WO2011007788A1 - シール材 - Google Patents
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- WO2011007788A1 WO2011007788A1 PCT/JP2010/061863 JP2010061863W WO2011007788A1 WO 2011007788 A1 WO2011007788 A1 WO 2011007788A1 JP 2010061863 W JP2010061863 W JP 2010061863W WO 2011007788 A1 WO2011007788 A1 WO 2011007788A1
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- sealing material
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- ethylene
- vinyl acetate
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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
- C08J9/06—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 by a chemical blowing agent
- C08J9/10—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 by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
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- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- 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
- C08J2400/00—Characterised by the use of unspecified polymers
- C08J2400/22—Thermoplastic resins
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C08L2312/00—Crosslinking
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0204—Elements
- C09K2200/0208—Carbon
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
- C09K2200/0405—Hydrocarbons
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
- C09K2200/062—Polyethylene
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0622—Polyvinylalcohols, polyvinylacetates
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0642—Copolymers containing at least three different monomers
Definitions
- the present invention relates to a sealing material for sealing between members, and particularly to a sealing material using an ethylene-c-olefin-diene copolymer rubber foam.
- a sealing material such as a synthetic resin or a foam of rubber is generally used. Since the foam has an appropriate repulsive force (compressive stress), the foam can follow and adhere to the unevenness of the surface of the material to be sealed with only a small amount of compressive deformation, and can provide excellent sealing properties.
- rubber foam obtained by foaming ethylene- ⁇ -olefin-diene copolymer rubber with a foaming agent such as azodicarbonamide is suitable as a sealing material because it has excellent weather resistance, heat resistance, and sealing properties.
- Patent Documents 1 and 2 In a rubber foam, it is effective for improvement of performance (water-stopping property, heat insulation, sound absorption, etc.) required for the foam that the bubble diameter is small and the foaming ratio and compression stress are appropriate. Therefore, bubble control is performed on the rubber foam by using a processing aid such as stearic acid.
- the sealing material using the conventional rubber foam has a problem that the compressive stress of the foam decreases with time, resulting in a decrease in sealing performance. Such a problem is particularly likely to occur during long-term use at high temperatures and long-term use in environments where high and low temperatures are repeated.
- an object of the present invention is to provide a sealing material capable of maintaining excellent sealing performance for a long period of time.
- the present invention relates to a rubber component containing a copolymer rubber of ethylene, an ⁇ -olefin having 3 or more carbon atoms and a non-conjugated diene, a vulcanizing agent, and a mixture containing a foaming agent to vulcanize and foam the mixture.
- a sealing material comprising The said subject is solved by the sealing material characterized by the said mixture containing the thermoplastic resin whose melting
- the sealing material of the present invention containing a thermoplastic resin having a melting point of 80 ° C. or lower increases in adhesion over time, whereby the adhesion between the surface of the sealing material and the surface to be sealed can be further improved. Therefore, the sealing material can maintain excellent sealing performance for a long period of time.
- the perspective view of the U-shaped sample used for water-stop evaluation is shown.
- the outline of the U-shaped test method by water-stop evaluation is shown.
- the sealing material of the present invention comprises a rubber component containing a copolymer rubber of ethylene, an ⁇ -olefin having 3 or more carbon atoms and a non-conjugated diene, a vulcanizing agent, a blowing agent, and a heat melting point of 80 ° C. or less. It consists of a rubber foam obtained by vulcanizing and foaming an admixture containing a plastic resin.
- thermoplastic resin having a melting point of 80 ° C. or less can bleed out to the surface of the sealing material over time, and thereby the adhesiveness of the sealing material surface to the sealed surface is expressed. Furthermore, by applying a repulsive force of the sealing material, the adhesion between the surface of the sealing material and the surface to be sealed can be further improved. Such a bleed-out of the thermoplastic resin is particularly promoted under a high temperature environment of 60 ° C. or higher. Therefore, even if the compressive stress is reduced due to deterioration of the sealing material, the adhesion between the sealing material and the surface to be sealed can be secured, and excellent sealing performance can be maintained over a long period of time.
- the thermoplastic resin since the thermoplastic resin has not yet bleeded out when the sealing material is attached, the thermoplastic resin can be easily repositioned and the workability of the sealing material can be ensured.
- the sealing material of the present invention is excellent in productivity because it is not necessary to newly provide an adhesive layer or the like for improving the adhesion to the surface to be sealed on the surface of the rubber foam.
