WO2017002957A1 - Mousse de caoutchouc d'éthylène-propylène-diène, et matériau d'étanchéité - Google Patents

Mousse de caoutchouc d'éthylène-propylène-diène, et matériau d'étanchéité Download PDF

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WO2017002957A1
WO2017002957A1 PCT/JP2016/069625 JP2016069625W WO2017002957A1 WO 2017002957 A1 WO2017002957 A1 WO 2017002957A1 JP 2016069625 W JP2016069625 W JP 2016069625W WO 2017002957 A1 WO2017002957 A1 WO 2017002957A1
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mass
ethylene
less
epdm
parts
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PCT/JP2016/069625
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English (en)
Japanese (ja)
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歩実 田中
崇行 岩瀬
鈴木　宏明
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日東電工株式会社
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Priority claimed from JP2016126839A external-priority patent/JP6757609B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention relates to an ethylene / propylene / diene rubber foam and a sealing material, and more particularly to an ethylene / propylene / diene rubber foam and a sealing material having the same.
  • EPDM ethylene, propylene, diene rubber
  • EPDM foam is generally produced by foaming EPDM with a foaming agent and crosslinking with a crosslinking agent.
  • an EPDM foam for example, an EPDM foam obtained by foaming a rubber composition containing EPDM, a quinoid crosslinking agent, a foaming agent, and the like has been proposed (see, for example, Patent Document 1).
  • An object of the present invention is to provide an ethylene / propylene / diene rubber foam having good water blocking properties and a sealing material provided with the same.
  • the present invention [1] is obtained by foaming a rubber composition containing an ethylene / propylene / diene rubber, a crosslinking agent, a crosslinking accelerator, a foaming agent, a foaming aid and a nonionic surfactant, and has an elongation percentage. And an ethylene / propylene / diene rubber foam of 300% or more and 1000% or less.
  • the present invention [2] includes the ethylene / propylene / diene rubber foam according to [1], wherein the nonionic surfactant is a fatty acid amide.
  • This invention [3] is [1] or [2] whose content rate of the said nonionic surfactant is 3 to 20 mass parts with respect to 100 mass parts of said ethylene-propylene-diene rubbers. It contains the described ethylene / propylene / diene rubber foam.
  • the rubber composition contains the ethylene / propylene / diene rubber foam according to any one of [1] to [3], which further contains an aromatic sulfinic acid compound.
  • the content ratio of the aromatic sulfinic acid compound is 10 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the nonionic surfactant.
  • the present invention [6], apparent density, a 0.050 g / cm 3 or more 0.200 g / cm 3 or less [1] to the ethylene-propylene-diene rubber foamed material according to any one of [5] Contains.
  • the invention [7] is a foam of ethylene / propylene / diene rubber according to any one of [1] to [6], wherein the 50% compression load is 0.1 N / cm 2 or more and 2.0 N / cm 2 or less. Contains the body.
  • the present invention [8] is a sealing material for filling gaps between members, and the ethylene / propylene / diene rubber foam according to any one of [1] to [7] and the ethylene / propylene /
  • a sealing material including an adhesive layer provided on at least one surface of the diene rubber foam is included.
  • the ethylene / propylene / diene rubber foam of the present invention is obtained by foaming a rubber composition containing ethylene / propylene / diene rubber, a crosslinking agent, a crosslinking accelerator, a foaming agent, a foaming aid and a nonionic surfactant.
  • the elongation is 300% or more and 1000% or less. Therefore, the water stopping property is good.
  • the sealing material of the present invention since the above-mentioned ethylene / propylene / diene rubber foam is provided, the gap between the members can be reliably filled and sealed.
  • FIG. 1 is a schematic view showing an embodiment of the sealing material of the present invention.
  • FIG. 2 is a schematic view showing an outline of the water-stop test.
  • the ethylene / propylene / diene rubber (hereinafter sometimes referred to as EPDM) foam of the present invention is a rubber containing EPDM, a crosslinking agent, a crosslinking accelerator, a foaming agent, a foaming aid, and a nonionic surfactant. It is obtained by foaming the composition.
  • EPDM is a rubber obtained by copolymerization of ethylene, propylene and dienes.
  • dienes are further copolymerized to introduce unsaturated bonds and to be crosslinked by a crosslinking agent described later. Is possible.
  • dienes examples include 5-ethylidene-2-norbornene, 1,4-hexadiene, dicyclopentadiene, and the like. These dienes can be used alone or in combination of two or more.
