WO2017170827A1 - Feuille imperméable en mousse à cellules fermées dotée d'une couche adhésive - Google Patents

Feuille imperméable en mousse à cellules fermées dotée d'une couche adhésive Download PDF

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Publication number
WO2017170827A1
WO2017170827A1 PCT/JP2017/013160 JP2017013160W WO2017170827A1 WO 2017170827 A1 WO2017170827 A1 WO 2017170827A1 JP 2017013160 W JP2017013160 W JP 2017013160W WO 2017170827 A1 WO2017170827 A1 WO 2017170827A1
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Prior art keywords
cell foam
sheet
closed
rubber
closed cell
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PCT/JP2017/013160
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English (en)
Japanese (ja)
Inventor
太 金澤
平池　宏至
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積水化学工業株式会社
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Priority to JP2017520994A priority Critical patent/JPWO2017170827A1/ja
Publication of WO2017170827A1 publication Critical patent/WO2017170827A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
    • 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
    • C08J9/36—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing

Definitions

  • the present invention relates to a closed cell foam waterproofing sheet with an adhesion layer used as a waterproof sealant.
  • a waterproof seal material made of foam is widely used in order to fill a gap between various structures and casings and prevent water from entering.
  • a water-stop sealing material is arranged on the adherend portion in a compressed state, and is configured to closely contact the interface of the adherend portion without a gap due to repulsive stress that attempts to recover the shape from the compressed state.
  • the compressibility of the water-stopping sealing material is low, the repelling stress of the water-stopping sealing material will be too strong, and damage or deformation may occur in the adherend part. The problem of becoming insufficient arises. Therefore, it is conceivable to use an open-cell foam excellent in compression flexibility as a water-stop sealing material.
  • Patent Documents 1 and 2 describe a water-stop sealing material using a rubber-based resin closed-cell foam sheet having closed cells as a water-stop seal material that solves this problem.
  • a water-stop sealing material using a rubber-based resin closed-cell foam sheet having closed cells as a water-stop seal material that solves this problem.
  • the rubber-based resin closed cell foam sheets described in Patent Documents 1 and 2 are excellent in moldability and have strong adhesion to the adherend, and on the other hand, the sheet is attached to a product. At that time, the peelability and re-stickability (hereinafter also referred to as “reworkability”) were improved to some extent so that the attachment position could be finely corrected. However, sufficient consideration has not been given to the requirement of weather resistance in vehicle applications. The present inventors considered that the weather resistance can be solved by simply adding a weathering agent to the closed-cell foam water-stop sheet, and studied a plurality of weathering agents.
  • crosslinking is often performed by electron beam crosslinking from the viewpoint of sulfur contamination and foaming ratio improvement, and the original function of the weathering agent is attenuated in the electron beam irradiation or foaming process. It came to the result that the effect of was not obtained.
  • the present invention has been made in view of the above, and has closed cells with an adhesion layer that have good moldability and reworkability, high adhesion to the adherend surface, excellent water blocking properties, and excellent weather resistance.
  • a foam waterproof sheet is provided.
  • the present invention includes a rubber component (A) having a total content of butyl rubber (a1) and ethylene-propylene-diene rubber (a2) of 80% by mass or more and a petroleum resin-based tackifier (B) having a thickness of 0
  • the closed cell foam sheet is obtained by foaming a foamable resin composition containing a thermoplastic resin or a rubber resin and a weathering agent and a foaming agent, and the content of the weathering agent is the thermoplastic resin or rubber system.
  • the amount ratio of the ethylene-propylene-diene rubber (a2) to the butyl rubber (a1) [(a2) / (a1)] is 0.1 / 8.0 to 100 parts by weight of the resin. 93/7, the content of the petroleum resin tackifier (B) with respect to 100 parts by mass of the rubber component (A) is 0.5 to 20 parts by mass, and the 25% compression stress is 10 to 800 kPa.
  • a closed-cell foam water-stop sheet with an adhesive layer that has good moldability and reworkability, has high adhesion to the adherend surface, is excellent in water-stopping properties, and is also excellent in weather resistance. be able to.
  • the closed cell foam water-stop sheet with an adhesion layer of the present invention comprises a rubber component (A) having a total content of butyl rubber (a1) and ethylene-propylene-diene rubber (a2) of 80% by mass or more and a petroleum resin-based tackifier.
