WO2019077989A1 - Composition de résine élastomère, et corps moulé - Google Patents

Composition de résine élastomère, et corps moulé Download PDF

Info

Publication number
WO2019077989A1
WO2019077989A1 PCT/JP2018/036764 JP2018036764W WO2019077989A1 WO 2019077989 A1 WO2019077989 A1 WO 2019077989A1 JP 2018036764 W JP2018036764 W JP 2018036764W WO 2019077989 A1 WO2019077989 A1 WO 2019077989A1
Authority
WO
WIPO (PCT)
Prior art keywords
elastomer resin
resin composition
mass
elastomer
less
Prior art date
Application number
PCT/JP2018/036764
Other languages
English (en)
Japanese (ja)
Inventor
金丸　正実
望 藤井
Original Assignee
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017252446A external-priority patent/JP2019077851A/ja
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Publication of WO2019077989A1 publication Critical patent/WO2019077989A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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 an elastomeric resin composition and a molded article comprising the elastomeric resin composition.
  • BACKGROUND ART Elastomers used in various fields such as automobiles, machinery, and electrical products are blended with additives such as oil for the purpose of improving mechanical properties and processability.
  • the anti-vibration rubber member described in Patent Document 1 contains a bleeding lubricant, and is designed to control the oil bleeding property in order to impart slidability.
  • the problem to be solved by the present invention is to provide a crosslinked elastomeric resin composition excellent in ozone resistance, and a molded article comprising the elastomeric resin composition.
  • Elastomer resin (A) using a differential scanning calorimeter (DSC), a sample is held at -10 ° C for 5 minutes in a nitrogen atmosphere, and then the melting endotherm obtained by raising the temperature at 10 ° C / min.
  • An elastomeric resin composition comprising a polypropylene resin (B) having a melting endotherm ( ⁇ H-D) obtained from a curve of 0 J / g to 80 J / g and an additive (D), 50% by mass or more and 99.5% by mass or less of the elastomer resin (A) with respect to the total amount 100% by mass of the elastomer resin (A) and the polypropylene resin (B), and the polypropylene resin (B) Elastomer resin composition containing 0.5 mass% or more and 50 mass% or less, and not showing fluidity at 230 ° C.
  • ⁇ H-D melting endotherm
  • the elastomer resin (A) contains a structural unit derived from at least one selected from the group consisting of styrene, diene, silicon-containing monomer, fluorine-containing monomer, ethylene and isoprene.
  • the elastomer resin composition as described in any one.
  • the diene is at least one selected from the group consisting of butadiene, isoprene, ⁇ -farnesene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 1,4-hexadiene.
  • the elastomer resin composition as described in. [7] The elastomer resin composition according to any one of the above [1] to [5], wherein the elastomer resin (A) contains a structural unit derived from styrene. [8] The elastomer resin composition according to any one of the above [1] to [5], wherein the elastomer resin (A) is a copolymer of styrene and a conjugated diene. [9] The elastomer resin composition according to any one of the above [1] to [5], wherein the elastomer resin (A) is an ethylene-propylene non-conjugated diene copolymer rubber.
  • the elastomer resin composition of the present invention is excellent in ozone resistance.
  • the elastomer resin composition of the present invention can control the bleed-out of the additive, and the surface of the resin composition can be coated with the bleed-out additive to improve the ozone resistance.
  • the elastomer resin composition of the present embodiment uses an elastomer resin (A) and a differential scanning calorimeter (DSC), holds the sample at -10 ° C for 5 minutes in a nitrogen atmosphere, and then raises the temperature at 10 ° C / min.
  • A elastomer resin
  • DSC differential scanning calorimeter
  • Elastomer resin composition containing a polypropylene resin (B) having an endothermic energy ( ⁇ H-D) of 0 J / g or more and 80 J / g or less obtained from the melt endothermic curve obtained thereby, and an additive (D) 50% by mass or more and 99.5% by mass or less of the elastomer resin (A) with respect to a total amount of 100% by mass of the elastomer resin (A) and the polypropylene resin (B), (B) is an elastomer resin composition which contains 0.5% by mass or more and 50% by mass or less and does not exhibit fluidity at 230 ° C.
  • ⁇ H-D endothermic energy
  • the elastomer resin (A) used in the present embodiment is not particularly limited, and various well-known olefin rubbers can be used.
  • the elastomer resin (A) contains a constitutional unit derived from at least one selected from the group consisting of styrene, diene, silicon-containing monomer, fluorine-containing monomer, ethylene and isoprene from the viewpoint of elastic recovery.
  • diene examples include conjugated dienes such as butadiene, isoprene and ⁇ -farnesene; and non-conjugated dienes such as cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 1,4-hexadiene.
  • the diene is preferably at least one selected from the group consisting of butadiene, isoprene, ⁇ -farnesene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 1,4-hexadiene.
  • Examples of the elastomer resin (A) include copolymers of styrene and conjugated diene, and hydrogenated products thereof, ethylene- ⁇ -olefin copolymer rubber, conjugated diene rubber, butadiene rubber, nitrile rubber and the like.
  • ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber composed of ethylene, ⁇ -olefin having 3 to 20 carbon atoms and nonconjugated polyene can also be mentioned, and specific examples thereof include ethylene-propylene-nonconjugated Mention may be made of diene copolymer rubbers.
  • the elastomer resin (A) is preferably a copolymer of styrene and a conjugated diene, and an ethylene-propylene-non-conjugated diene copolymer rubber.
  • the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber is preferably an amorphous random elastic copolymer composed of ethylene, ⁇ -olefin having 3 to 20 carbon atoms and nonconjugated polyene, and is mixed with a peroxide
  • An olefin copolymer rubber which is cross-linked to decrease fluidity or stops flowing by being kneaded under heating.
  • non-conjugated diene examples include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene.
  • non-conjugated diene copolymer rubber examples include ethylene-propylene non-conjugated diene copolymer rubber, ethylene 1-butene non-conjugated diene copolymer rubber are preferable, and in particular ethylene-propylene non-conjugated diene copolymer rubber, especially ethylene-propylene Particular preference is given to ethylidene norbornene copolymer rubbers.
  • non-conjugated polyenes other than non-conjugated dienes specifically, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 6, 9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene- 1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene 6, 7-Dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-de
  • the Mooney viscosity [ML (1 + 4), 125 ° C.] of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber is preferably 5 or more, more preferably 20 or more, from the viewpoint of the balance between moldability and physical properties, And preferably 150 or less, more preferably 100 or less.
  • the iodine value of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber is preferably 10 or less. When the iodine value is in such a range, a partially balanced crosslinked thermoplastic elastomer composition can be obtained.
  • the elastomer resin (A) include ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber (CR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), styrene-isoprene copolymer, butadiene-isoprene copolymer, polybutadiene, styrene-isoprene-butadiene terpolymer, acrylonitrile-chloroprene rubber (ACR), butyl rubber (IIR), styrene-butadiene-styrene block Copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene-styrene block copolymer (SBBS),
  • elastomer resin A
  • natural rubber NR
  • EPR ethylene-propylene rubber
  • SIBR styrene-isoprene-butadiene rubber
  • EA ethylene-acrylic rubber
  • CSM Chlorosulfonated polyethylene
  • urethane rubber epichlorohydrin rubber
  • acrylic rubber chlorinated polyethylene
  • silicone rubber fluororubber and the like
  • styrene-based elastomer resin Commercial products of styrene-based elastomer resin include “D series” and “G series” manufactured by Kraton Co., “TR series” manufactured by JSR Co., Ltd., “Dynalon”, and “Tuffuprene” manufactured by Asahi Kasei Co., Ltd. Asaprene, Tuftec, SEPTON manufactured by Kuraray Co., Ltd., Hybler and the like.
  • the content of the elastomer resin (A) in the elastomer resin composition is 50% by mass to 99.5% by mass with respect to 100% by mass of the total amount of the elastomer resin (A) and the polypropylene resin (B) is there. If it is less than 50% by mass, the elastomer property of the elastomer resin composition may be lowered, and if it exceeds 99.5% by mass, it may be difficult to control the bleed out of the additive of the elastomer resin composition.
  • the content of the elastomer resin (A) is preferably 60 mass% or more, more preferably 65 mass based on 100 mass% of the total amount of the elastomer resin (A) and the polypropylene resin (B). % Or more, more preferably 70% by mass or more, and preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less.
  • the polypropylene resin (B) used in the present embodiment is obtained by using a differential scanning calorimeter (DSC) and maintaining the sample at -10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min.
  • the melting endotherm ( ⁇ H-D) obtained from the melting endothermic curve is from 0 J / g to 80 J / g. If the melting endotherm ( ⁇ H-D) is less than 0 J / g, the bleed out of the additive can not be controlled in the elastomer resin composition, and if it exceeds 80 J / g, the flexibility of the elastomer resin composition is increased. There is a risk of lowering it.
  • the melting endotherm ( ⁇ H-D) is preferably 20 J / g or more, more preferably 25 J / g or more, further preferably 27 J / g or more, still more preferably 30 J / g or more. And preferably it is 50 J / g or less, more preferably 45 J / g or less, still more preferably 40 J / g or less.
  • the melting endotherm ( ⁇ H-D) is the highest temperature of the melting endothermic curve obtained by DSC measurement, with the line connecting the point on the low temperature side without change in calorific value and the point on the high temperature side without change in calorific value as a baseline It is calculated by obtaining an area surrounded by a line portion including a peak observed on the side and the baseline.
  • the melting endotherm ( ⁇ H-D) can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
  • a polypropylene resin (B) satisfy
  • DSC differential scanning calorimeter
  • the melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C. or more and 120 ° C. or less.
  • the melting point (Tm-D) of the polypropylene resin (B) is not observed or from 0 ° C. to 120 ° C. from the viewpoint of enhancing the flexibility of the elastomer resin composition and controlling the bleed out of the additive (D). Is preferred.
