WO2023013773A1 - Composition élastomère thermoplastique et corps moulé la comprenant - Google Patents

Composition élastomère thermoplastique et corps moulé la comprenant Download PDF

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WO2023013773A1
WO2023013773A1 PCT/JP2022/030142 JP2022030142W WO2023013773A1 WO 2023013773 A1 WO2023013773 A1 WO 2023013773A1 JP 2022030142 W JP2022030142 W JP 2022030142W WO 2023013773 A1 WO2023013773 A1 WO 2023013773A1
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thermoplastic elastomer
elastomer composition
mass
parts
olefin
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English (en)
Japanese (ja)
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武志 金原
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三井化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08L23/12—Polypropene
    • 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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a thermoplastic elastomer composition and a molded article made from it.
  • Olefin thermoplastic elastomers are lightweight, easy to recycle, and do not generate toxic gases when incinerated. , electrical and electronic parts, building materials, etc.
  • Patent Document 1 discloses that a composition obtained by blending a softening agent with a thermoplastic elastomer can be used as an interior and exterior material for automobiles.
  • Patent Document 2 a mixture containing an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer, an olefin resin, and a softening agent having a specific kinematic viscosity is dynamically heat-treated in the presence of a cross-linking agent.
  • a thermoplastic elastomer composition obtained by the method is disclosed.
  • Patent Document 2 discloses that the fogging phenomenon can be suppressed by using a softener having a specific kinematic viscosity.
  • Patent Document 3 also discloses a completely or partially crosslinked olefinic thermoplastic elastomer composition comprising a crystalline polyolefin, an olefinic copolymer rubber, and a paraffinic mineral oil softening agent. It has been shown that excellent fogging resistance and gloss can be obtained by employing agents having specific evaporation loss and kinematic viscosity.
  • thermoplastic elastomers with improved fogging properties often have poor moldability, and there is a demand for the realization of thermoplastic elastomers that can achieve both fogging properties and moldability.
  • an object of the present invention is to provide a thermoplastic elastomer and a molded article with improved fogging properties while maintaining a certain degree of moldability.
  • the inventors of the present invention have found that, in a thermoplastic elastomer containing a softening agent, a softening agent having a low content of components having a low relative molecular weight in terms of polystyrene is used as the softening agent.
  • a softening agent having a low content of components having a low relative molecular weight in terms of polystyrene is used as the softening agent.
  • the present invention relates to the following [1] to [11].
  • thermoplastic elastomer composition comprising the following components (A) to (C) and at least partially crosslinked.
  • A 100 parts by mass of ethylene/ ⁇ -olefin/non-conjugated polyene copolymer;
  • B polypropylene resin 50 to 200 parts by mass;
  • C 20 to 150 parts by mass of a softening agent in which the ratio (R) of components having a relative molecular weight of 600 or less in terms of polystyrene measured by gel permeation chromatography (GPC) is 25% or less.
  • thermoplastic elastomer composition according to [1], wherein the softening agent (C) has an evaporation loss of 0.2% by mass or less at 200° C. and normal pressure for 1 hour.
  • thermoplastic elastomer composition according to [1] or [2], wherein the softener (C) has a kinematic viscosity at 40° C. of 50 mm 2 /s or more.
  • thermoplastic elastomer composition according to any one of [1] to [3], wherein the softener (C) has a kinematic viscosity at 40° C. of 300 mm 2 /s or less.
  • the polypropylene resin (B) is selected from the group consisting of a propylene homopolymer, a random copolymer of propylene and an ⁇ -olefin other than propylene, and a block copolymer of propylene and an ⁇ -olefin other than propylene.
  • the thermoplastic elastomer composition according to any one of [1] to [4], which is at least one kind of
  • thermoplastic elastomer composition according to any one of [1] to [5], further comprising a cross-linking agent.
  • thermoplastic elastomer composition according to any one of claims [1] to [7], which satisfies the following requirements (1) to (2).
  • Melt flow rate (MFR, 230° C., 10 kg load) measured according to JIS K7210 is 1 to 150 g/10 minutes.
  • the Shore A hardness (instantaneous value) measured according to JIS K6253 in a state in which three press sheets with a thickness of 2 mm are stacked to form a thickness of 6 mm is 50-100.