  • Closed cell foam with an adhesive layer comprising an adhesive (B) and a closed layer having a thickness of 0.01 to 2.0 mm and a closed cell foam sheet having a closed cell ratio of 70% or more.
  • the closed-cell foam sheet is formed by foaming a foamable resin composition containing a thermoplastic resin or a rubber-based resin, a weathering agent and a foaming agent, and the content of the weathering agent is 0.1 to 8.0 parts by mass with respect to 100 parts by mass of the plastic resin or rubber-based resin, and the mass ratio of the ethylene-propylene-diene rubber (a2) to the butyl rubber (a1) [(a2) / (a1)] Is 0/10 To 93/7, the content of the petroleum resin tackifier (B) is 0.5 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A), and the 25% compression stress is 10 to 800 kPa. It is a closed cell foam waterproofing sheet with an adhesion layer.
  • the adhesion layer used in the present invention includes a rubber component (A) having a total content of butyl rubber (a1) and ethylene-propylene-diene rubber (a2) of 80% by mass or more and a petroleum resin-based tackifier (B).
  • the thickness is 0.01 to 2.0 mm.
  • the rubber component (A) and the petroleum resin tackifier (B) are used in the adhesion layer, an closed cell foam sheet with an adhesion layer excellent in reworkability and water-stopping property is provided. Can do.
  • the rubber component (A) in the present invention has a total content of butyl rubber (a1) and ethylene-propylene-diene rubber (a2) of 80% by mass or more. If the total content of butyl rubber (a1) and ethylene-propylene-diene rubber (a2) is less than 80% by mass, the water-stopping property is lowered.
  • the total content of butyl rubber (a1) and ethylene-propylene-diene rubber (a2) contained in the rubber component (A) is 80% by mass or more, preferably 85% by mass from the viewpoint of improving reworkability and water-stopping property. % Or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and still more preferably 100% by mass.
  • the rubber component (A) has a mass ratio [(a2) / (a1)] of the ethylene-propylene-diene rubber (a2) to the butyl rubber (a1) of 0/100 to 93/7. If the mass ratio [(a2) / (a1)] is within the above range, the moldability, reworkability and water stoppage are improved.
  • the mass ratio [(a2) / (a1)] is preferably from 1/99 to 85/15, more preferably from 2/98 to 70/30, from the viewpoints of moldability, reworkability, and water stoppage.
  • the ratio is preferably 3/97 to 50/50, more preferably 5/95 to 30/70.
  • butyl rubber (a1)) In addition to butyl rubber (IIR), halogenated butyl rubber can also be used as butyl rubber (a1) in the present invention.
  • the halogenated butyl rubber include chlorinated butyl rubber and brominated butyl rubber. Among these, it is preferable to use butyl rubber (IIR) from the viewpoint of improving kneadability during extrusion and flexibility after sheet molding.
  • the Mooney viscosity ML (1 + 8) at 125 ° C. of butyl rubber is preferably 20 to 60, more preferably 25 to 55, and further preferably 25 to 40.
  • the Mooney viscosity is within the above range, the cohesive force is improved, the strength of the molded body is improved, and the load applied to the kneading apparatus during kneading can be reduced, so that the moldability is improved.
  • EPM ethylene propylene rubber
  • DCP dicyclopentadiene
  • the diene content in the ethylene-propylene-diene rubber (a2) is preferably 1 to 15% by mass, more preferably 2 to 12% by mass from the viewpoint of preventing heat generation during extrusion kneading and improving mechanical properties such as elongation. %, More preferably 3 to 10% by mass.
  • the Mooney viscosity ML (1 + 4) at 125 ° C. of the ethylene-propylene-diene rubber (a2) is preferably 15 to 70, more preferably 15 to 60, still more preferably 20 to 50, and still more preferably 24 to 30.
  • the Mooney viscosity at 125 ° C. of the ethylene-propylene-diene rubber (a2) is equal to or higher than the lower limit, the cohesive force is increased, so that the strength of the molded body is improved. Formability is improved because the load is reduced.
  • Examples of commercially available ethylene-propylene-diene rubbers include EP21, EP22 and EP33 (manufactured by JSR Corporation), Esprene 567 (manufactured by Sumitomo Chemical Co., Ltd.), and EPT3045 (manufactured by Mitsui Petrochemical Industries, Ltd.). .