- thermoplastic resin such as EVA may be used for the purpose of improving the strength.
- EVA ethylene glycol dimethacrylate copolymer
- thermoplastic resin has a melting point of 80 ° C. or less, preferably 50 to 75 ° C., particularly preferably 60 to 70 ° C.
- the melting point of the thermoplastic resin is a value measured by a differential scanning calorimetry (DSC) method based on JIS K 6924-2.
- Thermoplastic resins having a melting point of 80 ° C. or lower include low density polyethylene, ethylene vinyl acetate copolymer resin, ethylene acrylic acid copolymer resin, ethylene ethyl acrylate copolymer resin, ethylene methyl acrylate copolymer resin, and ethylene methacrylic acid.
- a copolymer resin or the like is used.
- ethylene vinyl acetate copolymer resin (EVA) is particularly preferable.
- EVA exhibits excellent adhesiveness without contaminating the material to be sealed when bleeding out on the surface of the sealing material, and can further improve the sealing durability of the sealing material.
- EVA has water repellency and can form a film on the surface of the sealing material, so that it is possible to improve the water sealing property of the sealing material.
- EVA having a melting point of 80 ° C. or less and capable of bleeding out on the surface of the sealing material
- EVA has an appropriate melt flow rate (MFR) and vinyl acetate content.
- the melt flow rate of the ethylene vinyl acetate copolymer is preferably 1 to 2500 g / 10 min.
- the melt flow rate of EVA is more preferably 10 to 500 g / 10 min, and particularly preferably 30 to 400 g / 10 min.
- the EVA MFR is a value measured under the conditions of 190 ° C. and a load of 21.18 N in accordance with JIS K6924-1.
- the vinyl acetate content of the ethylene vinyl acetate copolymer is preferably 10 to 50% by mass.
- the vinyl acetate content of EVA is more preferably 15 to 35% by mass, and particularly preferably 25 to 35% by mass.
- the vinyl acetate content of EVA is a value measured according to JIS K 6924.
- the content of the thermoplastic resin is preferably 1 to 40 parts by mass, particularly 10 to 30 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the thermoplastic resin exceeds 40 parts by mass, the kneadability and molding processability may decrease, the bubble diameter may increase, the compression stress of the foam may decrease, and the amount is less than 1 part by mass. There is a possibility that the thermoplastic resin cannot sufficiently bleed out.
- the rubber component includes at least an ethylene- ⁇ -olefin-diene copolymer rubber.
- the ethylene- ⁇ -olefin-diene copolymer rubber is a copolymer of ethylene, ⁇ -olefin, and non-conjugated diene.
- the ⁇ -olefin is an ⁇ -olefin having 3 or more carbon atoms, specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like, and propylene is particularly preferably used.
- Non-conjugated dienes include 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 2-methyl-1,5-hexadiene, 6-methyl- 1,5-hexadiene, 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene Among them, 5-ethylidene-2-norbornene is preferable.
- the ethylene- ⁇ -olefin-diene copolymer rubber is preferably ethylene-propylene-diene copolymer rubber (EPDM).
- EPDM ethylene-propylene-diene copolymer rubber
- the content of non-conjugated diene in EPDM is preferably 3 to 20% by mass, particularly 5 to 15% by mass.
- the ethylene- ⁇ -olefin-diene copolymer rubber is preferably contained in an amount of 60% by mass or more, particularly 85% by mass or more based on the total amount of the rubber component. Thereby, it can suppress that the compressive stress of a sealing material falls with time.
- Rubber components used in addition to ethylene- ⁇ -olefin-diene copolymer rubber include ethylene-propylene rubber (EPM) and butyl rubber (IIR), isoprene rubber (IR), natural rubber (NR), and styrene-butadiene.
- EPM ethylene-propylene rubber
- IIR isoprene rubber
- NR natural rubber
- SBR rubber
- BR butadiene rubber
- RB 1,2-polybutadiene
- acrylic rubber ACM, ANM
- CSM chlorosulfonated polyethylene
- CR chloroprene rubber
- silicon rubber silicon rubber.
- EPM and IIR are preferable.
- vulcanizing agent examples include sulfur and sulfur compounds, zinc white, selenium, magnesium oxide, and organic peroxides. Considering the heat resistance and sealing durability of the foam, it is preferable to use at least sulfur.
- the content of the vulcanizing agent is preferably 1 to 30 parts by mass, particularly 5 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
- vulcanization is not limited to bridging with sulfur, but is used synonymously with “crosslinking”.