  • thermoplastic elastomer composition according to any one of [1] to [8].
  • thermoplastic elastomer and a molded article having a certain degree of moldability and improved fogging property.
  • polymer is used to encompass homopolymers and copolymers, unless otherwise specified.
  • a numerical range represented using “ ⁇ ” means a range including the numerical values described before and after " ⁇ " as lower and upper limits.
  • thermoplastic elastomer composition contains the following components (A) to (C) and is at least partially crosslinked: (A) 100 parts by mass of ethylene/ ⁇ -olefin/non-conjugated polyene copolymer; (B) polypropylene resin 50 to 200 parts by mass; (C) Softener 20 to 150 parts by mass.
  • thermoplastic elastomer composition according to the present invention will be described in detail below.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A) (hereinafter also referred to as “copolymer (A)”) used in the present invention comprises ethylene and an ⁇ -olefin other than ethylene, preferably having 3 carbon atoms. It is a copolymer of .about.20 ⁇ -olefins and non-conjugated polyenes, preferably non-conjugated dienes.
  • the copolymer (A) can be produced by various known methods using a Ziegler-Natta catalyst or a metallocene catalyst.
  • the ethylene/ ⁇ -olefin (molar ratio) in the copolymer (A) is usually 85/15 to 55/45, preferably 83/17 to 60/40.
  • ⁇ -olefin examples 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.
  • said ⁇ -olefin is propylene.
  • non-conjugated diene examples include dicyclopentadiene, cyclooctadiene, methylenenorbornene (eg, 5-methylene-2-norbornene), ethylidenenorbornene (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,
  • said non-conjugated diene is a cyclic diene.
  • cyclic dienes include 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
  • the Mooney viscosity ML 1+4 (125° C.) of the copolymer (A) is generally 10 to 200, preferably 20 to 160, more preferably 40 to 150, and the iodine value is generally 3 to 25, preferably is 5-25.
  • the copolymer (A) can exist in any crosslinked state such as uncrosslinked, partially crosslinked, or completely crosslinked in the thermoplastic elastomer. It is necessary that
  • the copolymer (A) preferably has a kinematic viscosity at 40° C. exceeding 500,000 mm 2 /s.
  • “exceeding 500,000 mm 2 /s” is a concept including cases where fluidity is low and kinematic viscosity cannot be measured.
  • the thermoplastic elastomer composition of the present invention contains a polypropylene resin (B).
  • the polypropylene resin (B) used in the present invention is preferably a propylene homopolymer or a copolymer of propylene and an olefin other than propylene.
  • the polypropylene resin (B) consists of a propylene homopolymer, a random copolymer of propylene and an ⁇ -olefin other than propylene, and a block copolymer of propylene and an ⁇ -olefin other than propylene. It is preferably at least one selected from the group.
  • Suitable raw material olefins other than propylene that constitute the polypropylene resin (B) include preferably ⁇ -olefins having 2 or 4 to 20 carbon atoms, specifically ethylene, 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. Of these olefins, ethylene is preferred.
  • the arrangement mode of the monomers constituting the polypropylene-based resin (B) is not particularly limited as long as a resinous material is obtained, but it may be random type or block type. These polypropylene-based resins may be used singly or in combination of two or more.
  • the polypropylene-based resin (B) used in the present invention is preferably a propylene-based polymer with a propylene content of 40 mol% or more, more preferably a propylene-based polymer with a propylene content of 50 mol% or more.
  • propylene homopolymers propylene/ethylene block copolymers, propylene/ethylene random copolymers, propylene/ethylene/butene random copolymers, and the like are particularly preferable.
  • the polypropylene resin (B) used in the present invention usually has a melting point of 80 to 170°C, preferably 120 to 170°C.
  • the polypropylene resin (B) used in the present invention has an MFR (ASTM D1238-65T, 230°C, 2.16 kg load) usually in the range of 0.01 to 100 g/10 minutes, particularly 0.05 to 50 g/10 minutes. Preferably.