  • the rubber component (A) may contain rubber other than butyl rubber (a1) and ethylene-propylene-diene rubber (a2).
  • Other rubbers are not particularly limited as long as they have rubber elasticity at room temperature (25 ° C.).
  • chloroprene rubber (CR), isoprene rubber (IR), natural rubber, styrene-butadiene copolymer Examples include polymerized rubber (SBR), butadiene rubber (BR), urethane rubber, fluororubber, acrylic rubber, and silicone rubber. These may be used alone or in combination of two or more.
  • the petroleum resin-based tackifier (B) is used for the purpose of improving the adhesion to the adherend surface of the closed cell foam water-stop sheet with an adhesion layer.
  • the petroleum resin tackifier (B) in the present invention refers to a tackifier obtained by cationic polymerization of a fraction containing an unsaturated hydrocarbon obtained by thermal decomposition of petroleum naphtha or the like.
  • the petroleum resin-based tackifier (B) when used, it is not clear why the adhesion to the adherend surface of the closed cell foam waterproofing sheet with the adhesion layer is improved, but the petroleum resin-based tackifier This is considered to be due to the good dispersibility of the rubber component in the rubber component.
  • Petroleum resin tackifiers (B) include C5 petroleum resin tackifiers, C9 petroleum resin tackifiers, C5-C9 copolymer petroleum resin tackifiers, coumarone resin tackifiers, coumarone-indenes Examples thereof include resin tackifiers, pure monomer resin tackifiers, ginclopentadiene petroleum resin tackifiers, and tackifiers composed of these hydrides.
  • C5 petroleum resin tackifier, C9 from the viewpoint of improving the adhesion with the adherend surface of the closed cell foam water-stop sheet with an adhesion layer and the compatibility with the rubber component (A). Based petroleum resin tackifiers and C5-C9 copolymerized petroleum resin tackifiers are preferred, and C5 petroleum resin tackifiers are more preferred.
  • the content of the petroleum resin-based tackifier (B) with respect to 100 parts by mass of the rubber component (A) maintains the waterproof property by improving the adhesion and maintains the appropriate flexibility, and the performance against water pressure. From the viewpoint of improvement, it is 0.5 to 20 parts by mass, preferably 1.5 to 15 parts by mass, more preferably 3 to 12 parts by mass, and still more preferably 3.5 to 9 parts by mass. If the content of the petroleum resin-based tackifier (B) with respect to 100 parts by mass of the rubber component (A) is less than the lower limit, the water stopping performance is lowered, and if it exceeds the upper limit, the extrusion moldability is lowered.
  • the adhesion layer may contain an additive.
  • the additive include a flame retardant, an antioxidant, a filler, a pigment, a colorant, an antifungal agent, a foaming aid, a lubricant, an inactivating agent, and a flame retardant aid.
  • the flame retardant include bromine-based flame retardants such as decabromodiphenyl ether and phosphorus-based flame retardants such as ammonium polyphosphate in addition to metal hydroxides such as aluminum hydroxide and magnesium hydroxide.
  • the antioxidant include a phenol-based antioxidant and a sulfur-based antioxidant.
  • the filler include talc, calcium carbonate, bentonite, carbon black, fumed silica, aluminum silicate, acetylene black, and aluminum powder. These additives may be used alone or in combination of two or more.
  • the thickness of the adhesion layer is 0.01 to 2.0 mm, preferably 0.03 to 1.0 mm, more preferably 0.05 to 0.3 mm. When the thickness is within the above range, the adhesion performance is exhibited and warpage is hardly generated, which is preferable.
  • “warping” in the present specification means that the closed-cell foam water-stop sheet of the present invention is cut into a size of 500 mm ⁇ 500 mm and placed on a flat table, and a part of the cut closed-cell foam water-stop sheet is removed from the table. The state where it is separated by 15 mm or more and is floating.
  • the closed cell foam sheet used in the present invention is obtained by foaming a foamable resin composition containing a thermoplastic resin or a rubber-based resin, a weathering agent and a foaming agent (foam), and has a closed cell ratio of 70. It is a closed cell foam sheet produced by a method in which the foamable resin composition is formed into a sheet, crosslinked by ionizing radiation, and then foamed through a heating furnace. From the viewpoint of water-stopping properties, it is preferable that the thermoplastic resin is a foamed olefin resin or a foamed rubber resin, more preferably a foamed olefin resin.