  • a melting point is observed, from the same viewpoint, more preferably 30 ° C. or more, further preferably 35 ° C. or more, still more preferably 40 ° C. or more, and more preferably 100 ° C. or less, more preferably It is 90 ° C. or less, more preferably 85 ° C. or less.
  • the melting point can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
  • the intrinsic viscosity [ ⁇ ] of the polypropylene resin (B) is preferably 0.01 dL / g or more, more preferably 0.10 dL / g or more, still more preferably 0.30 dL / g or more, still more preferably 0. .40 dL / g or more, and preferably 2.50 dL / g or less, more preferably 2.00 dL / g or less, still more preferably 1.80 dL / g or less, still more preferably 1.70 dL / g or less, Still more preferably, it is 1.00 dL / g or less.
  • the mixing property of the elastomer resin (A) and the polypropylene resin (B) can be further enhanced.
  • processability can be further improved by setting it as 2.50 dL / g or less.
  • a resin composition containing a filler such as talc, for example is set to 0.01 dL / g or more.
  • the intrinsic viscosity [ ⁇ ] is calculated by using a Ubbelohde viscometer to measure the reduced viscosity ( ⁇ SP / c) in tetralin at 135 ° C., and using the following equation (Hagins' equation).
  • ⁇ SP / c [ ⁇ ] + K [ ⁇ ] 2 c SP SP / c (dL / g):
  • Intrinsic viscosity c (g / dL): Polymer viscosity K 0.35 (Huggins constant)
  • the molecular weight distribution (Mw / Mn) of the polypropylene resin (B) is preferably 3.0 or less, more preferably 2.8 or less, still more preferably 2.6 or less, still more preferably 2.5 or less, And preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more, still more preferably 1.8 or more.
  • the molecular weight distribution (Mw / Mn) is a value calculated from the polystyrene equivalent weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC).
  • the polypropylene resin (B) is not particularly limited as long as the above-mentioned melting heat absorption amount ( ⁇ H-D) satisfies the above range, for example, a propylene homopolymer, a propylene-ethylene block copolymer, a propylene-butene block copolymer Polymer, propylene- ⁇ -olefin block copolymer, propylene-ethylene random copolymer, propylene-butene random copolymer, propylene-ethylene-butene ternary random copolymer, propylene- ⁇ -olefin random copolymer Or a propylene-based polymer selected from propylene- ⁇ -olefin graft copolymer etc., preferably a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-butene random copolymer, a propylene- ⁇ -Olefin random copolymer, propylene A
  • the polypropylene resin (B) is a copolymer
  • it contains at least 0 mol% and at most 20 mol% of at least one structural unit selected from the group consisting of ethylene and ⁇ -olefins having 4 to 30 carbon atoms It is preferable from the viewpoint of suppressing the occurrence of bumps due to crosslinking and enhancing the flexibility of the elastomer resin composition. From such a viewpoint, more preferably 0.5 mol% or more, further preferably 1.0 mol% or more, and more preferably 18.5 mol% or less, still more preferably 15.0 mol% or less Still more preferably, it is 10.0 mol% or less.
  • the polypropylene resin (B) preferably has a structural unit of an olefin having 2 carbon atoms (that is, an ethylene monomer), preferably 0 mol%. More than 20 mol% or less, more preferably more than 0 mol% and not more than 18 mol%, still more preferably more than 0 mol% and not more than 16 mol%, still more preferably more than 0 mol% and not more than 14 mol%.
  • the content of the ⁇ -olefin having 4 or more carbon atoms is preferably more than 0% by mole and 30% by mole or less, more preferably 0 It is more than 25% by mole, more preferably more than 0% by mole and not more than 20% by mole.
  • a commercial item can be used as polypropylene resin (B). Specific examples thereof include “S400”, “S600” and “S901” of “L-MODU” (registered trademark) (made by Idemitsu Kosan Co., Ltd.). Commercial products of amorphous poly- ⁇ -olefin include “REXtac” manufactured by REXtac, LLC, “Vestoplast” manufactured by Evonik, “Eastoflex” and “Aerafin” manufactured by Eastman (all of which are trade names) ).
  • propylene-based elastomers Commercial products of propylene-based elastomers include "Tafmer XM”, “Tafmer PN” and “Tafmer SN” manufactured by Mitsui Chemicals, Inc .; “Tuff Selenium” manufactured by Sumitomo Chemical Co., Ltd .; “Prime Polymer” manufactured by Prime Polymer Co., Ltd. TPO ";” Versify "manufactured by Dow Chemical Co., Ltd .;” Vistamaxx ",” Linxar “manufactured by Exxon Mobil,” Licocene “manufactured by Clariant;” Adflex "manufactured by Bacell, etc. Product name).
  • the coating layer formed on the surface of the resin composition is bled out and has high transparency compared to the wax, and it is characterized by excellent appearance.
  • the mechanical strength of the coating layer is also high when using “L-MODU”, and less brittle as compared to when using wax, making it less likely to crack and having higher durability. There is.
  • the polypropylene resin (B) can be obtained by polymerizing monomers in the presence of a Ziegler-Natta type catalyst or a polymerization catalyst such as a metallocene catalyst.
  • the polypropylene resin (B) is preferably a polypropylene resin obtained by a metallocene catalyst.
  • the metallocene catalyst is a kind of homogeneous catalyst, and the resulting polymer is a uniform polymer having a narrow molecular weight distribution and a narrow compositional distribution.