  • the polypropylene resin (B) used in the present invention preferably has an isotactic structure as a steric structure, but may have a syndiotactic structure. It may have a structure mixed with a tic structure, or may further contain a part of the atactic structure in addition to these structures.
  • the polypropylene resin (B) used in the present invention is polymerized by various known polymerization methods.
  • the blending amount of the polypropylene resin (B) is 50 to 200 parts by mass, preferably 55 to 180 parts by mass, more preferably 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A). 60 to 160 parts by mass, more preferably 70 to 130 parts by mass.
  • the content of the following softening agent (C) in the thermoplastic elastomer composition of the present invention is relatively large, for example, the following softening agent per 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A)
  • the amount of (C) is about 100 parts by mass (for example, more than 70 parts by mass and 150 parts by mass or less, particularly 80 to 120 parts by mass)
  • the amount of the polypropylene resin (B) is compared. It may be substantially less, for example, 50 to 60 parts by mass.
  • the polypropylene-based resin (B) is composed of two or more polymers, the above numerical range is applied to the total amount of these polymers.
  • the polypropylene-based resin (B) preferably has a kinematic viscosity at 40° C. exceeding 500,000 mm 2 /s.
  • “exceeding 500,000 mm 2 /s” is a concept including cases where fluidity is low and kinematic viscosity cannot be measured.
  • the ratio (R) of components having a polystyrene-equivalent relative molecular weight of 600 or less measured by gel permeation chromatography (GPC) is 29% or less.
  • the ratio (R) is preferably 27% or less, more preferably 25% or less, and even more preferably 23% or less. It is preferable that the ratio (R) is equal to or less than a certain amount, because good fogging characteristics can be obtained, such as reduction in fogging, especially at high temperatures.
  • the relative molecular weight can be specifically measured by the method described in Examples below.
  • the softening agent (C) used in the present invention preferably has a weight average molecular weight (Mw) of 100 to 2000, more preferably 300 to 1500, and even more preferably 500 to 500, as measured by gel permeation chromatography (GPC). 1000.
  • Mw weight average molecular weight
  • the softening agent (C) used in the present invention has a molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) of preferably 0.5 to 5.0, more preferably 0.5. to 3.0, more preferably 0.5 to 2.0. It is preferable that the Mw and Mw/Mn are within the above numerical ranges in that good fogging characteristics can be obtained.
  • Mw/Mn molecular weight distribution measured by gel permeation chromatography
  • the softening agent (C) usually has an evaporation loss of 0.3% by mass or less at 200° C. and normal pressure for 1 hour, and preferably 0.2% by mass or less from the viewpoint of fogging characteristics. It is more preferably 0.15% by mass or less, and even more preferably 0.13% by mass or less.
  • the evaporation loss at 200 ° C., normal pressure, 3 hours is preferably 1.2% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.8% by mass or less. preferable.
  • the evaporation loss at 200 ° C., normal pressure, 5 hours is preferably 2.5% by mass or less, more preferably 2.0% by mass or less, and further preferably 1.5% by mass or less. preferable.
  • the thermoplastic elastomer composition of the present invention has a low content of volatile components and good fogging properties.
  • the kinematic viscosity at 40° C. of the softener (C) is often 500,000 mm 2 /s or less, and is preferably 400 mm 2 /s or less from the viewpoint of compatibility with polypropylene resins and moldability. It is preferably 300 mm 2 /s or less, more preferably 200 mm 2 /s or less.
  • the softening agent (C) preferably has a kinematic viscosity at 40° C. of 40 mm 2 /s or more, more preferably 50 mm 2 /s or more.
  • the softening agent (C) Any oil can be used as the softening agent (C) as long as it satisfies the above properties.
  • refined mineral oil may be used, and synthetic oil obtained by polymerizing olefinic monomers or a mixture of refined mineral oil and synthetic oil.
  • the softening agent (C) may be a non-bio oil, which is an oil obtained from a fossil raw material, or a bio oil, which is an oil obtained from an animal or plant raw material.
  • the refined mineral oil may be a known refined mineral oil, and among them, those containing paraffin as a main component are preferable.
  • the flash points of such refined mineral oils are typically between 240°C and 300°C.
  • An example of such refined mineral oil is disclosed in JP-A-2000-302919.