  • EPDM for example, EPDM having a diene content (diene content) of less than 7.0% by mass (hereinafter, also referred to as “low diene EPDM”), EPDM having a diene content of 7.0% by mass or more. (Hereinafter also referred to as “high diene EPDM”).
  • the diene content of the low diene EPDM is less than 7.0% by mass, preferably 6.0% by mass or less, more preferably 5.0% by mass or less, and for example, 1.0% by mass or more, preferably Is 4.0 mass% or more.
  • the amount of diene can be calculated
  • the dienes in the low diene EPDM are preferably 5-ethylidene-2-norbornene among the above.
  • a known method such as polymerization with a catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst, or a vanadium catalyst is employed.
  • the Mooney viscosity of the low diene EPDM is, for example, 1 (ML1 + 4, at 125 ° C) or more, preferably 10 (ML1 + 4, at125 ° C) or more, more preferably 35 (ML1 + 4, at125 ° C) or more. 100 (ML1 + 4, at 125 ° C.) or less, preferably 50 (ML 1 + 4, at 125 ° C.) or less.
  • the diene content of the high diene EPDM is 7.0% by mass or more, preferably 9.0% by mass or more, and for example, 15.0% by mass or less, preferably 12.0% by mass or less.
  • the dienes in the high diene EPDM are preferably 5-ethylidene-2-norbornene among the above.
  • the elongation viscosity increases due to the entanglement of the side chains, so that the rubber composition can be foamed well and the density of the EPDM foam can be further reduced. .
  • Viscoelasticity measurement is performed using a rheometer (RPA2000; manufactured by Alpha Technologies).
  • a polymerization with a metallocene catalyst is preferable.
  • the Mooney viscosity of the high diene EPDM is, for example, 1 (ML1 + 4, at 100 ° C.) or more, preferably 10 (ML1 + 4, at 100 ° C.) or more, and for example, 100 (ML1 + 4, at 100 ° C.) or less, preferably 35 (ML1 + 4, at 100 ° C.).
  • the EPDM of the present invention may contain at least one of a low diene EPDM and a high diene EPDM, but preferably a low diene EPDM and a high diene EPDM are used in combination.
  • the mass ratio of low diene EPDM to high diene EPDM is, for example, 5:95 to 95: 5, preferably 15:85 to 85:15. More preferably, it is 50:50 to 85:15, further preferably 55:45 to 80:20, and particularly preferably 60:40 to 80:20.
  • the mass ratio of the low diene EPDM and the high diene EPDM in the above-mentioned range, in particular, by increasing the content ratio of the low diene EPDM to the content ratio of the high diene EPDM, the EPDM having a low density and a low compression set. A foam can be obtained reliably.
  • the content ratio of EPDM (total amount of high diene EPDM and low diene EPDM) in the rubber composition is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 80% by mass or less, preferably It is 50 mass% or less, More preferably, it is 40 mass% or less.
  • crosslinking agent examples include sulfur, for example, sulfur compounds such as 4,4′-dithiodimorpholine, for example, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, poly-p-dinitrosobenzene.
  • Quinoid compounds such as dicumyl peroxide, dimethyldi (t-butylperoxy) hexane, 1,1-di (t-butylperoxy) cyclohexane, ⁇ , ⁇ '-di (t-butylperoxy) diisopropyl
  • Organic peroxides such as benzene, for example, nitroso compounds such as p-dinitrosobenzene, for example, formaldehyde resins such as alkylphenol-formaldehyde resins, melamine-formaldehyde condensates, and ammonium salts such as ammonium benzoate, etc. It is done.
  • selenium, magnesium oxide, lead monoxide, polyamine and the like can be mentioned.
  • sulfur, sulfur compounds, and more preferably sulfur are preferable.
  • the content of the crosslinking agent is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less, with respect to 100 parts by mass of EPDM. More preferably, it is 5 parts by mass or less.
  • crosslinking accelerator examples include thiazoles such as dibenzothiazyl disulfide and 2-mercaptobenzothiazole, thioureas such as diethylthiourea, trimethylthiourea, and dibutylthiourea such as sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, Dithiocarbamates such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibenzyldithiocarbamate, for example, guanidines such as diphenylguanidine, di-o-tolylguanidine, for example, benzothiazyl-2-diethylsulfenamide, N- Sulfenamides such as cyclohexyl-2-benzothiazylsulfenamide, such as tetramethylthiuram monosulfide, tetra Thiurams such as tilthiuram disulf
  • Preferred crosslinking accelerators include thiazoles, thioureas, and dithiocarbamates, more preferably thiazoles and dithiocarbamates, and more preferably a combination of thiazoles and dithiocarbamates.
