Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/083—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic polyenes, i.e. containing two or more carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/04—Thermoplastic elastomer

Definitions

• One embodiment of the present invention relates to a thermoplastic elastomer composition or a molded product thereof.
• the olefin-based thermoplastic elastomer composition is a material having excellent moldability and appropriate flexibility and rubber elasticity, and is used for vehicle parts such as automobiles, mechanical parts, electrical parts, home appliances, daily miscellaneous goods, and kitchen utensils. It is used in various fields such as.
• Examples of vehicle parts in which an olefin-based thermoplastic elastomer composition is used include automobile interior materials such as a skin material (instrumental panel) for a cover of an airbag device.
• instrument panel When the airbag device is operated, the instrument panel is broken together with the airbag cover by the expansion force of the airbag inflated by the gas generated by the gas generator (inflator). Therefore, the instrumental panel is required to be a material that can be easily broken and the airbag can be reliably deployed.
• Patent Documents 1 and 2 disclose thermoplastic elastomer compositions that can be used for instrumental panels. However, neither Patent Documents 1 and 2 mentions the fracture property of the instrument panel.
• the values of elongation at break and tear strength in the tensile properties are moderately small. It has been found that if the values of elongation at break and tear strength are too low, the sheet may be torn during processing by sheet molding or vacuum forming. That is, conventionally, there has not been a molded product that simultaneously satisfies both excellent moldability and moderately small values of elongation at break and tear strength.
• thermoplastic elastomer composition capable of forming a molded product having excellent moldability but having appropriately small values of elongation at tensile break and tear strength.
• a configuration example of the present invention is as follows.
• "A to B" indicating a numerical range indicates A or more and B or less.
• Ethylene / ⁇ -olefin / non-conjugated polyene copolymer 100 parts by mass and 20 to 80 parts by mass of the propylene-based polymer (B) having a melt flow rate (based on the measurement method of ASTM D 1238-65T, 230 ° C., 2.16 kg load) of 1 to 100 g / 10 minutes.
• Inorganic filler C 0.1 to 50 parts by mass and A thermoplastic elastomer composition which is a composition in which a cross-linking agent (D) is dynamically cross-linked.
• thermoplastic elastomer composition according to [2] which satisfies the following (1) to (3).
• Shore A hardness instantaneous value (based on the measurement method of JIS K 6253, using a sample in which three 2 mm thick sheet-shaped thermoplastic elastomer compositions are stacked to make a thickness of 6 mm) is 40 to 80.
• Tear strength (according to the measurement method of JIS K 6252-1, using a sheet-shaped thermoplastic elastomer composition with a thickness of 2 mm) is 16 N / mm or more and less than 27 N / mm (3) Elongation at break (JIS) According to the measurement method of K 6251, a sheet-shaped thermoplastic elastomer composition with a thickness of 2 mm is used) is 200% or more and less than 450%.
• thermoplastic elastomer composition according to any one of [1] to [4], which comprises at least a partially crosslinked ethylene / ⁇ -olefin / non-conjugated polyene copolymer.
• thermoplastic elastomer composition according to any one of [1] to [5], wherein the inorganic filler (C) is talc or calcium carbonate.
• thermoplastic elastomer composition according to any one of [1] to [6].
• the vehicle component according to [8] which is an interior skin material.
• thermoplastic elastomer composition capable of forming a molded product having excellent moldability but having appropriately small values of elongation at tensile break and tear strength.
• the values of elongation at break and tear strength in tensile properties are moderately small, while having mechanical properties such as hardness, tensile properties and compression set necessary for practical use.
• a molded body can be formed.
• thermoplastic elastomer composition (hereinafter, also referred to as “the present composition”) according to the embodiment of the present invention is used.
• a composition containing 20 to 80 parts by mass of the propylene-based polymer (B) and 0.1 to 50 parts by mass of the inorganic filler (C) (hereinafter, also referred to as "this composition 1"), or Ethylene / ⁇ -olefin / non-conjugated polyene copolymer (A) 100 parts by mass and melt flow rate (based on the measurement method of ASTM D 1238-65T, 230 ° C., 2.16 kg load) 1 to 100 g
• the ethylene / ⁇ -olefin / non-conjugated polyene copolymer (A) (hereinafter, also referred to as “component (A)”; the same applies to other components) is a constituent unit derived from ethylene, a constituent unit derived from ⁇ -olefin, and the like.