  • the residual oil obtained by atmospheric distillation of paraffin-based crude oil is subjected to a conventional vacuum distillation operation to obtain an effluent oil, dewaxed by solvent extraction or hydrotreating, hydrofinishing, and vacuum distillation. It is preferable to obtain by removing the light fraction by.
  • the synthetic oil is preferably a copolymer of ethylene and an ⁇ -olefin having 3 to 10 carbon atoms, and may contain a small amount of polyene if necessary.
  • One type of ⁇ -olefin may be used, or two or more types may be used.
  • ethylene/propylene copolymers are particularly preferred.
  • the ethylene content of the synthetic oil used in the present invention is preferably in the range of 50 to 80 mol%, more preferably in the range of 60 to 75 mol%, particularly preferably in the range of 65 to 75 mol%.
  • the synthetic oil used in the present invention may be produced by any known method, but is preferably produced using a metallocene catalyst. Synthetic oil with a narrow molecular weight distribution can be easily obtained by manufacturing with a metallocene catalyst, and an olefinic thermoplastic elastomer with excellent fogging properties can be obtained.
  • the amount of the softener (C) blended is 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A). 20 to 150 parts by mass, preferably 20 to 100 parts by mass, more preferably 25 to 70 parts by mass, still more preferably 30 to 60 parts by mass.
  • the content of the polypropylene resin (B) in the thermoplastic elastomer composition of the present invention is relatively small, for example, the polypropylene per 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A)
  • the blending amount of the system resin (B) is about 50 parts by mass (for example, 30 parts by mass or more and less than 70 parts by mass, particularly 50 to 60 parts by mass)
  • the blending amount of the softening agent (C) is For example, it may be more than 70 parts by mass and 150 parts by mass or less, particularly 80 to 120 parts by mass.
  • thermoplastic elastomer composition of the present invention contains the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene-based resin (B), and the softener (C), and at least partially is crosslinked.
  • thermoplastic elastomer composition of the present invention preferably satisfies the following requirements (1) and (2): (1) Melt flow rate (MFR, 230° C., 10 kg load) measured according to JIS K7210 is 1 to 150 g/10 minutes. (2) The Shore A hardness (instantaneous value) measured according to JIS K6253 in a state in which three press sheets with a thickness of 2 mm are stacked to form a thickness of 6 mm is 50-100.
  • the melt flow rate defined in the requirement (1) is preferably 1 to 50 g/10 minutes, more preferably 1 to 30 g/10 minutes, even more preferably 1 to 20 g/10 minutes, and particularly preferably 5 to 20 g/10 minutes. minutes.
  • the softener (C ) is about 100 parts by mass (for example, more than 70 parts by mass and 150 parts by mass or less, particularly 80 to 120 parts by mass)
  • the melt flow rate may exceed 50 g/10 minutes. , for example, from 50 to 80 g/10 minutes.
  • the Shore A hardness (instantaneous value) defined in the requirement (2) is preferably 60-100, more preferably 70-97, even more preferably 75-95, and particularly preferably 80-95.
  • the softener (C ) is about 100 parts by mass (for example, more than 70 parts by mass and 150 parts by mass or less, particularly 80 to 120 parts by mass)
  • the Shore A hardness (instantaneous value) may be somewhat small, For example, it may be 60-70.
  • the Shore A hardness (instantaneous value) can be specifically measured by the method described in Examples below.
  • thermoplastic elastomer composition of the present invention comprises the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene resin (B), and the softening agent, as long as at least a portion of the thermoplastic elastomer composition is crosslinked. It may consist only of (C).
  • thermoplastic elastomer composition of the present invention in addition to the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene resin (B), and the softener (C), the Contains other components (hereinafter referred to as "other components") that do not correspond to the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene resin (B), or the softener (C). It's okay to be
  • the cross-linking is usually performed in the presence of a cross-linking agent. Therefore, in one preferred embodiment of the present invention, the thermoplastic elastomer composition of the present invention further contains a cross-linking agent, which will be described later. In this case, a cross-linking aid, which will be described later, may be further contained.
  • a cross-linking agent which will be described later.