- the foaming agent is not only used for generating gas for foaming but also has a function of adjusting the vulcanization of the rubber component.
- Examples thereof include dinitropentamethylenetetramine (DPT), azodicarbonamide (ADCA), 4,4′-oxybisbenzenesulfonylhydrazide (OBSH) sodium bicarbonate, and the like.
- DPT dinitropentamethylenetetramine
- ADCA azodicarbonamide
- OBSH 4,4′-oxybisbenzenesulfonylhydrazide
- ADCA is particularly preferably used in consideration of the heat resistance and sealing durability of the foam.
- the content of the foaming agent is preferably 5 to 40 parts by mass, particularly 10 to 30 parts by mass with respect to 100 parts by mass of the rubber component.
- the admixture used in the sealing material of the present invention may further contain other additives depending on the purpose.
- vulcanization accelerators such as thiazole, dithiocarbamate, thiourea, dithiophosphite, thiuram, stearic acid, lauric acid, zinc oxide (active zinc white), etc. Sulfur acceleration aids are used.
- Resin softeners such as paraffin oil, paraffin wax, blown asphalt, polybutene, rosin; calcium carbonate and magnesium carbonate, silicic acid or its salts and talc, clay and mica powder, bentonite, carbon black and silica, aluminum hydroxide and hydroxide Fillers such as magnesium, alumina, aluminum silicate, acetylene black, aluminum powder, ceramic, glass fiber, wood powder, fiber scraps; dehydrating agents such as potassium oxide, cesium oxide, sodium oxide, calcium oxide, urea or its derivatives Foaming aids, anti-aging agents, antioxidants, pigments, colorants, fungicides and the like can also be used. One or more of these additives can be added as necessary. Carbon black is also used as a reinforcing agent.
- a resin softening agent because a sealing material excellent in mechanical strength and adhesiveness to the surface to be sealed can be obtained.
- the content of the resin softening agent is preferably 50 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
- the sealing material of the present invention can be obtained by kneading the above-mentioned compounding agent, molding the mixture into a desired shape, and vulcanizing and foaming the obtained molded body.
- the sealing material thus obtained is made of a rubber foam having a closed cell structure.
- a foaming agent, a foaming aid, a vulcanizing agent, and a compounding agent excluding the vulcanizing aid are kneaded. Kneading can be performed using a closed mixer such as a Banbury mixer, a kneader, or an intermix, or an open mixer such as a roll. The kneading is preferably performed at a temperature of 80 to 170 ° C., particularly 90 to 140 ° C. for 2 to 20 minutes. Thereafter, a foaming agent, a foaming aid, a vulcanizing agent, and a vulcanizing aid are added to the kneaded product and kneaded.
- This kneading is preferably carried out at 40 to 90 ° C., particularly 50 to 80 ° C. for 5 to 30 minutes.
- the kneaded material obtained in this way is formed into a desired shape such as a sheet by a calendar molding machine, an extrusion molding machine or the like.
- the kneaded product is molded into a desired shape, introduced into a vulcanizing apparatus, and vulcanized and foamed by heating at 130 to 270 ° C., particularly 140 to 200 ° C. for 1 to 90 minutes. Thereby, a rubber foam having a closed cell structure is obtained.
- heating means such as a hot air vulcanizing tank (HAV), a glass bead fluidized bed, a microwave vulcanizing apparatus (UHF), steam or the like can be used.
- HAV hot air vulcanizing tank
- UHF microwave vulcanizing apparatus
- the foaming ratio (density ratio before and after foaming) of the rubber foam is preferably set to 5 to 30 times, particularly 10 to 20 times. Thereby, a rubber foam having an appropriate mechanical strength is obtained.
- the sealing material obtained by vulcanization foaming has a closed cell structure.
- the bubbles in the sealing material having a closed cell structure are fine and exist at a high density. Therefore, the rubber foam is excellent in properties such as water-stopping property, sound insulating property, and heat insulating property.
- the average bubble diameter of bubbles in the sealing material is 125 to 2500 ⁇ m, particularly 167 to 500 ⁇ m.
- the average bubble diameter is a value measured according to ASTM D3576-77.
- the number of bubbles (cells) in the sealing material is 10 to 200/25 mm, particularly 50 to 150/25 mm.
- the number of bubbles is the number of bubbles per 25 mm of the foam specified in JIS K 6767 (1999).