• the constitutional unit derived from the non-conjugated polyene is not particularly limited, and for example, it can be synthesized by a conventionally known method of copolymerizing ethylene, ⁇ -olefin and non-conjugated polyene.
• the component (A) contained in the present composition may be one kind or two or more kinds.
• the total of the content of the ethylene-derived structural unit in the component (A) (hereinafter, also referred to as “ethylene content”) and the content of the ⁇ -olefin-derived structural unit (hereinafter, also referred to as “ ⁇ -olefin content”).
• the ethylene content is preferably 50 mol% or more, more preferably 55 mol% or more, and further, from the viewpoint that a molded product having excellent mechanical strength and flexibility can be easily obtained. It is preferably 60 mol% or more, more preferably 95 mol% or less, still more preferably 85 mol% or less, and particularly preferably 83 mol% or less.
• the ethylene content and ⁇ -olefin content can be determined by measurement by 13 C-NMR.
• the ⁇ -olefin is not particularly limited, but an ⁇ -olefin having 3 to 20 carbon atoms is preferable.
• Specific examples of the ⁇ -olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene.
• One type of these ⁇ -olefins may be used, or two or more types may be used.
• propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene is more preferable.
• the ⁇ -olefin content is such that a molded product having excellent mechanical strength and flexibility can be easily obtained. Therefore, it is preferably 50 mol% or less, more preferably 45 mol% or less, further preferably 40 mol% or less, more preferably 5 mol% or more, still more preferably 15 mol% or more, and particularly preferably 17 mol% or more. Is.
• non-conjugated polyene examples include a chain non-conjugated diene, a cyclic non-conjugated diene, and a triene. One type of these non-conjugated polyenes may be used, or two or more types may be used.
• chain non-conjugated diene examples include 1,4-hexadiene, 1,5-hexadiene, 1,6-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-.
• Methyl-1,4-hexadiene 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadien, 3,7-dimethyl-1,6-octadien, 5,7-dimethyl-1, Examples thereof include 7-octadien, 8-methyl-4-ethylidene-1,7-nonadien, and 4-ethylidene-1,7-undecadien.
• Examples of the cyclic non-conjugated diene include tetrahydroinden, methyltetrahydroinden, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, and 5 -Vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, 5-cyclohexyl Examples thereof include den-2-norbornene, cyclopentadiene, dicyclopentadiene, cyclooctadien and norbornene.
• Trienes include 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornene, 4-ethylidene-8-methyl-1,7.
• non-conjugated polyene examples include 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene, dicyclopentadiene, and 4-ethylidene-8-methyl-1,7-nonadien.
• 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are more preferable.
• the content of the non-conjugated polyene-derived structural unit in the component (A) is such that the iodine value is preferably 1 or more, more preferably 5 or more, particularly preferably 10 or more, and preferably 50 or less.
• the amount is preferably 40 or less, particularly preferably 30 or less.
• the content of the structural unit derived from the conjugated polyene is usually 2 to 20% by mass with respect to 100% by mass of all the structural units constituting the component (A).
• 125 ° C.] is preferably 10 or more, more preferably 30 or more, preferably 250 or less, and more preferably 150 or less.
• a conventionally known method for example, oil-expanded with an oil-spreading agent such as the following softener may be used, if necessary.
• an oil-spreading agent such as the following softener may be used, if necessary.
• a petroleum-based softener such as a paraffin-based process oil is preferable.
• the amount of the oil spreading agent used at the time of this oil spreading is preferably an amount such that the Mooney viscosity of the oil spread is within the above range, and for example, from 0 to 100 parts by mass of the component (A). It is 150 parts by mass.
• the intrinsic viscosity [ ⁇ ] of the component (A) measured in a decalin solvent at 135 ° C. is preferably 1 dl / g or more, more preferably 1.5 dl / g or more, preferably 10 dl / g or less, and more. It is preferably 8 dl / g or less.