  • the content ratio of the crosslinking accelerator is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and, for example, 15 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of EPDM. Or less. Moreover, it is 1 mass part or more with respect to 100 mass parts of crosslinking agents, Preferably, it is 10 mass parts or more, for example, is 100 mass parts or less, Preferably, it is 50 mass parts or less.
  • the rubber composition contains a crosslinking accelerator, the speed of the crosslinking reaction by the crosslinking agent can be increased. Therefore, the obtained EPDM foam has a small stress relaxation and can retain a repulsive stress, and therefore has a good water stop characteristic.
  • foaming agent examples include organic foaming agents and inorganic foaming agents.
  • organic foaming agent examples include azo foaming agents such as azodicarbonamide (ADCA), barium azodicarboxylate, azobisisobutyronitrile (AIBN), azocyclohexylnitrile, azodiaminobenzene, and the like.
  • azo foaming agents such as azodicarbonamide (ADCA), barium azodicarboxylate, azobisisobutyronitrile (AIBN), azocyclohexylnitrile, azodiaminobenzene, and the like.
  • N-nitroso-based blowing agents such as N′-dinitrosopentamethylenetetramine (DTP), N, N′-dimethyl-N, N′-dinitrosoterephthalamide, trinitrosotrimethyltriamine, such as 4,4′-oxybis (Benzenesulfonyl hydrazide) (OBSH), paratoluenesulfonyl hydrazide, diphenylsulfone-3,3'-disulfonyl hydrazide, 2,4-toluene disulfonyl hydrazide, p, p-bis (benzenesulfonyl hydrazide) ether, benzene-1 , 3-Disulfo Hydrazide-based blowing agents such as nylhydrazide and allylbis (sulfonylhydrazide), for example, p-toluylenesulfonyl semicarbazide and semic
  • Examples of the organic foaming agent include thermally expandable fine particles in which a heat-expandable substance is enclosed in a microcapsule.
  • thermally expandable particles include microspheres (trade name, Matsumoto). And commercial products such as those manufactured by Yushi Corporation.
  • the inorganic foaming agent examples include hydrogen carbonates such as sodium hydrogen carbonate and ammonium hydrogen carbonate, for example, carbonates such as sodium carbonate and ammonium carbonate, for example, nitrites such as sodium nitrite and ammonium nitrite, for example hydrogen.
  • hydrogen carbonates such as sodium hydrogen carbonate and ammonium hydrogen carbonate
  • carbonates such as sodium carbonate and ammonium carbonate
  • nitrites such as sodium nitrite and ammonium nitrite
  • Other known inorganic foaming agents such as borohydride salts such as sodium borohydride, for example, azides, and the like can be mentioned.
  • foaming agents can be used alone or in combination of two or more.
  • an organic foaming agent more preferably an azo foaming agent, and even more preferably ADCA.
  • an organic foaming agent more preferably an azo foaming agent, and even more preferably ADCA.
  • the content of the foaming agent is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of EPDM.
  • foaming aids include salicylic acid-based foaming aids, benzoic acid-based foaming aids, urea-based foaming aids, and metal oxides (eg, zinc oxide). These foaming assistants can be used alone or in combination of two or more.
  • a metal oxide more preferably zinc oxide is used.
  • the content ratio of the foaming assistant is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and for example, 20 parts by mass or less, preferably 15 parts by mass or less with respect to 100 parts by mass of EPDM. . Moreover, it is 1 mass part or more with respect to 100 mass parts of foaming agents, Preferably, it is 10 mass parts or more, for example, is 100 mass parts or less, Preferably, it is 50 mass parts or less.
  • the foaming temperature (for example, the decomposition temperature of the organic foaming agent) can be lowered during foaming. Therefore, the EPDM foam obtained is a foam with a low density and a low compression load.
  • Nonionic surfactants contain hydrophilic groups (eg, amide groups, polyoxyethylene groups, monooxyethylene groups, hydroxyl groups) and hydrophobic groups (eg, C 6 -C 24 aliphatic groups). It is a nonionic compound.
  • nonionic surfactant examples include fatty acid amides, polyoxyethylenes, and monooxyethylenes.
  • fatty acid amides include fatty acid monoamides such as stearic acid monoamide, oleic acid monoamide, and erucic acid monoamide, such as ethylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and ethylene bishydroxystearic acid.