- the sealing material has a 50% compressive stress in the thickness direction at 25 ° C. of 0.5 to 100 kPa, particularly 45 to 70 kPa.
- the 50% compressive stress is a value measured according to JIS K 6767.
- the density (weight / volume) of the sealing material is 50 to 150 kg / m 3 , particularly 90 to 110 kg / m 3 .
- Such a sealing material has a low density and is excellent in cost because fine bubbles are highly dispersed.
- a density be the value measured according to the method prescribed
- the sealing material has a tensile strength at 300% elongation in the longitudinal direction of 50 to 500 kPa, particularly 200 to 300 kPa.
- the tensile strength is a value measured according to JIS K 6767 (A method).
- the sealing material of the present invention can ensure excellent adhesion between the rubber foam surface and the surface to be sealed over a long period of time. In particular, such effects are exhibited during long-term use at high temperatures (60 ° C or higher) and for long-term use in environments where high temperatures (60 ° C or higher) and low temperatures (30 ° C or lower) are repeated. Is done.
- Such sealing materials include, for example, vehicles such as window dams; electrical equipment such as air conditioners, washing machines, refrigerators, vending machines; acoustic equipment; It is suitably used for sealing gaps between members in housing equipment such as water heaters; structures, roads and bridge joints, and civil engineering works such as water channel joints. *
- the sealing material is used for dustproofing, heat insulating, soundproofing, vibration proofing, buffering, watertightness and airtightness, for example, dustproofing material, heat insulating material, soundproofing material, vibration proofing material, shock absorbing material, filler, etc. You can also.
- the thickness of the sealing material may be determined according to the application, but is preferably 3 to 50 mm.
- Example 1 In the composition shown in Table 1, the composition excluding the foaming agent, foaming aid, vulcanizing agent, and vulcanization accelerator was kneaded with a kneader at 120 ° C. for 8 minutes. Next, a foaming agent, a foaming aid, a vulcanizing agent, and a vulcanization accelerator are further added to the kneaded product whose surface temperature has been cooled to 20 ° C., as shown in Table 1, and 80 ° C. by a kneader. For 5 minutes. The obtained kneaded product is molded into a sheet by a rubber extruder, put in a heating furnace, vulcanized and foamed at 140 ° C. for 80 minutes, and made of a rubber foam having a closed cell structure. Got.
- EPDM and EVA1 in Table 1 are as follows. Details of other components are omitted.
- EPDM product name 501A, manufactured by Sumitomo Chemical Co., Ltd., ethylene content 52 mass%, diene (5-ethylidene-2-norbornene) content 5 mass%)
- EVA1 melting point 71 ° C., melt flow rate 18 g / 10 min, vinyl acetate content 28% by mass
- Example 2 A sealing material made of a rubber foam having a closed cell structure was prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 1. Details of EVA2 to 4 in Table 1 are as follows.
- EVA2 (melting point 67 ° C., melt flow rate 400 g / 10 min, vinyl acetate content 28% by mass)
- EVA3 (melting point 66 ° C., melt flow rate 30 g / 10 min, vinyl acetate content 32% by mass)
- EVA4 (melting point 79 ° C., melt flow rate 2500 g / 10 min, vinyl acetate content 14% by mass)
- Example 1 a rubber foam having a closed cell structure was produced in the same manner as in Example 1 except that the composition was changed as shown in Table 2. Next, the foamed foam was subjected to a foam breaking treatment by roll crushing. This obtained the sealing material which consists of a rubber foam which has a semi-continuous cell structure.
- Example 4 a rubber foam having a closed cell structure was produced in the same manner as in Example 1 except that EVA was not used.
- EVA1 melting point: 71 ° C., melt flow rate: 18 g / 10 minutes, vinyl acetate content: 28% by mass
- EVA1 melting point: 71 ° C., melt flow rate: 18 g / 10 minutes, vinyl acetate content: 28% by mass
- an EVA coating film could not be formed to such an extent that water-stopping evaluation was possible.
- Example 5 A sealing material made of a rubber foam having a closed cell structure was prepared in the same manner as in Example 1 except that the composition was changed as shown in Table 2. Details of EVA5 in Table 2 are as follows.
- the water-proof sealing material is punched into a U shape with a thickness (a) of 10 mm, a width (e) of 10 mm, a height (f) of 130 mm, and a distance (g) between both ends of 45 mm.