  • the content of the polypropylene resin (B) in the elastomer resin composition is 0.5% by mass or more and 50% by mass or less based on 100% by mass of the total amount of the elastomer resin (A) and the polypropylene resin (B) It is. If the amount is less than 0.5% by mass, the flexibility of the elastomer resin composition may be reduced, and if it exceeds 50% by mass, the elastic recovery of the elastomer resin composition may be reduced. From such a viewpoint, the content of the polypropylene resin (B) is preferably 1% by mass or more, more preferably 2 with respect to 100% by mass of the total amount of the elastomer resin (A) and the polypropylene resin (B). It is preferably at least 40% by mass, more preferably at most 35% by mass, and still more preferably at most 30% by mass.
  • the total content of the elastomer resin (A) and the polypropylene resin (B) in the elastomer resin composition is preferably 35% by mass or more, more preferably 50% by mass or more based on 100% by mass of the elastomer resin composition More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more.
  • the elastomer resin composition of the present embodiment is further obtained by using a differential scanning calorimeter (DSC), maintaining the sample at -10 ° C. for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C./min.
  • the polypropylene resin (C) having a melting point (Tm-D) defined as the peak top observed at the highest temperature side of the melting endothermic curve is more than 120 ° C. and 180 ° C. or less from the viewpoint of strength preferable.
  • the melting point (Tm-D) of the polypropylene resin (C) is preferably 130 ° C. or more, more preferably 140 ° C. or more, and preferably 170 ° C. or less, more preferably 165 ° C. or less. If the melting point of the polypropylene resin (C) is within the above range, it is preferable from the viewpoint of maintaining the hardness at high temperature.
  • a polypropylene resin (C) a propylene homopolymer, a propylene-ethylene block copolymer, a propylene-butene block copolymer, a propylene- ⁇ -olefin block copolymer, a propylene-ethylene random copolymer, propylene- It is preferable that it is a propylene-based polymer (C ′) selected from butene random copolymer, propylene- ⁇ -olefin random copolymer, propylene- ⁇ -olefin graft copolymer and the like.
  • the propylene-based polymer (C ′) preferably contains 1% by mole or less of the ethylene structural unit contained in the polymer, and contains the ethylene structural unit It is more preferable that there be no propylene homopolymer.
  • the above-mentioned polymer may be a polymer using a monomer derived from petroleum or coal, or may be a polymer using a monomer derived from biomass.
  • the elastomer resin composition of the present embodiment contains a polypropylene resin (C)
  • the content thereof is preferably 5% by mass or more, more preferably 8% by mass or more based on 100% by mass of the elastomer resin composition. , More preferably, it is 11% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less. If it is 5% by mass or more, strength improvement of the composition can be expected, and if it is 30% by mass or less, the flexibility is not impaired.
  • thermoplastic resin composition of the present embodiment depending on the purpose, a part of the elastomer resin (A), or a part or all of the polypropylene resin (C), the elastomer resin (A) and the polypropylene It is possible to replace with other thermoplastic resins other than the resin (C).
  • specific examples of other thermoplastic resins are not particularly limited, and acrylic resins such as polymethyl acrylate, polymethyl methacrylate, ethylene-ethyl acrylate copolymer, polystyrene resin, nylon 6, nylon 66, nylon 12, etc.
  • Polyamide resin polyimide resin, acetate resin, polyether sulfonic acid resin, saturated ester resin such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, thermoplastic urethane resin, thermoplastic elastomer, vinyl chloride resin, poly fluoride Examples thereof include vinyl fluoride resins such as vinyl and polyvinylidene fluoride, and silicone resins.
  • the elastomer resin composition of the present embodiment contains an additive (D).
  • the type of additive is appropriately determined according to the purpose of use of the elastomeric resin composition.
  • the additive (D) preferably contains an oil.
  • the elastomer resin composition of the present embodiment may contain one type of additive, or may contain two or more types of additive.
  • the oil is not particularly limited, and mineral oil such as paraffinic process oil, naphthenic process oil, isoparaffinic oil, mineral oil hydrocarbon of aromatic series, polybutene, polybutadiene, poly ( ⁇ -olefin), etc.
  • Synthetic resin hydrocarbon such as molecular weight, alkyl benzene and castor oil, fatty oil softener such as linseed oil, rapeseed oil, rapeseed oil etc, ester plasticizer such as dibutyl phthalate, dioctyl phthalate, dioctyl adipate and dioctyl sebacate Can be illustrated.
  • mineral oil type hydrocarbons mineral oil type hydrocarbons, paraffin type process oils and naphthene type process oils are preferably used.
  • paraffinic oils in which the carbon number of paraffinic hydrocarbons accounts for 50% of the total carbon number are preferred.
  • the mineral oil hydrocarbon has a weight average molecular weight of 50 to 2,000, preferably 100 to 1,500, and a kinematic viscosity at 40 ° C. of 3 to 800 cSt, preferably 5 to 600 cSt.
  • the pour point is preferably ⁇ 40 to 0 ° C., particularly preferably ⁇ 30 to 0 ° C.
  • the flash point (COC method) is preferably 200 to 400 ° C., particularly preferably 250 to 350 ° C.
  • the kinematic viscosity is a value measured in accordance with ISO 3104
  • the pour point is a value measured in accordance with JIS K 2269: 1987
  • the flash point is JIS K 2265-4: 2007 (ASTM-D92, Cleveland open It is a value measured based on a formula.