  • propylene- ⁇ -olefin copolymers having a main component ethylene-propylene-butene terpolymers having propylene as a main component, polybutene and polymethylpentene are preferred.
  • polyethylene resin examples include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer containing ethylene as a main component, and ethylene-ethyl containing ethylene as a main component.
  • An acrylate copolymer etc. are mentioned.
  • the ⁇ -olefin constituting the ethylene- ⁇ -olefin copolymer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene. Can be mentioned.
  • Examples of the ⁇ -olefin constituting the propylene- ⁇ -olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Can be mentioned. These olefinic resins may be used alone or in combination of two or more. Among these, from the viewpoint of improving water-stopping properties, low-density polyethylene and high-density polyethylene are preferable, and it is preferable to use a mixture of low-density polyethylene and high-density polyethylene.
  • acrylonitrile-butadiene rubber is preferable from the viewpoint of improving the water-stopping property.
  • the acrylonitrile-butadiene rubber preferably has an acrylonitrile component content of preferably 30 to 50% by mass, more preferably 35 to 50% by mass, and even more preferably 40 to 45% by mass.
  • the weight average value is the content of the acrylonitrile component.
  • the rubber other than acrylonitrile-butadiene rubber constituting the rubber-based resin is not particularly limited as long as it has rubber elasticity at room temperature (25 ° C.).
  • CR chloroprene rubber
  • IR isoprene rubber
  • IIR butyl rubber
  • SBR styrene-butadiene copolymer rubber
  • BR butadiene rubber
  • EPDM ethylene-propylene-diene rubber
  • urethane rubber fluorine rubber
  • acrylic rubber silicone rubber, etc.
  • a thermal decomposition type foaming agent that decomposes by heat to generate gas is preferable.
  • the thermally decomposable foaming agent include azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, toluenesulfonylhydrazide, 4,4-oxybis (benzenesulfonylhydrazide), and the like. These may be used alone or in combination of two or more.
  • the amount of the pyrolytic foaming agent is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, and even more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin or rubber resin. is there.
  • the blending amount of the pyrolytic foaming agent is within the above range, it is possible to obtain a closed-cell foamed water-stop sheet with an adhesive layer having excellent water-stopping properties over a long period of time.
  • the closed cell foam sheet of the present invention contains a weathering agent as an essential component.
  • the weathering agent is not particularly limited as long as the original function is not attenuated or lost in the electron beam irradiation process.
  • Examples of the weathering agent include carbon black, a radical scavenger, and a radical chain initiation inhibitor. From the viewpoint of weather resistance, carbon black alone or at least one selected from carbon black, a radical scavenger and a radical chain initiation inhibitor is preferable.
  • the content of the weathering agent is 0.1 to 8.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin or rubber resin.
  • the weather resistance is excellent while maintaining the original basic characteristics (see evaluation items of Examples described later) possessed by the closed cell foam water-stop sheet with an adhesion layer.
  • a closed-cell foam water-stop sheet with an adhesion layer can be obtained.
  • Carbon black is not particularly limited, and examples thereof include acetylene black, ketjen black, furnace black, channel black, and thermal black. Among these, furnace black is preferable from the viewpoint of processing characteristics. Carbon black may be used alone or in combination of two or more carbon blacks.
  • the average particle size of carbon black is preferably 8 to 60 ⁇ m, more preferably 10 to 50 ⁇ m. In addition, the average particle diameter of the carbon black used for this invention was computed with the electron microscope (SEM observation).
  • hindered amine light stabilizer As the radical scavenger, a hindered amine light stabilizer is preferable.
  • HALS hindered amine light stabilizers
  • examples of hindered amine light stabilizers (HALS) include 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2,6, 6-pentamethyl-4-piperidyl), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1 , 2,3,4-tetracarboxylate (ADK STAB LA-52), 1,2,3,4-but
  • the radical chain initiation inhibitor is preferably an ultraviolet absorber (UVA).
  • UVA ultraviolet absorber
  • UVA itself does not have antioxidant ability, it can detoxify light degradation factors and suppress the initiation of chain reaction. UVA absorbs in the ultraviolet region and is rendered harmless by converting the absorbed ultraviolet energy into thermal energy. Examples of UVA include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, salicylate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.