- S 1 is obtained, and this is compressed 60% in the thickness direction with two acrylic plates 2 and 3 as shown in FIG. 2, and water is poured to a height of 100 mm in the U-shape until the water leaks. Was measured.
- Table 3 The results are shown in Table 3.
- the sealing materials of Examples 1 to 6 maintain excellent water-tight sealing properties because the rubber foam surface and the acrylic plate surface are in close contact with each other even after being left in a high temperature environment. can do.
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Sealing Material Composition (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
Description
前記混和物が、融点が80℃以下の熱可塑性樹脂を含むことを特徴とするシール材により上記課題を解決する。
熱可塑性樹脂は、融点が80℃以下、好ましくは50~75℃、特に好ましくは60~70℃である。
ゴム成分は、エチレン-α-オレフィン-ジエン共重合ゴムを少なくとも含む。エチレン-α-オレフィン-ジエン共重合ゴムは、エチレン、α-オレフィン、及び非共役ジエンの共重合体である。
加硫剤としては、硫黄や硫黄化合物類、亜鉛華、セレンや酸化マグネシウム、有機過酸化物類などが挙げられる。発泡体の耐熱性、シール耐久性を考慮すると、硫黄を少なくとも用いるのが好ましい。
発泡剤は、発泡のためのガス発生のために使用されるばかりでなく、ゴム成分の加硫調整の作用も有する。例えば、ジニトロペンタメチレンテトラミン(DPT)、アゾジカルボンアミド(ADCA)、4、4’-オキシビスベンゼンスルホニルヒドラジッド(OBSH)重炭酸ナトリウムなどが挙げられる。なかでも、発泡体の耐熱性、シール耐久性を考慮すると、ADCAが特に好ましく用いられる。
本発明のシール材に用いられる混和物は、他の添加剤を目的に応じてさらに含んでいてもよい。例えば、加硫を促進させるために、チアゾール系、ジチオカルバミン酸塩系、チオウレア系、ジチオホスファイト系、チウラム系の加硫促進剤、ステアリン酸、ラウリン酸、酸化亜鉛(活性亜鉛華)などの加硫促進助剤などが用いられる。
本発明のシール材は、上述した配合剤を混練した後、所望の形状に成形し、得られた成形体を加硫及び発泡させることにより得られる。このようにして得られたシール材は、独立気泡構造を有するゴム発泡体からなる。
表1に示す配合組成において、発泡剤、発泡助剤、加硫剤、加硫促進剤を除いた配合物をニーダーにより、120℃で8分間混練した。次に、表面温度を20℃まで冷ました混練物に、表1に示す配合組成の通りに、発泡剤、発泡助剤、加硫剤、及び加硫促進剤をさらに加え、ニーダーにより、80℃で5分間混練した。そして、得られた混練物を、ゴム用押出し機によりシート状に成形し、これを加熱炉に入れて、140℃で80分間加硫発泡し、独立気泡構造を有するゴム発泡体からなるシール材を得た。
EVA1(融点71℃、メルトフローレート18g/10min、酢酸ビニルの含有量28質量%)
表1に示すように配合組成を変更した以外は、実施例1と同様にして独立気泡構造を有するゴム発泡体からなるシール材を作製した。表1におけるEVA2~4の詳細については、下記の通りである。
EVA3(融点66℃、メルトフローレート30g/10min、酢酸ビニルの含有量32質量%)
EVA4(融点79℃、メルトフローレート2500g/10min、酢酸ビニルの含有量14質量%)
まず、表2に示すように配合組成を変更した以外は、実施例1と同様にして独立気泡構造を有するゴム発泡体を作製した。次に、独立気泡構造を有するゴム発泡体を、ロールクラッシュすることにより破泡処理を行った。これにより、半連続気泡構造を有するゴム発泡体からなるシール材を得た。
表2に示すように配合組成を変更した以外は、実施例1と同様にして独立気泡構造を有するゴム発泡体からなるシール材を作製した。
まず、EVAを用いなかった以外は、実施例1と同様にして独立気泡構造を有するゴム発泡体を作製した。次に、EVA1(融点71℃、メルトフローレート18g/10分、酢酸ビニル含有量28質量%)を80℃で30分間加熱することにより溶融させ、ゴム発泡体表面上にバーコーターにより塗工し、20℃で60分間乾燥させた。しかしながら、止水性評価が可能な程度にEVA塗膜を形成することができなかった。
表2に示すように配合組成を変更した以外は、実施例1と同様にして独立気泡構造を有するゴム発泡体からなるシール材を作製した。表2におけるEVA5の詳細については、下記の通りである。
1.密度
シール材の密度を、JIS K 7222に準拠し、厚さ計(ダイヤルシックネス、テクロック社製)及び天秤(デジタル天秤、株式会社島津製作所製)を用いて測定した。結果を表3に示す。