  • paraffin-based process oil Commercial products of paraffin-based process oil include “Diana Process Oil PW-32” manufactured by Idemitsu Kosan Co., Ltd., “Diana Process Oil PW-90”, “Diana Process Oil PW-150”, and “Diana Process Oil PS- 32 ",” Diana Process Oil PS-90 “,” Diana Process Oil PS-430 “;” Kaydol Oil “manufactured by Chevron USA,” ParaLux Oil “, etc. (all trade names).
  • additives other than oil for example, surface modifiers; anti-aging agents (amines, phenols, sulfurs, phosphoruss, waxes); vulcanizing agents; vulcanization accelerators (sulfenamides, thiurams) , Thiazole type, guanidine type), vulcanization accelerators such as zinc flower, etc., vulcanization inhibitor, peptizer, white filler, coupling agent, radical generator, polyolefin, slip agent, anti blocking agent, heat Stabilizers; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; light stabilizers; ultraviolet light absorbers; crystal nucleating agents; antiblocking agents; sealability improvers; , Release agents such as silicone oil; Lubricants such as polyethylene wax; Color agents; Ceramic, carbon black, amber, shenna, kaolin, nickel titanium oxide Pigments such as cobalt blue, plastic blue, quinophthalone, diketopyrrolopyrrole, qui
  • Organic fillers such as; foaming agents; fire retardants such as hydrated compounds, red phosphorus, ammonium polyphosphate, antimony, silicone etc; antistatic agents; antibacterial agents; tackifiers such as dispersants, compatibilizers, rosin derivatives etc. Tackfire); "Leostmar Trademark) B "(trade name, Riken Technos Co., Ltd.) adhesive elastomers such as; coumarone resins, coumarone - indene resin, phenol terpene resins.
  • antioxidants examples include trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, Adekastab 1178 (manufactured by ADEKA Co., Ltd., "Adekastab” is a registered trademark), Sumilizer TNP (Sumitomo Chemical Co., Ltd., Sumilizer) Phosphorus-based antioxidants such as Irgafos 168 (BASF, "Irgafos” is a registered trademark), Sandostab P-EPQ (San, "Sandostab” is a registered trademark), etc .; t-Butyl-4-methylphenol, n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, Irganox 1010 (manufactured by BASF, "Irganox” is registered Phenolic antioxidants such as Trademarks, Dilauryl
  • the elastomer resin composition of the present embodiment may be foamed.
  • foaming agent azo compounds such as carbon dioxide gas, nitrogen gas, azobisisobutyronitrile, azodicarbonamide, barium azodicarboxylate, etc .; N, N'-dinitrosopentamethylenetetramine, trimethylene trinitroamine etc.
  • Sulfonylhydrazine compounds such as paratoluenesulfonylhydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 4,4'-oxybis (benzenesulfonylhydrazide), allylbis (sulfonylhydrazide);
  • p- Mention may be made of sulfonyl semicarbazide compounds such as toluylene sulfonyl semicarbazide and 4,4′-oxybis (benzene sulfonyl semicarbazide). One of these may be used alone, or two or more may be used in combination.
  • the content when the additive (D) is an oil is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 70% by mass, with respect to 100% by mass of the elastomer resin composition.
  • the content is more preferably 60% by mass or less, still more preferably 50% by mass or less. If it is 10 mass% or more, the effect derived from an additive can be anticipated, and if 70 mass% or less, control of the bleed-out of an additive can be anticipated.
  • the elastomer resin composition of this embodiment it is also possible to add a crosslinking agent, a crosslinking auxiliary agent, etc. and to carry out partial crosslinking.
  • the crosslinking agent include organic peroxides, sulfur, sulfur compounds, and phenol-based vulcanizing agents such as phenol resins. Among these, organic peroxides are preferred.
  • organic peroxides include 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3 -Hexin; 2,5-dimethyl-2,5-di (benzoylperoxy) -hexane; t-butylperoxybenzoate; dicumyl peroxide; t-butylcumyl peroxide; diisopropylbenzene hydroperoxide; 1,3 Benzoyl peroxide; 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane; di-t-butyl peroxide; n-butyl- 4,4-Bis (t-butylperoxy) valerate; p-chlorobenzoyl peroxide; 2,4-dichloro Benzoyl peroxide; t-butyl peroxy is
  • crosslinking assistant for example, N-methyl-N, 4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, divinylbenzene, trimethylolpropane tri (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, allyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, quinone dioxime, p, p'-dibenzoylquinone dioxime, bismaleimide, phenylenebismaleimide, trimethylolpropane-N, N'-m- Phenylene maleimide, ethylene glycol dimethacrylate, vinyl butyrate, vinyl stearate, unsaturated silane compounds, sulfur and the like can be mentioned.
  • crosslinking assistant By using such a crosslinking assistant, a uniform and mild crosslinking reaction can be expected.
  • crosslinking assistants triallyl cyanurate, ethylene glycol dimethacrylate, divinyl benzene and bismaleimide are preferable. They are easy to handle, have good compatibility between the elastomer resin (A), which is the main component of the product to be crosslinked, and the polypropylene resin (B), and solubilize the organic peroxide Since it has an action and acts as a dispersant for the organic peroxide, an elastomeric resin composition is obtained in which the crosslinking effect of the heat treatment is homogeneous and the balance between flexibility and physical properties is achieved.
  • the crosslinking agent and the crosslinking coagent may be used alone or in combination of two or more.
  • the crosslinking degree is adjusted by optionally using in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (D) be able to.
  • an unsaturated silane compound when used as a crosslinking assistant, it can be made to contact with water in the presence of a silanol condensation catalyst to further advance crosslinking.