  • benzotriazole ultraviolet absorber examples include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4 -Methylphenol (Adekastab LA-36), 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, polyethylene glycol 3- [3- (benzotriazol-2-yl) -5- and tert-butyl-4-hydroxyphenyl] propionic acid ester.
  • benzophenone-based ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy- And benzophenone-5-sulfonic acid.
  • triazine ultraviolet absorber examples include 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 85% 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and oxirane [(C10-C16 mainly C12-C13 alkyloxy) methyl] oxirane Reaction product of 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine with (2-ethylhexyl) -glycidic acid ester Products, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5-triazine-2,4, (IH, 3H, 5H) - trione, 1,
  • Examples of salicylate-based ultraviolet absorbers include phenyl salicylate and 4-t-butylphenyl salicylate.
  • Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, and the like.
  • Examples of the oxanilide ultraviolet absorber include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxyn-5-t-butyl-2′-ethyloxalic acid bisanilide, and the like. Of these, 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol (ADK STAB LA-36) is preferred from the viewpoint of thermal stability.
  • the closed cell foam sheet may contain an additive.
  • the additive include a flame retardant, an antioxidant, a filler, a pigment, a colorant, an antifungal agent, a foaming aid, a lubricant, an inactivating agent, and a flame retardant aid.
  • the flame retardant include bromine-based flame retardants such as decabromodiphenyl ether and phosphorus-based flame retardants such as ammonium polyphosphate in addition to metal hydroxides such as aluminum hydroxide and magnesium hydroxide.
  • the antioxidant include a phenol-based antioxidant and a sulfur-based antioxidant.
  • the filler include talc, calcium carbonate, bentonite, carbon black, fumed silica, aluminum silicate, acetylene black, and aluminum powder. These additives may be used alone or in combination of two or more.
  • the thickness of the closed cell foam sheet is appropriately selected depending on the intended use and is not particularly limited, but is preferably 0.05 to 15 mm, more preferably 0.1 to 10 mm, and further preferably 1 to 8 mm. It is preferable for the thickness to be in the above-mentioned range since warpage is unlikely to occur.
  • the apparent density of the closed cell foam sheet is preferably 15 to 700 kg / m 3 , more preferably 17 to 600 kg / m 3 , and still more preferably 20 to 500 kg / m 2 .
  • m is 3.
  • the apparent density is within the above range, the repulsive force does not become too high, so that the workability is improved.
  • the apparent density of the closed cell foam sheet is high, it can be used by lowering the compressibility.
  • the closed cell foam sheet used in the present invention has a closed cell ratio of 70% or more, and some of the cells may contain open cells.
  • the closed cell ratio of the closed cell foam sheet is preferably 70 to 100%, more preferably 80 to 100%, and still more preferably 83 to 100%, from the viewpoint of water blocking.
  • the closed cell rate in this invention says what was measured in the following ways. First, a test piece having a flat square shape with a side of 5 cm and a constant thickness is cut out from the closed cell foam sheet. Then, the thickness of the test piece is measured to calculate the apparent volume V 1 of the test piece, and the weight W 1 of the test piece is measured.
  • the volume V 2 occupied by the bubbles is calculated based on the following formula.
  • the density of the resin constituting the test piece is ⁇ g / cm 3 .
  • Volume occupied by bubbles V 2 V 1 ⁇ W 1 / ⁇
  • the method for producing the closed cell foam sheet used in the present invention is not particularly limited, but a foamable resin composition containing a thermoplastic resin or rubber resin, a weathering agent and a foaming agent, and optional additives is kneaded into a sheet shape. It is preferable to prepare a foamable resin sheet by molding, then cross-link with ionizing radiation or the like, and then foam by passing through a heating furnace.
  • the foamable resin composition is kneaded using a kneader such as a Banbury mixer or a pressure kneader, and then continuously extruded by an extruder, a calender, a conveyor belt casting or the like.
  • a kneader such as a Banbury mixer or a pressure kneader
  • Crosslinking method of foamable resin sheet crosslinking by ionizing radiation
  • examples of the ionizing radiation include light, ⁇ -rays, and electron beams.
  • the dose of ionizing radiation is preferably 0.5 to 15 Mrad, more preferably 0.7 to 10 Mrad.