  • fatty acid monoamides such as stearic acid monoamide, oleic acid monoamide, and erucic acid monoamide, such as ethylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and ethylene bishydroxystearic acid.
  • Ethylene bis behenic acid amide Hexamethylene bis stearic acid amide, Hexamethylene bis behenic acid amide, Hexamethylene bishydroxy stearic acid amide, Ethylene bis oleic acid amide, Ethylene bis erucic acid amide, Hexamethylene bis oleic acid amide, m Bis-fatty acid amides such as xylylene bis-stearic acid amide, m-xylylene bis-hydroxystearic acid amide, such as N, N′-distearyl adipic acid amide, N, N′-dialkyl fatty acids such as N, N′-distearyl sebacic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide, N, N ′ distearyl isophthalic acid amide
  • Examples include amides.
  • polyoxyethylenes examples include polyoxyethylene ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene Examples thereof include polyoxyethylene esters such as oxyethylene monostearate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monostearate.
  • Examples of monooxyethylenes include ethylene glycol esters such as ethylene glycol distearate.
  • nonionic surfactants can be used alone or in combination of two or more.
  • fatty acid amides more preferably fatty acid monoamides, bis fatty acid amides, still more preferably bis fatty acid amides, and particularly preferably ethylene bis stearic acid amide.
  • the water stop of EPDM foam can be made still better. Further, the density and compressive load of the EPDM foam can be further reduced.
  • the content ratio of the nonionic surfactant is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 4 parts by mass or more, with respect to 100 parts by mass of EPDM. Part or less, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 8 parts by weight or less.
  • the adhesion between the EPDM foam and the adherend can be improved, and the waterstop property of the EPDM foam can be improved.
  • the rubber composition preferably contains an aromatic sulfinic acid compound.
  • the aromatic sulfinic acid compound is preferably an aromatic sulfinic acid metal salt.
  • aromatic sulfinic acid metal salts include sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, zinc di-benzenesulfinate, calcium di-benzenesulfinate, lead di-benzenesulfinate, and di-benzene.
  • Benzenesulfinate metal salts such as barium sulfinate, cadmium di-benzenesulfinate, magnesium di-benzenesulfinate; for example, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, bis- zinc p-toluenesulfinate, calcium bis-p-toluenesulfinate, lead bis-p-toluenesulfinate, barium bis-p-toluenesulfinate, bis-p-toluenesulfinate Toluene sulfinate metal salts such as magnesium, bis-p-toluenesulfinate magnesium; for example, sodium p-chlorobenzenesulfinate, potassium p-chlorobenzenesulfinate, lithium p-chlorobenzenesulfinate, zinc bis-p-chloro
  • toluenesulfinic acid metal salts are used, more preferably zinc bis-p-toluenesulfinate.
  • the content ratio of the aromatic sulfinic acid compound is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 4 parts by mass or more with respect to 100 parts by mass of EPDM. Yes, for example, 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 8 parts by mass or less.
  • the content rate of an aromatic sulfinic acid compound is 10 mass parts or more with respect to 100 mass parts of nonionic surfactants, Preferably, it is 50 mass parts or more, More preferably, it is 70 mass parts or more. Also, for example, it is 300 parts by mass or less, preferably 150 parts by mass or less, and more preferably 90 parts by mass or less.
  • the aromatic sulfinic acid compound plays a role as a foaming aid, promotes the foamability of the foaming agent, and improves the foamability and flexibility of the EPDM foam. Can be improved. Moreover, since the aromatic sulfinic acid compound suppresses generation of fogging-causing substances such as urea, fogging of the EPDM foam can be suppressed.
  • the rubber composition preferably contains a basic metal compound.
  • the basic metal compound examples include basic oxides such as calcium oxide, magnesium oxide, ferrous oxide (FeO), and ferric oxide (Fe 2 O 3 ), such as calcium hydroxide and magnesium hydroxide. And basic hydroxides. These basic metal compounds can be used alone or in combination of two or more.
  • calcium oxide and magnesium hydroxide are preferable, and calcium oxide is more preferable.
  • the content of the basic metal compound is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less with respect to 100 parts by mass of EPDM. is there.
  • the rubber composition contains a basic metal compound
  • the basic metal compound traps a decomposition product (for example, cyanic acid) generated by the decomposition of the foaming agent (for example, ADCA).
  • a decomposition product for example, cyanic acid
  • the foaming agent for example, ADCA
  • the rubber composition may contain a softener, a filler, a processing aid, a pigment, and the like as appropriate, if necessary.
