were laminated according to JIS K6250, and a compression set test was performed according to JIS K6262.
Test conditions were measured using a laminated sheet with a thickness of 12 mm (four pieces of 3 mm thick pieces) under conditions of 25% compression, 70 ° C., 24 hours, and 30 minutes after strain removal (compression). did.
[Foging properties]
According to DIN 75201, the glass was tested with 10 g of pellets, “100 ° C. × 5 hours” or “110 ° C. × 20 hours”, and the degree of glass (%) was measured.
[Heating loss] (Table 2)
A press sheet having a thickness of 2 mm prepared by a press molding machine was cut into a size of 60 × 40 mm, and the weight before heating was measured. The sheet was heated using an oven under the conditions of “100 ° C. × 100 hours, in air”, “100 ° C. × 200 hours, in air” and “100 ° C. × 300 hours, in air”. The weight after standing to cool for the time was measured, and the difference from the weight before heating was calculated.

[Production Example 1]
A terpolymer composed of ethylene, propylene and 5-ethylidene-2-norbornene (ENB) was synthesized continuously at a temperature of 60 ° C. using a polymerization vessel equipped with a stirring blade having a volume of 300 liters.

At this time, hexane (feed amount 26.5 kg / h) was used as a polymerization solvent, ethylene feed amount 4.6 kg / h, propylene feed amount 3.0 kg / h, ENB feed amount 420 g / h, hydrogen feed The amount was continuously fed to the polymerization vessel at 2 normal liters / h. While maintaining the polymerization pressure at 1.6 MPa-G, as the main catalyst:
The compound represented by the formula (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene is fed so that the feed amount becomes 0.003 mmol / h. Was continuously fed to the polymerization vessel. (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ as a cocatalyst and 0.017 mmol / h as an organoaluminum compound, and triisobutylaluminum as an organoaluminum compound were continuously supplied to the polymerizer at 10 mmol / h, respectively.

  Thus, a polymerization solution containing 17.2% by weight of a copolymer composed of ethylene, propylene and ENB (hereinafter also referred to as “EPT-1”) was obtained (polymerization time: 2.12 hours). The obtained polymerization solution was poured into a large amount of methanol to precipitate EPT-1, and then the precipitate was dried under reduced pressure at 80 ° C. for 24 hours.

  The physical properties of the obtained ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (EPT-1) are shown below.

(Physical properties of EPT-1)
Ethylene unit content 66wt%
Iodine number 9.8
Mooney viscosity ML _{1 + 4} (125 ° C) 61

[Production Example 2]
A copolymer (hereinafter also referred to as “EPT-2”) composed of ethylene, propylene and ENB was obtained in the same manner as in Production Example 1 except that the amount of monomer feed was adjusted and further oil extended.

  The physical properties of the obtained ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (EPT-1) are shown below.

(Physical properties of EPT-2)
Ethylene unit content 64wt%
Iodine number 11.5
Mooney viscosity ML _{1 + 4} (125 ° C) 51

[Example 1]
Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (EPT-1) obtained in Production Example 1 (ethylene unit content 66 wt%; iodine value 9.8; Mooney viscosity ML _{1 + 4} (125 ° C.) 61) Propylene / ethylene block copolymer (PP-1: trade name EL-Pro P740J) having 49 parts by weight and a melt flow rate (ASTM-D-1238-65T; 230 ° C., 2.16 kg load) of 27 g / 10 min. Linear low density polyethylene (PE) having 32 parts by weight (manufactured by SCG Chemicals) (melting point: 163 ° C.) and a melt flow rate (ASTM-D-1238-65T; 190 ° C., 2.16 kg load) of 2 g / 10 min. -1: 19 parts by weight of a trade name, Ultrazex 2021L (manufactured by Mitsui Chemicals), and an organic peroxide (P Hexin 25B (manufactured by Nippon Oil & Fats Co., Ltd.) 0.14 parts by weight, 0.14 part by weight of divinylbenzene as a crosslinking aid, phenolic antioxidant (Irganox 1010, manufactured by BASF Japan Co., Ltd.) as an antioxidant ) 0.07 parts by weight, 0.06 parts by weight of weathering stabilizer-1 (Tinuvin 326, manufactured by BASF Japan Ltd.) and 0.06 parts by weight of weathering stabilizer-2 (Tinubin 622, manufactured by BASF Japan Co., Ltd.) 0.06 Part by weight is sufficiently mixed with a Henschel mixer, and an extruder (product number KTX-46, manufactured by Kobe Steel), cylinder temperature: C1 120 ° C, C2 to C3 130 ° C, C4 140 ° C, C5 180 ° C, C6 200 Kinematic viscosity at 40 ° C. (AS) at C ° C., C7 to C14 230 ° C., die temperature: 220 ° C., screw rotation speed: 400 rpm, extrusion rate: 60 kg / h) M-D445) performs kneading while injecting 7.6 mm ² / s GTL (Risella X430, manufactured by Royal Dutch Shell Co.) 20 parts by weight of the cylinder, partially or fully crosslinked thermoplastic elastomer composition A product pellet was obtained.