  • cross-linking is performed by ionizing radiation, a closed cell foam sheet having a uniform cell with a small diameter can be obtained.
  • Such a closed cell foam sheet having a small diameter and uniform bubbles has a smooth surface, a large contact area with respect to the adherend surface, and improved adhesion, and thus has excellent water-stopping properties.
  • Foaming method of foamable resin sheet examples include a batch system such as an oven and a continuous foaming system in which the foamable resin sheet is formed into a long sheet shape and continuously passed through a heating furnace.
  • the temperature at which the foamable resin sheet is foamed is preferably 200 to 300 ° C., more preferably 220 to 280 ° C., although it depends on the type of foaming agent used.
  • the 25% compressive stress of the closed cell foam water-stop sheet with an adhesive layer of the present invention is 10 to 800 kPa, preferably 20 to 700 kPa, more preferably 25 to 500 kPa.
  • the 25% compressive stress of the closed cell foam water-proof sheet with the adhesion layer is within the above range, the workability is improved and the assemblability is improved.
  • 25% compressive stress can be measured by the method as described in an Example.
  • Petroleum resin tackifier (1) “QuintoneR-100” manufactured by Nippon Zeon Co., Ltd.
  • Petroleum resin-based tackifier (2) “QuintoneA-100” manufactured by Nippon Zeon Co., Ltd.
  • Phenolic antioxidant (1) "ADEKA STAB AO-60P” manufactured by ADEKA CORPORATION ⁇ Phenolic antioxidant (2) "ADEKA STAB AO-50” manufactured by ADEKA CORPORATION ⁇ Sulfur-based antioxidant "NOCRACK 400S” manufactured by Ouchi Shinsei Chemical Co., Ltd. ⁇ Carbon black (for adhesion layer) "# 60" made by Asahi Carbon Co., Ltd.
  • Example 1 Manufacture of closed cell foam sheet> 100 parts by weight of low density polyethylene, 10 parts by weight of ADCA, 0.5 parts by weight of phenolic antioxidant (1), 2.0 parts by weight of zinc stearate, 5.0 parts by weight of carbon black, 1 part by weight of lubricant, inert A mixture containing 0.5 parts by mass of the agent and 1 part by mass of titanium oxide was continuously charged into the extruder, and melt-kneaded and extruded by the extruder to obtain an uncrosslinked / unfoamed sheet. By irradiating the obtained sheet with an electron beam having a dose of 2.9 Mrad and an acceleration voltage of 800 kV, a crosslinked / non-foamed sheet was obtained.
  • the obtained crosslinked / non-foamed sheet is heated to 240 ° C. in a foaming furnace to decompose and foam ADCA (azodicarbonamide), whereby an apparent density of 35 kg / m 3 (the apparent density conforms to JIS K 7222). ), An closed cell foam sheet having an average thickness of 5.0 mm and a variation in thickness in the width direction within ⁇ 20% of the average thickness was obtained. In addition, about the variation in the said thickness, it measured by the method similar to the extrusion moldability evaluation of the below-mentioned contact
  • ADCA azodicarbonamide
  • Example 2 A closed cell foam water-stop sheet with an adhesive layer was obtained in the same manner as in Example 1 except that the carbon black and the foaming agent were blended as shown in Table 1.
  • Example 3 Closed-cell foam waterproofing sheet with an adhesive layer by the same method as in Example 1 except that the amount of carbon black was reduced and the radical scavenger 1 and radical chain initiation inhibitor were added to obtain the formulation shown in Table 1. Got.
  • Example 4 A closed cell foam water-stop sheet with an adhesive layer was obtained in the same manner as in Example 3 except that the radical scavenger 1 was changed to the radical scavenger 2 and the formulation shown in Table 1 was used.
  • Example 5 A closed cell foam water-stop sheet with an adhesive layer was obtained in the same manner as in Example 3 except that the radical scavenger 1, radical chain initiation inhibitor and foaming agent were blended as shown in Table 1.
  • Example 6 A closed cell foam water-stop sheet with an adhesive layer was obtained in the same manner as in Example 3 except that the radical scavenger 1, radical chain initiation inhibitor and foaming agent were blended as shown in Table 1.
  • Comparative Example 1 A closed cell foam water-stop sheet with an adhesive layer was obtained in the same manner as in Example 1 except that the carbon black and the foaming agent were blended as shown in Table 1.