  • softener examples include dry oils, animal and vegetable oils (eg flaxseed oil), asphalts (eg blown asphalt), petroleum oils (eg paraffinic process oil, naphthenic process oil, aroma Process oils), low molecular weight polymers, organic acid esters (eg, phthalate esters (eg, di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP)), phosphate esters, higher fatty acid esters , Alkyl sulfonic acid ester, etc.). These softeners can be used alone or in combination of two or more. Preferably, asphalt and petroleum oils are used.
  • the content ratio of the softening agent is, for example, 50 parts by mass or more, preferably 110 parts by mass or more, and for example, 250 parts by mass or less, preferably 180 parts by mass or less with respect to 100 parts by mass of EPDM.
  • the filler examples include inorganic fillers such as calcium carbonate, magnesium carbonate, silicic acid and salts thereof, clay, talc, mica powder, bentonite, silica, alumina, aluminum silicate, aluminum powder, and organic materials such as cork. System fillers and other known fillers. These fillers can be used alone or in combination of two or more. Preferably, an inorganic filler, more preferably calcium carbonate is used.
  • the content of the filler is, for example, 50 parts by mass or more, preferably 80 parts by mass or more, more preferably 110 parts by mass or more, and for example, 250 parts by mass or less, preferably 100 parts by mass of EPDM. Is 180 parts by mass or less, more preferably 130 parts by mass or less.
  • processing aids include stearic acid and esters thereof, and zinc stearate. These processing aids can be used alone or in combination of two or more.
  • the content of the processing aid is, for example, 0.1 parts by mass or more, preferably 3 parts by mass or more, and, for example, 20 parts by mass or less, preferably 15 parts by mass or less with respect to 100 parts by mass of EPDM. It is.
  • the pigment examples include carbon black.
  • the average particle diameter of the pigment is, for example, 1 ⁇ m or more and 200 ⁇ m or less. These pigments can be used alone or in combination of two or more.
  • the content ratio of the pigment is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of EPDM.
  • the rubber composition can be used, for example, in the range that does not affect the excellent effect of the obtained EPDM foam, depending on its purpose and application, for example, polymer, flame retardant, tackifier, anti-aging agent, antioxidant, coloring Known additives such as agents and fungicides can be contained in an appropriate ratio.
  • the rubber composition is preferably substantially free of urea. Thereby, generation
  • the content ratio of urea is 1.0% by mass or less, preferably 0.5% by mass or less, and more preferably 0% by mass with respect to the rubber composition.
  • the above-described components are blended and kneaded using a kneader, a mixer, a mixing roll, or the like to knead the rubber composition as an admixture (kneading step).
  • a component other than a crosslinking agent, a crosslinking accelerator, a nonionic surfactant, an aromatic sulfinic acid compound, and a basic metal compound is kneaded to obtain a primary mixture, , Adding a cross-linking agent, a cross-linking accelerator, a nonionic surfactant, an aromatic sulfinic acid compound, and a basic metal compound to the primary mixture and kneading to obtain a rubber composition (secondary mixture) You can also. Further, in the kneading step, kneading can be performed while appropriately heating.
  • the obtained rubber composition (admixture) is extruded into a sheet or the like using an extruder (molding step), and then the extruded rubber composition is heated to foam (foaming). Process).
  • the rubber composition is appropriately selected according to the crosslinking start temperature of the blended crosslinking agent, the foaming temperature of the blended foaming agent, and the like, for example, using a hot air circulating oven, for example, 40 ° C. or higher, preferably 60 ° C. or higher, for example, 200 ° C. or lower, preferably 160 ° C. or lower, for example, 1 minute or longer, preferably 5 minutes or longer, and for example, 60 minutes or shorter, preferably 40 minutes or shorter, Preheat.
  • a hot air circulating oven for example, 40 ° C. or higher, preferably 60 ° C. or higher, for example, 200 ° C. or lower, preferably 160 ° C. or lower, for example, 1 minute or longer, preferably 5 minutes or longer, and for example, 60 minutes or shorter, preferably 40 minutes or shorter, Preheat.
  • After preheating for example, 450 ° C. or less, preferably 250 ° C. or less, for example, 100 ° C. or more, preferably 160 °
  • the rubber composition is crosslinked while being foamed to obtain an EPDM foam.
  • an EPDM foam having good water-stopping and elongation can be produced easily and reliably.
  • the obtained rubber composition is extruded into a sheet shape (molding step) while being heated using an extruder (that is, a rubber composition sheet is produced) to obtain a sheet-like rubber composition.