  • the elastomer resin composition of the present embodiment is blended, melt-kneaded with the above-mentioned elastomer resin (A), polypropylene resin (B), additives (D) and, if necessary, polypropylene resin (C). Obtained by The elastomer resin composition of the present embodiment can be manufactured by employing a method of manufacturing a vulcanized rubber. Moreover, the elastomer resin composition of this embodiment can also be manufactured using the manufacturing method of a thermoplastic resin composition.
  • the pellet can be charged into the hopper of the extruder and melt-kneaded.
  • the polypropylene resin (B) is produced by the polymerization device, pellets of the elastomer resin (A) may be added and melt-kneaded using an extruder connected to the polymerization device.
  • the elastomer resin (A) may be added in the presence of the polypropylene resin (B) in the solvent, and the solvent may be removed and dried to obtain pellets or bales.
  • the polypropylene resin (B) is mixed and desolvated to produce a composition of the elastomer resin (A) and the polypropylene resin (B). It is also good. After that, pelletizing can be performed as needed.
  • the composition after the kneading comprising the elastomer resin (A) and the polypropylene resin (B), the additive (D), and, if necessary, the polypropylene resin (C) regardless of the presence or absence of the pelletizing step It is also possible to knead.
  • both of them may be prepared without immersing the elastomer resin (A) in the oil in advance. It becomes possible to knead easily. Kneading can be carried out using a commonly used apparatus such as a high speed mixer, a Banbury mixer, a continuous kneader, a single screw or twin screw extruder, a roll, a Brabender plastograph, etc. After kneading with a kneader other than the extruder, it may be pelletized using an extruder.
  • the elastomer resin composition of the present embodiment needs to exhibit no flowability at 230 ° C. from the viewpoint of heat resistance.
  • “does not exhibit flowability at 230 ° C.” means that a 5 mm ⁇ 5 mm ⁇ 1 mm thick molded body obtained by heat press molding an elastomer resin composition is heated at 230 ° C. for 15 minutes under oven air. It means that the shape is maintained.
  • the elastomer resin composition of the present embodiment is excellent in ozone resistance.
  • the number and size of cracks are combined and evaluated. The number of cracks is evaluated in three stages of A, B, and C, and an A evaluation with less cracks is preferable. Further, the size of the crack is evaluated in five steps of 1 to 5, and one evaluation with a small crack is preferable.
  • the molded article of the present invention is a molded article made of the above resin composition.
  • a molded body having a desired shape can be obtained.
  • a molded object can also be obtained by heating and bridge
  • D ⁇ Additive (D)> (D1-1) "Diana Process Oil PW-90”: Paraffin oil, manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity at 40 ° C 90 cSt, pour point -17.5 ° C, flash point 266 ° C (D1-2) “Diana Process Oil NS-100”: Naphthenic oil, manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity at 40 ° C. 95 cSt, pour point ⁇ 37.5 ° C., flash point 226 ° C.
  • the physical properties of the polypropylene resin (B-1) were measured by the following method.
  • [DSC measurement] A sample of 10 mg was held at -10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (Perkin Elmer, “DSC-7”), and then obtained by raising the temperature at 10 ° C./min. It was determined as the melting endotherm ( ⁇ H-D) from the melting endothermic curve. Further, the melting point (Tm-D) was determined from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
  • the melting endotherm ( ⁇ H-D) is a differential scanning calorimeter (manufactured by Perkin-Elmer Co., Ltd.) with a line connecting the point on the low temperature side with no change in calorific value and the point on the high temperature side with no change in calorific value as a baseline.
  • DSC-7 differential scanning calorimeter
  • the following apparatus and conditions were used for the measurement, and the weight average molecular weight and number average molecular weight of polystyrene conversion were obtained.
  • the molecular weight distribution (Mw / Mn) is a value calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn).
  • ⁇ GPC measuring device Column: "TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation Detector: RI detector for liquid chromatography Waters Corporation "WATERS 150C” ⁇ Measurement conditions> Solvent: 1,2,4-Trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL Injection volume: 160 ⁇ L Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)
  • Oil Bleedability Aluminum sheet (45 mm ⁇ 45 mm) above and below the sample sandwiched by oil absorbent paper after holding the sample press board with oil absorbent paper (65 mm ⁇ 97 mm) whose weight has been measured in advance. I further pinched. This was placed on a vat, and a 0.5 kg weight was placed thereon, and placed in a thermostatic chamber previously set at 70 ° C. After 24 hours, the sample was taken out of the thermostat, and after standing at room temperature for 24 hours, the weight of the oil removing paper was measured, and the increased weight was made the weight of the bleed oil. If the weight of the bleed oil was more than 0 g / m 2 and not more than 0.40 g / m 2 , it was judged as pass.
  • Ozone Deterioration Test The elastomer resin composition was heat-pressed at 160 ° C. for 12 minutes using an electric heat press (manufactured by Ohtake Machine Industry Co., Ltd.) to obtain a dumbbell-shaped No. 1 shape test piece .