[Example 2]
Oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (EPT-2) obtained in Production Example 2 (ethylene content 64 wt%; iodine value 11.5; Mooney viscosity ML _{1 + 4} (125 51 ° C.) 51; oil extended amount 100 parts by weight of rubber, rubber softener (D-1) (40 parts by weight of Diana Process Oil PW-100, manufactured by Idemitsu Kosan Co., Ltd.) 83 parts by weight, and melt flow rate ( ASTM-D-1238-65T; 230 ° C., 2.16 kg load) 9 g / 10 min propylene / ethylene block copolymer (melting point 166 ° C., PP-2: trade name Prime Polypro ™ J705UG (prime polymer) 17 parts by weight) and carbon black masterbatch (trade name PEONY BLACK F32387MM (manufactured by DIC Corporation)) 2.5 parts by weight, 0.39 parts by weight of an organic peroxide (Perhexa 25B, manufactured by NOF Corporation) as a crosslinking agent, 0.26 parts by weight of divinylbenzene as a crosslinking aid, and phenol as an antioxidant -Based antioxidant (Irganox 1010, manufactured by BASF Japan Ltd.) 0.1 part by weight, weathering stabilizer-1 (Tinuvin 326, manufactured by BASF Japan Co., Ltd.) 0.1 part by weight, and weathering stabilizer- 3 (Tinubin 770, manufactured by BASF Japan Ltd.) and 0.05 part by weight were sufficiently mixed with a Henschel mixer, and an extruder (product number KTX-46, manufactured by Kobe Steel Co., Ltd., cylinder temperature: C1 120 ° C., C2). ~ C3 130 ° C, C4 140 ° C, C5 180 ° C, C6 200 ° C, C7 to C14 230 ° C, Die temperature: 220 ° C, Screw rotation speed: 400rpm, Extrusion amount: 60k At / h), and the mixture was kneaded while kinematic viscosity (ASTM-D445) are injected 7.6 mm ² / s GTL (Risella X430, manufactured by Royal Dutch Shell Co.) 45 parts by weight of the cylinder at 40 ° C., Partially or fully crosslinked thermoplastic elastomer composition pellets were obtained.

[Comparative Example 1]
As described in Example 1, except that Diana process oil (PW-100, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. (ASTM-D445) of 101 mm ² / sec was used instead of GTL as a rubber softener. A pellet of a thermoplastic elastomer composition partially or completely cross-linked with the raw material and conditions was obtained.

[Comparative Example 2]
As described in Example 2, except that Diana process oil (PW-100, manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. (ASTM-D445) of 101 mm ² / sec was used instead of GTL as a rubber softener. A pellet of a thermoplastic elastomer composition partially or completely cross-linked with the raw material and conditions was obtained.

  Table 1 shows the physical properties of the softeners used in Examples and Comparative Examples, and Table 2 and FIG. 1 show the physical properties and evaluation results of the pellets obtained in Examples and Comparative Examples.

  From the results shown in Table 2 and FIG. 1, it can be seen that the thermoplastic elastomer composition of the present invention achieves both high fluidity of the compound and fogging resistance.

Claims (6)

90 to 10 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A), 10 to 90 parts by weight of the olefin resin (B), and 100 parts by weight of the total amount of (A) and (B), consists Fischer over-Tropsch derived base oil, the mixture kinematic viscosity comprises 3 to 100 parts by weight of a softening agent (C) is less than 50cSt at 40 ° C., it is obtained by dynamically heat-treated in the presence of a crosslinking agent thermal A thermoplastic elastomer composition , wherein the Fischer-Tropsch derived base oil is a hydrocarbon liquid derived from a liquid fuel production process, comprising hydroisomerized Fischer-Tropsch wax .   The olefin resin (B) is one or more propylene resins selected from homopolypropylene, a random copolymer of propylene and an α-olefin other than propylene, and a block copolymer of propylene and an α-olefin other than propylene. The thermoplastic elastomer composition according to claim 1, which is a polymer.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the crosslinking agent is an organic peroxide.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the crosslinking agent is a phenol resin. The molded object obtained by shape | molding the thermoplastic elastomer composition of any one of Claims 1-4 . The molded article according to claim 5 , which is an automobile interior part.