  • the (rubber composition sheet) can also be continuously crosslinked and foamed (foaming step). According to this method, the EPDM foam can be produced with high production efficiency.
  • the thickness of the obtained EPDM foam is, for example, 0.1 mm or more, preferably 1 mm or more, and for example, 50 mm or less, preferably 45 mm or less.
  • the EPDM foam has, for example, an open-cell structure (open cell ratio: 100%) or a semi-continuous semi-closed cell structure (open-cell ratio exceeds, for example, 0%, and preferably has an open-cell ratio of 10% or more, For example, it is less than 100%, preferably 98% or less.
  • a semi-continuous semi-closed cell structure is preferable.
  • the average cell diameter of the EPDM foam is, for example, 100 ⁇ m or more, preferably 500 ⁇ m or more, more preferably 800 ⁇ m or more, and, for example, 1500 ⁇ m or less, preferably 1200 ⁇ m or less, more preferably 900 ⁇ m or less. .
  • the sealing property and flexibility can be improved.
  • the volume expansion ratio (density ratio before and after foaming) of the EPDM foam is, for example, 5 times or more, preferably 15 times or more, and for example, 30 times or less.
  • the apparent density (according to JIS K 6767 (1999)) of the EPDM foam is, for example, 0.050 g / cm 3 or more, preferably 0.080 g / cm 3 or more, more preferably 0.090 g / cm 3. or more, also, for example, 0.200 g / cm 3 or less, preferably 0.150 g / cm 3 or less, more preferably 0.120 g / cm 3 or less.
  • the apparent density is in the above range, the flexibility of the EPDM foam can be improved.
  • the 50% compressive load value (according to JIS K 6767 (1999)) of the EPDM foam is, for example, 0.1 N / cm 2 or more, preferably 0.2 N / cm 2 or more, more preferably 0.3 N. / cm 2 or more, also, for example, 2.0 N / cm 2 or less, preferably, 1.0 N / cm 2 or less, more preferably 0.5 N / cm 2 or less.
  • the 50% compression load value is in the above range, the flexibility of the EPDM foam is good.
  • the load concerning a member can be reduced when compressing and sealing to a member, while being able to seal a member easily, a deformation
  • EPDM strength of the foam JIS K 6767 (maximum load in a tensile test according to 1999)
  • 1.0 N / cm 2 or more preferably, 5.0 N / cm 2 or more, more preferably 7. and at 0N / cm 2 or more, and is, for example, 20 N / cm 2 or less, preferably, 15N / cm 2 or less, more preferably 10 N / cm 2 or less.
  • the strength of the EPDM foam is good.
  • the elongation of the EPDM foam is not less than 300% and not more than 1000%. Preferably, it is 500% or more, more preferably 600% or more, and preferably 900% or less, more preferably 800% or less. When the elongation is within the above range, the flexibility of the EPDM foam is good. Further, the EPDM can be brought into close contact with the shape and unevenness of the adherend as various members, and the gaps between the various members can be reliably sealed.
  • the volatilization amount by fogging of the EPDM foam is, for example, 3.0 mg or less, preferably 1.0 mg or less under the condition that an EPDM foam having a length of 100 mm, a width of 50 mm, and a thickness of 10 mm is left in a sealed container at 100 ° C. for 20 hours. It is.
  • the volatilization amount is in the above range, it is possible to suppress the occurrence of fogging (fogging) such as glass in the peripheral member.
  • the EPDM foam is not particularly limited, and seals gaps between various members for automobile use, residential use use, home appliance use, etc. for the purpose of water stop, vibration control, sound absorption, sound insulation, dust prevention, heat insulation, buffering, etc. can do.
  • it can be used as a water-stopping material, a vibration-proofing material, a sound-absorbing material, a sound-insulating material, a dust-proofing material, a heat-insulating material, a shock-absorbing material and the like.
  • it can be used as a water stop material for the purpose of water stop.
  • gaps between automobile casings and parts for example, instrument panels, door trims, air ducts, door speakers, taillights, etc.
  • electrical and electrical equipment casings and parts for example, engine control units (ECUs) Etc.
  • the EPDM foam is obtained by foaming a rubber composition containing ethylene / propylene / diene rubber, a crosslinking agent, a crosslinking accelerator, a foaming agent, a foaming aid and a nonionic surfactant. Therefore, the water stopping property is good.
  • the elongation percentage of the EPDM foam is 300% or more and 1000% or less. Therefore, EPDM can be brought into close contact with the shape and unevenness of the adherend that is various members, and the gaps between the various members can be reliably sealed.