• the component (A) may be present in the present composition in any crosslinked state such as uncrosslinked, partially crosslinked, and completely crosslinked.
• the timing of the cross-linking is not particularly limited, and for example, the component (A) is used before being mixed with the components (B) and (C) constituting the present composition.
• At least a part of the component (A) may be (dynamically) crosslinked, or at least a part of the component (A) may be (dynamically) crosslinked after or while being mixed with other components constituting the present composition. good.
• a composition containing at least a partially crosslinked component (A) can be obtained.
• the component (A) is crosslinked.
• the degree of cross-linking of the component (A) is high, the component (A) having a high degree of cross-linking and the component (B) and the component (C) having an MFR in the following range are used in combination to be produced from the present composition.
• the elongation of the molded product can be suppressed, and the value of elongation at break in the tensile properties can be easily adjusted within a predetermined range. Therefore, by using this composition containing such a component, an instrumental panel that is easily broken can be manufactured.
• the degree of cross-linking of the component (A) increases, the compression set of the molded product produced from the present composition tends to decrease. Therefore, the degree of cross-linking of the component (A) can be estimated from the compression set of the molded product produced from the present composition.
• the content of the component (A) in the present composition is such that a molded product having a hardness required for practical use and having an appropriately small value of elongation at break and tear strength in tensile properties can be easily obtained. From the point of view, it is preferably 50% by mass or less, more preferably 10 to 50% by mass.
• the component (B) is a polymer other than the component (A).
• the component (B) refers to a polymer in which the content of the structural unit derived from propylene is 50 mol% or more among the structural units constituting the polymer, and is derived from the propylene in the component (B).
• the content of the structural unit is preferably 90 mol% or more.
• the component (B) contained in the present composition may be one kind or two or more kinds.
• the component (B) may be a propylene homopolymer or a copolymer of propylene and a comonomer other than propylene.
• the structure of the component (B) is not particularly limited.
• the structural unit portion derived from propylene may have an isotactic structure, a syndiotactic structure, or an atactic structure, but an isotactic structure is preferable.
• the copolymer it may be any of a random type, a block type and a graft type.
• the comonomer may be any other monomer copolymerizable with propylene, and an ⁇ -olefin having 2 or 4 to 10 carbon atoms is preferable. Specific examples thereof include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene and the like. , Ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene, 1-octene are preferred. As the comonomer, one type may be used, or two or more types may be used. The content of the comonomer-derived structural unit in the copolymer is preferably 10 mol% or less from the viewpoint of flexibility and the like.
• the component (B) may be synthesized by a conventionally known method, or a commercially available product may be used.
• the component (B) may be a crystalline polymer or a non-crystalline polymer.
• the crystallinity means that the melting point (Tm) is observed in the differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• its melting point is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint of heat resistance and the like. It is preferably 180 ° C. or lower, more preferably 170 ° C. or lower.
• the MFR (based on the measurement method of ASTM D 1238-65T, 230 ° C., 2.16 kg load) of the component (B) is 1 to 100 g / 10 minutes, preferably 2 g / 10 minutes or more, and more preferably 3 g /. It is 10 minutes or more, more preferably 5 g / 10 minutes or more, preferably 80 g / 10 minutes or less, more preferably 70 g / 10 minutes or less, still more preferably 55 g / 10 minutes or less.
• a composition having excellent moldability can be easily obtained, and a molded product having moderately small values of elongation at break and tear strength in tensile properties can be easily obtained. be able to.
• the content of the component (B) in the present composition is 20 to 80 parts by mass, preferably 25 parts by mass or more, more preferably 30 parts by mass or more, preferably 30 parts by mass or more, based on 100 parts by mass of the component (A). Is 70 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less.
• the content of the component (B) is within the above range, it is possible to easily obtain a molded product having hardness required for practical use and having an appropriately small value of elongation at break and tear strength in tensile properties.
• the component (C) is not particularly limited, and examples thereof include carbonates, sulfates, phosphates, oxides, hydroxides, inorganic substances containing silicon, sulfides, carbon materials, and cements.