  • the thermoplastic elastomer composition of the present invention also includes the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A). It may further contain other rubbers (hereinafter referred to as "other rubbers") that do not correspond to the polypropylene resin (B), in which case the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A) Other rubbers are preferably used in an amount of 50 parts by mass or less with respect to 100 parts by mass.
  • diene rubbers such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), natural rubber (NR), butyl rubber (IIR), SEBS, polyisobutylene, etc. can be used.
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • NR natural rubber
  • IIR butyl rubber
  • SEBS polyisobutylene, etc.
  • thermoplastic elastomer composition of the present invention contains the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene resin (B), the softening agent (C), an optional cross-linking agent, and an optional Additives such as cross-linking aids and optional components other than the above "other rubbers", such as heat stabilizers, antistatic agents, weather stabilizers, anti-aging agents, fillers, coloring agents, lubricants, etc. Depending on the circumstances, they can be blended within a range that does not impair the object of the present invention.
  • the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene resin (B) and the softening agent (C ) that is, the above-mentioned “other components”) in an amount of 30 parts by mass or less, but the present invention is not limited to this.
  • thermoplastic elastomer composition of the present invention may further contain a crosslinking agent in addition to the above components (A) to (C).
  • a crosslinking agent examples include organic peroxides, phenol resins, sulfur, hydrosilicone compounds, amino resins, quinones or derivatives thereof, amine compounds, azo compounds, epoxy compounds, isocyanates, thermosetting elastomers, and the like.
  • Cross-linking agents used may be mentioned.
  • the cross-linking agent is preferably an organic peroxide.
  • organic peroxide examples 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-butylperbenzoate, tert-butylperoxy isopropyl carbonate, diacetyl peroxide, lauroyl
  • Such an organic peroxide is 0.05 to 3 parts by mass, preferably 0.10 to 1 part by mass, with respect to 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A). used in such amounts. If the amount of the organic peroxide is less than the above range, the resulting thermoplastic elastomer composition will have a low degree of cross-linking, resulting in insufficient heat resistance, tensile properties and rubber elasticity. On the other hand, if the amount is more than the above range, the resulting thermoplastic elastomer composition may have an excessively high degree of cross-linking, resulting in deterioration of moldability.
  • the amount of the organic peroxide compounded may be appropriately adjusted according to the amount of the softener (C) compounded.
  • the amount of the organic peroxide to be blended may also be relatively large accordingly.
  • a cross-linking aid can be blended in the cross-linking treatment with the organic peroxide. That is, when the thermoplastic elastomer composition of the present invention contains the organic peroxide as the cross-linking agent, the thermoplastic elastomer composition may further contain a cross-linking aid.
  • such coagents include sulfur, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane.
  • -N,N'-m-phenylene dimaleimide a cross-linking aid commonly used in cross-linking treatment with an organic peroxide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol Polyfunctional methacrylate monomers such as dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate.
  • Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin resin and the ethylene-based copolymer elastomer, which are the main components of the material to be crosslinked, and has the effect of solubilizing the organic peroxide. Since it functions as a dispersant for the organic peroxide, the cross-linking effect of the heat treatment is uniform, and a thermoplastic elastomer composition having well-balanced fluidity and physical properties can be obtained.
  • the cross-linking aid as described above is usually 5 parts by mass or less, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A). Can be used in quantity.
  • the amount of the cross-linking coagent compounded may be appropriately adjusted according to the amount of the softener (C) compounded. When it is included, the amount of the cross-linking coagent may be relatively large accordingly.
  • tertiary amines such as triethylamine, tributylamine and 2,4,6-tri(dimethylamino)phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium,
  • a decomposition accelerator such as a naphthenate of manganese, magnesium, lead, mercury or the like may be used.
  • thermoplastic elastomer composition of the present invention is obtained by cross-linking a mixture containing the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene resin (B), and the softener (C).
  • the cross-linking can be performed by a known dynamic cross-linking method.
  • the dynamic cross-linking method is to perform dynamic heat treatment in the presence of a cross-linking agent, and "dynamic heat treatment" means kneading in a molten state.
  • Dynamic heat treatment in the presence of a cross-linking agent typically dynamically cross-links the mixture in the presence of the cross-linking agent (i.e., the mixture is kneaded in the melt in the presence of the cross-linking agent).