  • this EPDM foam can reliably prevent water from entering in the gaps between the various members.
  • the EPDM foam is preferably obtained by foaming a rubber composition further containing an aromatic sulfinic acid compound. Therefore, fogging can be suppressed while improving flexibility.
  • FIG. 1 is a schematic configuration diagram showing an embodiment of a sealing material of the present invention.
  • the sealing material 1 includes the above-described EPDM foam 2 and an adhesive layer 3 provided on one surface (surface) of the EPDM foam 2.
  • the adhesive layer 3 is formed from, for example, a known adhesive.
  • adhesives examples include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, urethane adhesives, polyamide adhesives, epoxy adhesives, vinyl alkyl ether adhesives, fluorine System adhesives and the like.
  • pressure sensitive adhesive examples include hot melt pressure sensitive adhesive. These pressure-sensitive adhesives can be used alone or in combination of two or more.
  • an acrylic pressure-sensitive adhesive and a rubber-based pressure-sensitive adhesive are preferable.
  • the acrylic pressure-sensitive adhesive is, for example, a pressure-sensitive adhesive mainly composed of (meth) acrylic alkyl ester, and can be obtained by a known method.
  • the rubber-based pressure-sensitive adhesive can be obtained by a known method from, for example, natural rubber and / or synthetic rubber, specifically, rubber such as polyisobutylene rubber, polyisoprene rubber, chloroprene rubber, butyl rubber, and nitrile butyl rubber.
  • the form of the pressure-sensitive adhesive is not particularly limited, and various forms such as an emulsion-based pressure-sensitive adhesive, a solvent-based pressure-sensitive adhesive, an oligomer-based pressure-sensitive adhesive, and a solid pressure-sensitive adhesive can be employed.
  • the thickness of the pressure-sensitive adhesive layer 3 is, for example, 10 ⁇ m or more, preferably 50 ⁇ m or more, and for example, 10,000 ⁇ m or less, preferably 5000 ⁇ m or less.
  • the method for forming the sealing material 1 is not particularly limited, and a known method can be employed. Specifically, for example, the adhesive layer 3 is laminated on the surface of the EPDM foam 2 by a known method.
  • the adhesive layer 3 is provided only on one surface of the EPDM foam 2, but although not illustrated, for example, the adhesive layer 3 is provided on both surfaces (front surface and back surface) of the EPDM foam 2. It can also be provided.
  • Examples 1 to 6 and Comparative Examples 1 to 5 (1) Manufacture of EPDM Foam EPDM, foaming agent, foaming aid, softening agent, filler, processing aid and pigment are blended in the blending amounts shown in the blending prescription shown in Table 1 into a 3 L pressure kneader. And kneaded to prepare a primary mixture.
  • a crosslinking agent, a crosslinking accelerator, a surfactant, an aromatic sulfinic acid compound, a basic metal compound, and the like are blended, blended into a primary blend, kneaded with a 10 inch mixing roll, and a rubber composition. (Secondary mixture) was prepared (kneading step).
  • the rubber composition was extruded into a sheet having a thickness of about 8 mm using a single screw extruder (45 mm ⁇ ) to produce a rubber composition sheet (molding step).
  • the rubber composition sheet was preheated at 140 ° C. for 20 minutes in a hot air circulating oven. Thereafter, the temperature was raised to 180 ° C. in a hot air circulation oven over 11 minutes, and the rubber composition sheet was heated at 180 ° C. for 10 minutes to be foamed (foaming step) to produce an EPDM foam.
  • the apparent density of the EPDM foam was measured according to JIS K 6767 (1999). Specifically, the skin layer of the EPDM foam was removed to prepare a test piece having a thickness of about 10 mm. Then, mass was measured and the mass per unit volume (apparent density) was computed.
  • the compression load value of the EPDM foam was measured according to JIS K 6767 (1999). Specifically, the skin layer of the EPDM foam was removed to prepare a test piece having a thickness of about 10 mm. Thereafter, the compression load value was measured 10 seconds after 50% compression at a compression speed of 10 mm / min using a compression tester.
  • ⁇ Tensile strength and elongation> The tensile strength and elongation of the EPDM foam were measured according to JIS K 6767 (1999). Specifically, the skin layer of the EPDM foam was removed to prepare a test piece having a thickness of about 10 mm. Then, using the dumbbell No. 1, the test piece was punched out to obtain a measurement sample. With a tensile tester, the measurement sample was pulled at a pulling speed of 500 mm / min, and the load (tensile strength) and elongation (breaking elongation) when the measurement sample was cut at the dumbbell-shaped parallel portion were measured.