• the component (C) contained in the present composition may be one kind or two or more kinds.
• Examples of the carbonate include calcium carbonate, barium carbonate, magnesium carbonate, and zinc carbonate.
• Examples of the sulfate include calcium sulfate, barium sulfate, and magnesium sulfate.
• Examples of the phosphate include calcium phosphate.
• Examples of the oxide include zinc oxide, iron oxide, calcium oxide, magnesium oxide, aluminum oxide, titanium oxide, and barium oxide.
• Examples of the hydroxide include magnesium hydroxide.
• Examples of the silicon-containing inorganic substance include calcium silicate, clay (including brazing clay, calcined clay, etc.), kaolin, talc, silica (humped silica, calcined silica, precipitated silica, ground silica, molten silica, etc.).
• Silicic acid clay mica, asbestos, glass fiber, glass bulb, silas balloon, silicic acid clay, zeolite.
• sulfide include tungsten sulfide and molybdenum sulfide.
• carbon material include graphite and carbon black.
• calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, calcium sulfate, barium sulfate, magnesium sulfate, zinc oxide, iron oxide, calcium oxide, magnesium oxide, aluminum oxide, titanium oxide, barium oxide, calcium silicate, Clay, kaolin, talc and carbon black are preferable, talc, clay and calcium carbonate are more preferable, talc and calcium carbonate are further preferable, and talc is particularly preferable.
• the shape of the component (C) is not particularly limited, and may be various shapes such as powder, spherical, and flake, but spherical is preferable.
• the average particle size of the component (C) (d50 value obtained by the laser diffraction method) is not particularly limited, but the values of elongation at break and tear strength in tensile properties are moderately small while having the hardness required for practical use. From the viewpoint that a molded product can be easily obtained, it is preferably 10.0 ⁇ m or less, more preferably 9.0 ⁇ m or less, still more preferably 0.5 ⁇ m or more, and 5.0 ⁇ m or less.
• the component (C) is preferably composed of an inorganic substance, but the surface of the inorganic substance may be coated with a fatty acid, a fatty acid derivative, or the like.
• a fatty acid include linear saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, lignoseric acid, cellotic acid, montanic acid and melicic acid, sethic acid and sorbic acid.
• Examples include unsaturated fatty acids.
• the fatty acid derivative include fatty acid esters and fatty acid metal salts.
• fatty acid esters examples include esters of higher fatty acids having 8 or more carbon atoms, such as stearyl stearate, lauryl stearate, stearyl palmitate, and palmitin. Examples thereof include lauryl acid, glyceride tristearate, and glyceride tripalmitate, and examples of the fatty acid metal salt include sodium salt, potassium salt, calcium salt, aluminum salt, and zinc salt of fatty acids having 10 to 25 carbon atoms.
• the content of the component (C) in the present composition is 0.1 to 50 parts by mass, preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further, with respect to 100 parts by mass of the component (A). It is preferably 7 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more, preferably 45 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, particularly preferably. Is 30 parts by mass or less.
• the content of the component (C) is within the above range, it is possible to easily obtain a molded product having hardness required for practical use and having an appropriately small value of elongation at break and tear strength in tensile properties.
• the present composition may contain other additives other than the components (A) to (C), if necessary, as long as the object of the present invention is not impaired.
• the other additives include styrene-based thermoplastic elastomers, propylene / ⁇ -olefin random copolymers, cross-linking agents (D), cross-linking aids, softeners, heat-resistant stabilizers, antistatic agents, and weather-resistant stabilizers. , Anti-aging agents, fillers, flame retardants, colorants.
• one type may be used, or two or more types may be used.
• the present composition may or may not contain an ethylene polymer, but it is preferable that the composition does not contain the ethylene polymer.
• the ethylene-based polymer include an ethylene homopolymer and a copolymer of ethylene and one or more types of ⁇ -olefins having 3 to 20 carbon atoms.
• styrene-based thermoplastic elastomer examples include a styrene / isoprene block copolymer, a styrene / isoprene block copolymer hydrogenated product (SEP), and a styrene / isoprene / styrene block copolymer hydrogenated product.