  • the cross-linking agent i.e., the mixture is kneaded in the melt in the presence of the cross-linking agent.
  • at least a portion of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A) is crosslinked while a shearing force is applied to the mixture) to obtain a crosslinked thermoplastic elastomer composition.
  • the cross-linking agent is in the form of a cross-linking agent mixture containing the cross-linking agent and the softening agent (C) diluted with the softening agent (C), and the ethylene/ ⁇ -olefin/non-conjugated polyene It may be blended in a mixture containing the copolymer (A) and the polypropylene resin (B).
  • the cross-linking agent mixture may further contain the organic peroxide.
  • the order of mixing the optional cross-linking aids is not particularly limited, for example, the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), the polypropylene-based resin (B), and the cross-linking agent mixture are added first. After mixing, the softener (C) may be further blended.
  • the dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and preferably in an inert gas atmosphere such as nitrogen or carbon dioxide gas.
  • the heat treatment temperature ranges from the melting point of the polypropylene resin (B) to 300°C, usually 150 to 290°C, preferably 170 to 270°C.
  • the kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes.
  • the applied shearing force has a shear rate of 10 to 10,000 sec -1 , preferably 100 to 5,000 sec -1 .
  • a mixing roll As a kneading device, a mixing roll, an intensive mixer (eg, Banbury mixer, kneader), a single-screw or twin-screw extruder, etc. can be used, but a non-open type device is preferred, and a twin-screw extruder is particularly preferred.
  • an intensive mixer eg, Banbury mixer, kneader
  • a single-screw or twin-screw extruder etc.
  • a twin-screw extruder is particularly preferred.
  • thermoplastic elastomer of the present invention is desirably statically heat treated in hot air after the dynamic heat treatment as described above.
  • the heat treatment is preferably performed at 80 to 130° C. for about 1 to 10 hours.
  • a molded article according to the present invention contains the thermoplastic elastomer composition.
  • the molded article can be a film or a sheet.
  • Applications of the molded product include interior materials for automobiles.
  • the molded article can be suitably used, for example, as a skin layer of an automobile interior material.
  • thermoplastic elastomer composition of the present invention comprises an ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A), a polypropylene resin (B), and a softening agent (C). Since it is excellent, it can be molded using molding equipment conventionally used in compression molding, transfer molding, injection molding, extrusion molding, and the like.
  • thermoplastic elastomer composition when manufacturing an interior material for automobiles from the thermoplastic elastomer composition, it can usually be manufactured according to the following conventional method.
  • the skin layer of the automotive interior material of the present invention can be provided with a surface layer made of at least one compound selected from the group consisting of polyurethane, saturated polyester, acrylic acid ester resin, polyvinyl chloride and isocyanate resin.
  • polyethylene terephthalate, polybutylene terephthalate and derivatives thereof are used as the saturated polyester used to form such a surface layer.
  • Polymethyl (meth) acrylate, polyisobutyl (meth) acrylate, poly 2-ethylhexyl (meth) acrylate, and the like are used as acrylic acid ester resins.
  • polyhexamethylene diisocyanate, polyisophorone diisocyanate and the like are used as the isocyanate resin.
  • Such a surface layer is preferably 300 ⁇ m or less.
  • a primer layer can be interposed between the skin layer and such a surface layer.
  • the automobile interior material of the present invention can constitute a laminate with a polyolefin foam or a laminate with a polyolefin resin.
  • polyolefins used here include polyethylene and polypropylene.
  • polypropylene include the polypropylene-based resins used in the production of the thermoplastic elastomer composition of the present invention.
  • Such a laminate can be obtained, for example, by extruding a thermoplastic elastomer composition using an extruder with a T-die, and laminating the extruded sheet-like thermoplastic elastomer composition in a molten state with a polyolefin foam sheet. It is manufactured by passing between a pair of rolls or by sequential injection molding of a polyolefin resin and a thermoplastic elastomer.
  • the automobile interior material of the present invention is mainly used as a skin layer for door trims, instrument panels, ceilings, handles, console boxes, seat seats, and the like.