  • a static ozone deterioration test was conducted under the following conditions. Ozone concentration: 50 ⁇ 5 pphm Test temperature: 40 ⁇ 2 ° C Conditioning temperature: 23 ⁇ 2 ° C
  • Tensile strain 20% Testing machine used: "Ozone weather meter OMS-HE" (Suga Test Machine Co., Ltd.)
  • test piece After the test piece was exposed to ozone, it was taken out of the test tank 24 hours, 48 hours, 72 hours and 96 hours after the start of the test, and the state of cracks was observed and recorded.
  • the evaluation was performed in accordance with Annex JA of JIS K6259-1: 2015. As described in Annex JA of JIS K6259-1: 2015, the number and size of cracks were evaluated in combination. The number of cracks is evaluated in three stages of A, B, and C, and an A evaluation with less cracks is preferable. Further, the size of the crack is evaluated in five steps of 1 to 5, and one evaluation with a small crack is preferable.
  • the size of the cracks is more important than the number of cracks, and it is preferable that the cracks be small.
  • the number of cracks is smaller in the A-5 rating than in the B-4 rating, but the cracks are larger.
  • the tensile stress is concentrated to the small number of cracks. Therefore, even if the number of cracks is large, cleavage is more likely to occur in the A-5 evaluation than in the B-4 evaluation whose length is short.
  • Examples 3 to 4 and Comparative Example 2 The components of the types and amounts described in Table 2 were kneaded with a roll under the following conditions to prepare an elastomer resin composition. In Table 2, blanks indicate no blending.
  • Testing machine manufactured by Ikeda Machine Industry Co., Ltd., 6 inch high temperature roll size: 6′′ ⁇ ⁇ 16 ′ ′ Front roll speed: 25 rpm Front and rear roll rotation ratio: 1 (front): 1.22 (rear) Roll temperature: 80 ⁇ 5 ° C Number of turns: 3/4 round 3 round trip rounds: 6
  • Example 5 The components of the types and amounts described in Table 3 were kneaded with a roll under the following conditions to prepare an elastomeric resin composition.
  • Testing machine 8-inch water-cooled roll "HF-2R" manufactured by Daihan Co., Ltd.
  • Roll size 8 " ⁇ ⁇ 18"
  • Front roll speed 20 rpm
  • Front and rear roll rotation ratio 1 (front): 1.15 (rear)
  • Roll temperature 23 ° C
  • the elastomer resin composition of the present invention is excellent in ozone resistance. Further, from the results of Table 1, it can be seen that the elastomer resin composition of the present invention can control the bleed out of oil in the elastomer resin composition. By controlling the amount of bleed to an appropriate range, it is considered that the surface of the resin composition is coated with the additive that bleeds out, and the ozone resistance is improved. Moreover, according to the results of Table 2, in comparison with Comparative Example 2 in which the wax-based antioxidant (D7-1) was used, the examples 3 and 4 in which the polypropylene resin (B) was used had better ozone resistance. I understand.
  • the elastomer resin composition of the present invention is a tire; automobile exterior materials such as moldings, wipers, bumpers, etc .; automobile interior materials such as instrumental panels, center panels, center console boxes, door trims, pillars, assist grips, steering wheels, airbag covers etc. Automotive functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots etc. Remote control switches, various key tops of OA equipment, home appliances parts such as TVs, stereos, vacuum cleaners, etc. Electrical appliances, underwater glasses, underwater cameras etc.
  • the elastomer resin composition of the present invention is excellent in ozone resistance, it is possible to suppress the aging of a molded article made of the elastomer resin composition. Further, according to the present invention, in the molded article made of the elastomer resin composition, the effect of the additive is exerted on the surface of the molded article by gradually bleeding out the additive by appropriately controlling the bleeding speed of the additive. It can be done. In particular, when an oil is contained as an additive in tire applications, it is possible to suppress tire cracking due to oil omission. In the case of containing a wax as an additive in tires, cables, etc., the surface of the tire is coated by gradually bleeding out the wax from the tire by appropriately controlling the bleeding speed of the wax. Aging can be prevented.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine élastomère qui comprend : une résine élastomère (A) ; une résine à base de polypropylène (B) qui présente une quantité d'énergie endothermique （ΔＨ－Ｄ） obtenue à partir d'une courbe d'énergie endothermique résultant d'une élévation de température de 10°C/minute, après maintien d'un échantillon pendant 5 minutes à -10°C sous une atmosphère d'azote, à l'aide d'un calorimètre à compensation de puissance (DSC), supérieure ou égale à ０Ｊ／ｇ et inférieure ou égale à ８０Ｊ／ｇ; et un additif (D). La composition de résine élastomère de l'invention contient 50% en masse ou plus à 99,5% en masse ou moins de ladite résine élastomère (A), et 0,5% en masse ou plus à 50% en masse ou moins d'une résine à base de polypropylène (B) pour 100% en masse de quantité totale de ladite résine élastomère (A) et de ladite résine à base de polypropylène (B), et ne se montre pas fluide à 230°C.
PCT/JP2018/036764 2017-10-19 2018-10-02 Composition de résine élastomère, et corps moulé WO2019077989A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017-202703 2017-10-19
JP2017202703 2017-10-19
JP2017252446A JP2019077851A (ja) 2017-10-19 2017-12-27 エラストマー樹脂組成物及び成形体
JP2017-252446 2017-12-27