• SEPS polystyrene / polyethylene / propylene / polystyrene block copolymer
• styrene / butadiene copolymer eg, styrene / butadiene block copolymer
• SEBS hydrogenated product of styrene / butadiene block copolymer
• SEBS polystyrene / Polyethylene / butylene / polystyrene block copolymer
• Propylene / ⁇ -olefin random copolymers are obtained using propylene, one or more ⁇ -olefins and, if necessary, other monomers copolymerizable with one or more propylenes. Examples thereof include copolymers that are used.
• the ⁇ -olefin an ⁇ -olefin having 2 or 4 to 10 carbon atoms is preferable. Specific examples thereof include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. Among these, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene are preferable.
• Crosslinking agent (D) In the present composition 1, it is preferable to use the component (D) when it is desired to partially or completely crosslink the component (A), particularly when dynamically cross-linking each component to be blended in the present composition 1. , in this composition 2, the component (D) is used.
• the component (D) is not particularly limited, and conventionally known cross-linking agents can be used, and specific examples thereof include organic peroxides, sulfur, sulfur compounds, and phenol-based cross-linking agents. Among these, an organic peroxide is preferable because the obtained composition and its molded product are not easily colored by a cross-linking agent, and a molded product whose hue can be easily adjusted can be easily obtained.
• organic peroxide examples include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-.
• 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane are used in terms of odor, scorch stability, etc.
• Hexin-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.
• the content of the component (D) in the present composition can easily obtain a molded product having an excellent balance between hardness, elongation at break and tear strength. From this point of view, it is preferably 0.5 parts by mass or more, more preferably 0.6 parts by mass or more, still more preferably 0.7 parts by mass or more, and preferably 5.0 parts by mass with respect to 100 parts by mass of the component (A). It is less than or equal to parts by mass, more preferably 2.9 parts by mass or less, still more preferably 2.0 parts by mass or less, and particularly preferably 1.5 parts by mass or less.
• Cross-linking aid When the component (D) is used, it is preferable to use a cross-linking aid from the viewpoint of making the cross-linking reaction uniform.
• the cross-linking aid is not particularly limited, and conventionally known cross-linking aids can be used and may be appropriately selected depending on the type of the component (D).
• the cross-linking aid may be, for example, sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N, 4-.
• divinylbenzene has good compatibility with each component constituting the present composition and has a solubilizing effect of organic peroxide, so that it can be used as a dispersion aid for organic peroxide. It also works, so that homogeneous cross-linking is likely to occur during heat treatment, which is preferable. Therefore, by using divinylbenzene as a cross-linking aid, there is a tendency that the present composition having a well-balanced fluidity and physical properties can be easily obtained.
• the content of the cross-linking aid in the present composition is preferably 0.5 parts by mass or more, more preferably 0.6 parts by mass with respect to 100 parts by mass of the component (A).
• mass or more more preferably 0.7 parts by mass or more, preferably 5.0 parts by mass or less, more preferably 2.9 parts by mass or less, still more preferably 2.0 parts by mass or less, particularly preferably 1. It is 5 parts by mass or less.
• Softener In this composition, it is preferable to use a softening agent for the purpose of adjusting fluidity and hardness.
• the softening agent include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and vaseline; Fat oil-based softeners such as sunflower oil, flaxseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil; sub (factis); waxes such as beeswax, carnauba wax, and lanolin; Fatty or fatty acid salts such as barium stearate, calcium stearate, zinc laurate; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer softeners such as terpene resin, petroleum resin, kumaron inden resin, and atactic polypropylene.
• petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropy
• Ester softeners such as dioctylphthalate, dioctyl adipate, dioctyl sebacate; microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal modified polyisoprene, hydrogenated terminal modified polyisoprene, liquid thiocol, hydrocarbons
• Examples include synthetic lubricating oil.
• the softener for example, one that has been mixed (oil-expanded) in advance with the component (A) may be used, or may be used when preparing the present composition, and each compounded in the present composition. It may be post-added when the components are dynamically heat treated.
• the content of the softening agent in the present composition is usually 10 parts by mass or more, preferably 15 parts by mass or more, and more preferably 20 parts by mass with respect to 100 parts by mass of the component (A). It is 5 parts by mass or more, usually 200 parts by mass or less, preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.