  • melt flow rate (MFR) The melt flow rates of the thermoplastic elastomer compositions obtained in Examples and Comparative Examples were measured at 230° C. and a load of 10 kg according to JIS K 7210.
  • thermoplastic elastomer compositions obtained in Examples and Comparative Examples were pressed with 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
  • Shore A hardness Using a press sheet with a thickness of 2 mm produced by the method described above in "(2) Production of press sheet”, Shore A hardness (instantaneous value ) (hereinafter, “A hardness”) was determined.
  • Shore A hardness instantaneous value
  • the Shore A hardness (instantaneous value) was measured with respect to a test piece obtained by stacking three press sheets having a thickness of 2 mm prepared in (2) above.
  • the heating is performed under three conditions: "100°C x 100 hours in air”, “100°C x 200 hours in air” and “100°C x 300 hours in air”. Heat evaporation loss was determined.
  • the heating is performed under three conditions: "200°C x 1 hour in air”, “200°C x 3 hours in air” and "200°C x 5 hours in air”. Heat evaporation loss was determined.
  • the iodine value of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A) was obtained by a titration method. Specifically, the following method was used.
  • 0.5 g of the copolymer was dissolved in 60 ml of carbon tetrachloride, added with a small amount of Wiss reagent and 20% potassium iodide solution, and titrated with 0.1 mol/L sodium thiosulfate solution. Near the end point, a starch indicator was added, and the solution was titrated until the light purple color disappeared while stirring well.
  • Mooney Viscosity (125° C.) of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A) is 125° C. in accordance with the measurement method of ASTM D 1646-19a. measured in
  • the softening agent is subjected to gel permeation chromatography (GPC) measurement under the following conditions, and the relative molecular weight (polystyrene equivalent molecular weight) and its weight fraction (dW/dlogM) at each elution time are obtained. , a molecular weight distribution curve was prepared, and the polystyrene-equivalent weight average molecular weight Mw, number average molecular weight Mn, and Mw/Mn were obtained.
  • GPC gel permeation chromatography
  • hexane feed rate: 26.5 kg/h
  • ethylene feed rate 4.6 kg/h
  • propylene feed rate 3.0 kg/h
  • ENB feed rate 420 g/h
  • hydrogen feed rate It was continuously supplied to the polymerization reactor at an amount of 2 normal liters/h. While maintaining the polymerization pressure at 1.6 MPa-G, the following formula as the main catalyst:
  • the compound (t-butylamido)-dimethyl( ⁇ 5 -2-methyl-s-indacen-1-yl)silantitanium (II) 1,3-pentadiene represented by the formula was fed at a feed rate of 0.003 mmol/h. was continuously fed to the polymerization vessel. 0.017 mmol/h of (C 6 H 5 ) 3 CB(C 6 F 5 ) 4 as a cocatalyst and 10 mmol/h of triisobutylaluminum as an organoaluminum compound were continuously fed to the polymerization vessel.
  • A-1 The physical properties of the obtained copolymer (hereinafter referred to as "A-1") are shown below.
  • (Physical properties of A-1) Ethylene unit content 66% by mass Iodine value 9.8 Mooney viscosity ML 1+4 (125°C) 61
  • B-1 propylene/ethylene block copolymer
  • B-1 Propylene/ethylene block copolymer
  • C-1 a softening agent having physical properties shown in Table 1 below was used.
  • softening agent C-2 Idemitsu Kosan Co., Ltd., trade name "Diana Process Oil PW-380"
  • softening agent C-2 is also shown in Table 1 shows physical properties.
  • softening agents (C'-1) having physical properties shown in Table 1 below (manufactured by Idemitsu Kosan Co., Ltd., trade name “Diana Process Oil PW-100") ( hereinafter referred to as "C'-1") was used.
  • softening agent (C'-2) manufactured by Idemitsu Kosan Co., Ltd., trade name "Diana Process Oil PW-90" (hereinafter referred to as "C'-2") as a softening agent related to C' also shows the physical properties in Table 1.
  • C softening agent having the physical properties shown in the table below, which is obtained by preparing according to Example 1 described in JP-A-2001-294714 ( C'-3) (hereinafter referred to as "C'-3") was used.