  • ⁇ Foging properties> The skin layer of the EPDM foam was removed to prepare a test piece having a length of 100 mm, a width of 50 mm, and a thickness of 10 mm. Thereafter, a test piece was placed on the bottom of a glass bottle having an opening inner diameter of 40 mm, a bottom inner diameter of 70 mm, and a height of 160 mm, and the glass bottle was immersed in a 100 ° C. silicone oil bath (oil depth 110 mm). Next, a glass plate was placed in the opening of the glass bottle to cover the opening and left for 20 hours. After being allowed to stand, the mass of the glass plate was measured, and the amount of increase in the mass with respect to the glass plate before being left was measured.
  • the EPDM foam sample 2 was punched into a U shape with a thickness of 10 mm, a width of 10 mm, a height of 148 mm, and a distance between both ends of 54 mm.
  • the sample 2 was bolted 7 with a spacer 6 via an acrylic plate 4 and an aluminum plate 5 and compressed in the thickness direction by 70% (that is, compressed until the thickness of the sample 2 became 3 mm).
  • Water 8 was put in a U-shape of sample 2 to a height of 100 mm, and the time until water leakage was measured.
  • “X” when there is a water leak within 1 to 12 hours
  • ⁇ when there is no water leak after 12 hours, “ ⁇ ” ".
  • the ethylene-propylene-diene rubber foam and the sealing material of the present invention can be applied to various industrial products, for example, suitable for a sealing material that seals gaps of various members such as automobile use, housing use use, and home appliance use. Can be used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Sealing Material Composition (AREA)

Abstract

Mousse de caoutchouc d'éthylène-propylène-diène obtenue par moussage d'une composition de caoutchouc contenant un caoutchouc d'éthylène-propylène-diène, un agent de réticulation, un accélérateur de réticulation, un agent moussant, un agent auxiliaire de moussage, et un agent tensio-actif non ionique, et présentant un taux d'étirage de 300 à 1000 %.
PCT/JP2016/069625 2015-07-02 2016-07-01 Mousse de caoutchouc d'éthylène-propylène-diène, et matériau d'étanchéité WO2017002957A1 (fr)

Applications Claiming Priority (4)

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JP2015-133765 2015-07-02
JP2015133765 2015-07-02
JP2016126839A JP6757609B2 (ja) 2015-07-02 2016-06-27 エチレン・プロピレン・ジエンゴム発泡体およびシール材
JP2016-126839 2016-06-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106739355A (zh) * 2017-03-16 2017-05-31 天津市浩迪橡塑科技有限公司 复合空腔吸音材料结构阻尼板及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59148646A (ja) * 1983-02-14 1984-08-25 Sumitomo Chem Co Ltd 水膨潤性発泡製品
JPS61174242A (ja) * 1985-01-30 1986-08-05 Sanwa Kako Kk 架橋ポリオレフイン連続気泡体
JP2005281579A (ja) * 2004-03-30 2005-10-13 Canon Chemicals Inc 発泡ゴムローラ
JP2007063450A (ja) * 2005-09-01 2007-03-15 Denki Kagaku Kogyo Kk 水膨張性発泡シール材
JP2009126881A (ja) * 2007-11-20 2009-06-11 Inoac Corp 連続気泡発泡体とその製造方法
JP2014180816A (ja) * 2013-03-19 2014-09-29 Nitto Denko Corp 発泡積層体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59148646A (ja) * 1983-02-14 1984-08-25 Sumitomo Chem Co Ltd 水膨潤性発泡製品
JPS61174242A (ja) * 1985-01-30 1986-08-05 Sanwa Kako Kk 架橋ポリオレフイン連続気泡体
JP2005281579A (ja) * 2004-03-30 2005-10-13 Canon Chemicals Inc 発泡ゴムローラ
JP2007063450A (ja) * 2005-09-01 2007-03-15 Denki Kagaku Kogyo Kk 水膨張性発泡シール材
JP2009126881A (ja) * 2007-11-20 2009-06-11 Inoac Corp 連続気泡発泡体とその製造方法
JP2014180816A (ja) * 2013-03-19 2014-09-29 Nitto Denko Corp 発泡積層体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106739355A (zh) * 2017-03-16 2017-05-31 天津市浩迪橡塑科技有限公司 复合空腔吸音材料结构阻尼板及其制备方法

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