• the content of the softening agent is within the above range, the present composition having fluidity suitable for molding tends to be easily obtained, and further, a molded product having excellent mechanical properties, heat resistance, and heat aging resistance. Tends to be easily obtained.
• the present composition can be produced by mixing and kneading the components (A) to (C) and, if necessary, the other additives described above.
• a conventionally known mixing / kneading machine such as a Banbury mixer, a mixing roll, a Henschel mixer, a kneader, or a single-screw or twin-screw extruder.
• the order of addition of each component during this mixing / kneading is not particularly limited.
• the present composition 1 is preferably produced by dynamically cross-linking (dynamically heat-treating) the above-mentioned components (A) to (C) and, if necessary, the above-mentioned other additives.
• the present composition 2 is produced by dynamically cross-linking (dynamically heat-treating) the components (A) to (D) and, if necessary, the other additives described above.
• the dynamic cross-linking includes, for example, mixing and kneading the components (A) to (C) and, if necessary, the other additives described above by a mixing / kneading device while heating, and applying a shearing force. However, it is preferable to crosslink.
• a cross-linking agent as the above-mentioned other additive.
• a composition containing a component in a state where at least a part of the component (A) is cross-linked can be obtained.
• “at least partially crosslinked” means that the gel content is in the range of 5 to 98% by mass, preferably 10 to 95% by mass.
• the dynamic cross-linking is preferably performed in a non-open type device, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide.
• the heating temperature in the dynamic crosslinking is usually 125 ° C. or higher, preferably 145 ° C. or higher, usually 280 ° C. or lower, preferably 240 ° C. or lower, and the mixing / kneading time is usually 1 minute or longer, preferably 3 minutes or longer, usually. It is 30 minutes or less, preferably 20 minutes or less.
• the maximum shear rate for example 10 sec -1 or more, preferably 100 sec -1 or more, more preferably 1,000 sec -1 or more, more preferably 2,000sec Shear force such as -1 or more, for example 100,000 sec -1 or less, preferably 50,000 sec -1 or less, more preferably 10,000 sec -1 or less, still more preferably 7,000 sec -1 or less.
• the melt flow rate of this composition is preferably 1 g / 10 minutes or more and 170 g / 10 minutes from the viewpoint of being a composition having excellent moldability. Less than, more preferably 1 to 160 g / 10 minutes, still more preferably 1 g / 10 minutes or more, less than 130 g / 10 minutes, still more preferably 1 g / 10 minutes or more, less than 110 g / 10 minutes, still more preferably 1 g / 10 minutes. As mentioned above, it is less than 100 g / 10 minutes, particularly preferably 1 g / 10 minutes or more and less than 50 g / 10 minutes.
• the melt flow rate of this composition is preferably 6.0 g / 10 minutes or less, more preferably from the viewpoint of producing a composition having excellent moldability. Is 5.0 g / 10 minutes or less, more preferably less than 4.0 g / 10 minutes.
• the shore A hardness (instantaneous value) (according to the measurement method of JIS K 6253) of the present composition 2 is preferably 40 or more, more preferably 50 or more, still more preferably 55 or more, preferably 80 or less, more preferably. Is 75 or less, more preferably 70 or less.
• the composition 2 can be suitably used for vehicle parts, particularly instrumental panels. Specifically, the shore A hardness (instantaneous value) can be measured by the method described in the following Examples.
• the elongation at break of the present composition 2 is preferably 200% or more and less than 450%, more preferably 200% or more and less than 350%.
• a molded product having an appropriately small elongation at break can be easily formed, and when the molded product is, for example, an instrumental panel, air is used. It is possible to obtain an instrumental panel that is easily broken by the expansion force of the bag. Specifically, the elongation at break can be measured by the method described in the following Examples.
• the tear strength of the composition 2 (based on the measurement method of JIS K 6252-1) is preferably 16 N / mm or more and less than 27 N / mm, more preferably 16 to 24 N / mm, still more preferably 16 N / mm or more. It is less than 21 N / mm.