Publications (1)

Publication Number Publication Date
WO2019077989A1 true WO2019077989A1 (fr) 2019-04-25

Family

ID=66173596

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/036764 WO2019077989A1 (fr) 2017-10-19 2018-10-02 Composition de résine élastomère, et corps moulé

Country Status (1)

Country Link
WO (1) WO2019077989A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022190631A1 (fr) * 2021-03-10 2022-09-15 三井化学株式会社 Composition de résine et corps moulé

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002201313A (ja) * 2000-12-28 2002-07-19 Jsr Corp 熱可塑性エラストマー組成物及びその製造方法
JP2004018818A (ja) * 2002-06-20 2004-01-22 Asahi Kasei Corp 耐熱性熱可塑性ゴム組成物
JP2006328306A (ja) * 2005-05-30 2006-12-07 Asahi Kasei Chemicals Corp オレフィン系重合体組成物
JP2018095763A (ja) * 2016-12-15 2018-06-21 東洋ゴム工業株式会社 ゴム組成物
WO2018147391A1 (fr) * 2017-02-13 2018-08-16 出光興産株式会社 Composition de résine thermoplastique, et corps moulé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002201313A (ja) * 2000-12-28 2002-07-19 Jsr Corp 熱可塑性エラストマー組成物及びその製造方法
JP2004018818A (ja) * 2002-06-20 2004-01-22 Asahi Kasei Corp 耐熱性熱可塑性ゴム組成物
JP2006328306A (ja) * 2005-05-30 2006-12-07 Asahi Kasei Chemicals Corp オレフィン系重合体組成物
JP2018095763A (ja) * 2016-12-15 2018-06-21 東洋ゴム工業株式会社 ゴム組成物
WO2018147391A1 (fr) * 2017-02-13 2018-08-16 出光興産株式会社 Composition de résine thermoplastique, et corps moulé

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022190631A1 (fr) * 2021-03-10 2022-09-15 三井化学株式会社 Composition de résine et corps moulé

Similar Documents

Publication Publication Date Title
JP2019077851A (ja) エラストマー樹脂組成物及び成形体
JP6699853B2 (ja) 熱可塑性エラストマー組成物、架橋物、成形体、部材、ウェザーシール、及びウェザーシール用コーナー部材
US6531546B2 (en) Rubber composition
JP3693017B2 (ja) 熱可塑性エラストマー組成物
JP5972200B2 (ja) 熱可塑性エラストマー組成物、それを用いた成形体、および用途
KR102001799B1 (ko) 열가소성 엘라스토머 조성물 및 그의 성형체
TW201837104A (zh) 熱塑性樹脂組合物及成形體
JP2014080488A (ja) 熱可塑性エラストマー組成物および該組成物からなる成形体
US7411017B2 (en) Thermoplastic elastomer and molded article thereof
CN110461933B (zh) 成型外观优异的热塑性弹性体组合物及其成型体
JP5055072B2 (ja) 熱可塑性エラストマー組成物の製造方法、及び成形体
WO2019077989A1 (fr) Composition de résine élastomère, et corps moulé
WO2019176796A1 (fr) STRATIFIÉ CONTENANT UNE COMPOSITION DE COPOLYMÈRE D'ÉTHYLÈNE - α－OLÉFINE - POLYÈNE NON CONJUGUÉ, ET COMPOSITION DE COPOLYMÈRE D'ÉTHYLÈNE - α－OLÉFINE - POLYÈNE NON CONJUGUÉ
WO2008000493A1 (fr) Adhésion de structures polymériques
KR102387508B1 (ko) 중합체 조성물 및 그의 용도
JP5204512B2 (ja) 熱可塑性エラストマー組成物
JP2019044112A (ja) 複合成形体用動的架橋型熱可塑性エラストマー組成物及び複合成形体
JP2019085440A (ja) カレンダー成形用樹脂組成物並びに自動車内装表皮材及び成形体の製造方法
JP6792522B2 (ja) 柔らかい触感の熱可塑性エラストマー組成物及びその成形体
JP2019044111A (ja) 動的架橋型熱可塑性エラストマー組成物及びその成形体
JP2008231210A (ja) 熱可塑性エラストマー組成物およびその用途
JP5089156B2 (ja) 熱可塑性エラストマー組成物およびその用途
JP2023014023A (ja) 熱可塑性エラストマー組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18868660

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18868660

Country of ref document: EP

Kind code of ref document: A1