シール材の気泡数を、JIS K 6767(1999)に準拠して測定した。結果を表3に示す。
シール材の厚さ方向における50%圧縮応力を、JIS K 6767(1999)に準拠し、硬度試験機(オートグラフ、株式会社島津製作所製)を用いて測定した。結果を表3に示す。
シール材を、図1に示すように、厚さ(a)10mm、幅(e)10mm、高さ(f)130mm、両先端の間隔(g)を45mmとしてU字状に打ち抜いてサンプルS1を得、これを図2に示すように2枚のアクリル板2、3にて厚さ方向に60%圧縮し、U字内に100mmの高さまで水を入れ、水が漏れるまでの時間を測定した。結果を表3に示す。
シール材を、80℃、0%RH環境下に24時間放置した後、上記と同様にして、止水性を評価した。結果を表3に示す。表2において、「◎」、「○」、「×」はそれぞれ下記の状態を示す。
◎:24時間以上水漏れなし。
○:8時間以上水漏れなし。
×:8時間未満内に水漏れ有り。
2、3:アクリル板
Claims (7)
- エチレンと炭素原子数が3個以上のα-オレフィンと非共役ジエンとの共重合体ゴムを含むゴム成分、加硫剤、及び発泡剤を含む混和物を、加硫及び発泡させてなるシール材であって、
前記混和物が、融点が80℃以下の熱可塑性樹脂を含むことを特徴とするシール材。 - 前記熱可塑性樹脂が、エチレン酢酸ビニル共重合体であることを特徴とする請求項1に記載のシール材。
- 前記エチレン酢酸ビニル共重合体のメルトフローレートが、1~2500g/10minであることを特徴とする請求項2に記載のシール材。
- 前記エチレン酢酸ビニル共重合体の酢酸ビニル含有量が、25~35質量%であることを特徴とする請求項2~3のいずれか1項に記載のシール材。
- 前記熱可塑性樹脂の含有量が、ゴム成分100質量部に対して、1~40質量部であることを特徴とする請求項1~4のいずれか1項に記載のシール材。
- 前記加硫剤が、硫黄を含むことを特徴とする請求項1~5のいずれか1項に記載のシール材。
- 前記発泡剤が、アゾジカルボンアミドである請求項1~6のいずれか1項に記載のシール材。
Priority Applications (4)
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US13/384,140 US9403957B2 (en) | 2009-07-14 | 2010-07-14 | Sealing material |
EP10799846.0A EP2455437B1 (en) | 2009-07-14 | 2010-07-14 | Sealing material |
CN201080031704.5A CN102471668B (zh) | 2009-07-14 | 2010-07-14 | 密封材料 |
JP2011522822A JP5746622B2 (ja) | 2009-07-14 | 2010-07-14 | シール材 |
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PCT/JP2010/061863 WO2011007788A1 (ja) | 2009-07-14 | 2010-07-14 | シール材 |
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US (1) | US9403957B2 (ja) |
EP (1) | EP2455437B1 (ja) |
JP (1) | JP5746622B2 (ja) |
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WO2013161920A1 (ja) * | 2012-04-26 | 2013-10-31 | 株式会社ブリヂストン | シール材 |
US20150133572A1 (en) * | 2011-06-02 | 2015-05-14 | Bridgestone Corporation | Sealing material |
JP2017014814A (ja) * | 2015-07-02 | 2017-01-19 | 株式会社鶴見製作所 | ウォーターフェンス |
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JP2013221061A (ja) * | 2012-04-16 | 2013-10-28 | Mitsufuku Industry Co Ltd | ゴム組成物及びその製造方法 |
CN103613898A (zh) * | 2013-11-12 | 2014-03-05 | 铜陵市肆得科技有限责任公司 | 一种电容器用多种橡胶混炼胶密封圈及其制备方法 |
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CN102471668B (zh) | 2015-06-10 |
US20120123003A1 (en) | 2012-05-17 |
JPWO2011007788A1 (ja) | 2012-12-27 |
EP2455437A1 (en) | 2012-05-23 |
EP2455437A4 (en) | 2012-12-05 |
US9403957B2 (en) | 2016-08-02 |
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