• a molded product having an appropriately small tear strength value can be easily formed. An instrumental panel that is easily broken by expansion force can be obtained. Specifically, the tear strength can be measured by the method described in the following Examples.
• the compression set (based on the measurement method of JIS K 6262) of the present composition 2 is preferably 15% or more, more preferably 16% or more, still more preferably 18% or more, and particularly preferably 19% or more. Is 30% or less, more preferably 27% or less, still more preferably 25% or less, and particularly preferably 23% or less.
• the compression set can be measured by the method described in the following Examples.
• the molded product according to one embodiment of the present invention is not particularly limited as long as the composition is included, and is a molded product molded by any known molding method depending on the intended use.
• the molding method include, for example, press molding, injection molding, extrusion molding, calendar molding, hollow molding, vacuum forming, and compression molding.
• the molded body is preferably used for vehicle parts.
• vehicle parts it is preferably used as an interior skin material.
• the interior skin material include an instrumental panel, a door trim, a console, and an armrest.
• an instrumental panel is particularly preferable from the viewpoint of more exerting the effects of the present invention.
• the molded body can be used not only for vehicle parts but also for, for example, sports equipment and building materials.
• Crosslinking aid Divinylbenzene (trade name: DVB-810, manufactured by Nittetsu Chemical & Materials Co., Ltd.)
• Crosslinking agent (D-1) Organic peroxide (2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, trade name: Perhexa 25B, manufactured by NOF CORPORATION)
• the melting point of the propylene-based polymer (B) was measured using a differential scanning calorimeter (DSC) in accordance with JIS K 7121. Specifically, the pellet of the propylene polymer (B) is heated at 230 ° C. for 10 minutes, then lowered to 30 ° C. at a rate of 10 ° C./min, held for 1 minute, and then held at 10 ° C./min. The temperature was raised at the rate of. In the DSC curve at this time, the temperature at which the amount of heat absorbed was maximum was defined as the melting point.
• DSC differential scanning calorimeter
• Example 1 140 parts by mass of copolymer (A-1) (100 parts by mass as rubber component), 50 parts by mass of propylene-based polymer (B-1), 15 parts by mass of inorganic filler (C-1), cross-linking agent (D-) 1) 1 part by mass, 1 part by mass of the cross-linking aid, and the softening agent were sufficiently mixed with a Henschel mixer.
• the numerical value (content (parts by mass)) in the column of the softener in Table 1 is a mixture of the softener contained in the copolymer (A-1) used and the cross-linking agent (D-1). It is the total amount of the softener used at the time of preparation and the softening agent used at the time of preparing the following pellets.
• thermoplastic elastomer composition Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the type and amount of the raw materials used were changed as shown in Table 1.
• the numerical values in the column of raw materials in Table 1 indicate parts by mass.
• melt flow rate (MFR)> The melt flow rate of the thermoplastic elastomer compositions obtained in Examples and Comparative Examples was measured at 230 ° C. under a 10 kg load or a 5 kg load according to JIS K 7210. The results are shown in Table 1. If the MFR is too low to be measured, it is described as "impossible”.
• thermoplastic elastomer composition obtained in Examples or Comparative Examples were press-processed by a hot press molding machine (press temperature: 190 ° C., cooling temperature: 20 ° C., preheating time: 6 minutes, pressure melting time. : 4 minutes).
• press temperature 190 ° C.
• cooling temperature 20 ° C.
• preheating time 6 minutes
• pressure melting time 4 minutes
• a flat plate press sheet having a length of 12 cm, a width of 14.7 cm and a thickness of 2 mm was obtained for each composition.
• ⁇ Tear strength> The tear strength was measured according to JIS K 6252-1 using a test piece obtained by punching a dumbbell-shaped No. 3 test piece from a press sheet having a thickness of 2 mm produced by the above method (measurement temperature). : 23 ° C.). The results are shown in Table 1.
• Tear strength of 16 N / mm or more and less than 21 N / mm B: Tear strength of 21 N / mm or more and less than 27 N / mm C: Tear strength of 27 N / mm or more and less than 30 N / mm
• D Tear strength of 16 N / mm Less than or more than 30 N / mm

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