  • C-1, C'-1 and C'-3 are shown in Table 1 below together with the physical properties of C-2 and C'-2.
  • Cross-linking agent organic peroxide (2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, trade name: Perhexyne 25B, manufactured by NOF Corporation)
  • Crosslinking aid divinylbenzene (trade name: DVB-810, manufactured by Nippon Steel Chemical & Materials Co., Ltd.)
  • the cross-linking agent and the cross-linking aid were used in the form of a cross-linking agent mixture in which 100 parts by mass of the cross-linking aid and 100 parts by mass of the softening agent were mixed with 100 parts by mass of the cross-linking agent.
  • the softening agent (C-1), the softening agent (C'-1), or the softening agent (C'-1) described above in “(C) Softening agents and other softening agents"C'-3) was used.
  • Example 1 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer (A-1); 100 parts by mass of the polypropylene resin (B-1), 0.28 parts by mass of an organic peroxide (manufactured by NOF Corporation, trade name: Perhexyne 25B) as a cross-linking agent, 0.28 parts by mass of divinylbenzene as a cross-linking aid, and a softening agent (C-1) 0. 28 parts by weight of a cross-linking agent mixture was thoroughly mixed with a Henschel mixer.
  • A-1 100 parts by mass of the ethylene/ ⁇ -olefin/non-conjugated polyene copolymer
  • B-1 100 parts by mass of the polypropylene resin
  • an organic peroxide manufactured by NOF Corporation, trade name: Perhexyne 25B
  • thermoplastic elastomer composition Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1, except that the raw materials used and the compounding amounts were changed as shown in Table 2 or Table 3 below.

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Abstract

Cette composition élastomère thermoplastique contient : 100 parties en masse de (A) un copolymère d'éthylène-α-oléfine-polyène non conjugué ; de 50 à 200 parties en masse de (B) une résine à base de polypropylène ; et de 20 à 150 parties en masse de (C) un agent adoucissant dans lequel la proportion (R) de constituants ayant un poids moléculaire relatif inférieur ou égal à 600 en termes de polystyrène, telle que mesurée par chromatographie par perméation de gel, est inférieure ou égale à 25 %. Au moins une partie de la composition élastomère thermoplastique est réticulée.
PCT/JP2022/030142 2021-08-06 2022-08-05 Composition élastomère thermoplastique et corps moulé la comprenant WO2023013773A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000302919A (ja) * 1999-02-16 2000-10-31 Idemitsu Kosan Co Ltd ゴムプロセス油及びゴム組成物
JP2001294714A (ja) * 2000-02-09 2001-10-23 Mitsui Chemicals Inc 低フォギング性熱可塑性エラストマー組成物並びに該組成物の製造方法及び用途
JP2003213050A (ja) * 2001-11-13 2003-07-30 Mitsubishi Chemicals Corp オレフィン系熱可塑性エラストマー
WO2007060843A1 (fr) * 2005-11-25 2007-05-31 Mitsui Chemicals, Inc. Composition d’huile a usiner, elastomere allonge a l’huile la contenant et composition olefinique d'elastomere thermoplastique
WO2019189310A1 (fr) * 2018-03-30 2019-10-03 三井化学株式会社 Adhésif de masque et pellicule comportant ledit adhésif

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000302919A (ja) * 1999-02-16 2000-10-31 Idemitsu Kosan Co Ltd ゴムプロセス油及びゴム組成物
JP2001294714A (ja) * 2000-02-09 2001-10-23 Mitsui Chemicals Inc 低フォギング性熱可塑性エラストマー組成物並びに該組成物の製造方法及び用途
JP2003213050A (ja) * 2001-11-13 2003-07-30 Mitsubishi Chemicals Corp オレフィン系熱可塑性エラストマー
WO2007060843A1 (fr) * 2005-11-25 2007-05-31 Mitsui Chemicals, Inc. Composition d’huile a usiner, elastomere allonge a l’huile la contenant et composition olefinique d'elastomere thermoplastique
WO2019189310A1 (fr) * 2018-03-30 2019-10-03 三井化学株式会社 Adhésif de masque et pellicule comportant ledit adhésif

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