  • Comparative Example 2 A closed cell foam water-stop sheet with an adhesive layer was obtained in the same manner as in Example 3 except that the radical scavenger 1, radical chain initiation inhibitor and foaming agent were blended as shown in Table 1.
  • Comparative Example 3 A closed cell foam water-stop sheet with an adhesive layer was obtained in the same manner as in Example 1 except that carbon black was formulated as shown in Table 1.
  • the weather resistance test was performed on the closed-cell foamed water-stop sheet with an adhesive layer produced in the examples and comparative examples under the following conditions.
  • ⁇ Weather resistance evaluation> Evaluation method In accordance with JIS B7753 (2007), using a sunshine weather meter (Suga Test Instruments Co., Ltd., “model number: S80”; sunshine carbon arc (ultra long life carbon 4 pair) light source), discharge voltage 50V The discharge current is set to 60 A, irradiation is performed, surface spraying (rainfall) is performed for 12 minutes per hour, and 500 hours and 1000 are applied to the surface of the test piece under the conditions of a black panel temperature of 63 ° C. and a relative humidity of 50%. Time irradiation treatment was performed.
  • distilled water was filled from the through hole into the ring-shaped sealing material while maintaining the compressibility, and water pressure was applied to the inner side of the ring-shaped sealing material to determine the presence or absence of water leakage.
  • the water pressure is maintained at 5 kPa for 5 minutes, then the pressure is increased by 5 kPa, maintained for 5 minutes for each pressure, the pressure is increased until the water inside the ring-shaped sealing material leaks, and the maximum pressure is increased. Asked.
  • 200 kPa was set as the upper limit of the measurement. Evaluation criteria In this test, the measured value is preferably 10 kPa or more, and more preferably 30 kPa or more.
  • the test piece is a rectangular parallelepiped having a length of 50 mm, a width of 50 mm, and a thickness of 10 mm. After measuring the thickness of the test piece at the center, the test piece is sandwiched between jigs and closed cell foam with an adhesion layer Both surfaces of the water stop sheet were bonded to a jig with the same double-sided tape (“# 5782” manufactured by Sekisui Chemical Co., Ltd.). After the bonding was completed, a tensile test was performed at a tensile speed of 10 mm / min. -Evaluation criteria Based on the value of tensile strength, evaluation was performed according to the following evaluation criteria. ⁇ : 1 kgf / cm 2 or more (good adhesion) ⁇ : Less than 1 kgf / cm 2 (insufficient adhesion)

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • General Engineering & Computer Science (AREA)
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Abstract

L'invention concerne une feuille imperméable en mousse à cellules fermées dotée d'une couche adhésive, obtenue en faisant adhérer : une couche adhésive contenant un agent poisseux à base de résine de pétrole (B) et un composant caoutchouc (A) contenant un total d'au moins 80 % en masse d'un caoutchouc butylique (a1) et d'un caoutchouc d'éthylène-propylène-diène (a2), et ayant une épaisseur de 0,01 à 2,0 mm; et une feuille en mousse à cellules fermées ayant un rapport de cellules fermées de 70 % ou plus, l'une à l'autre. La feuille en mousse à cellules fermées est obtenue par l'expansion d'une composition de résine expansible contenant une résine thermoplastique ou une résine à base de caoutchouc, un agent résistant aux intempéries et un agent d'expansion. La teneur en agent résistant aux intempéries est de 0,1 à 8,0 partis en masse pour 100 parts en masse de la résine thermoplastique ou de la résine à base de caoutchouc. Le rapport de masse du caoutchouc d'éthylène-propylène-diène (a2) sur le caoutchouc butylique (a1) est de 0/100 à 93/7. La teneur en agent poisseux à base de résine de pétrole (B) est de 0,5-20 parts en masse pour 100 parts en masse du composant de caoutchouc (A). La feuille imperméable en mousse à cellules fermées dotée d'une couche adhésive présente une contrainte de compression à 25 % de 10 à 800 kPa.
PCT/JP2017/013160 2016-03-30 2017-03-30 Feuille imperméable en mousse à cellules fermées dotée d'une couche adhésive WO2017170827A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031810A (ja) * 1999-07-23 2001-02-06 Mitsui Chemicals Inc 架橋可能なゴム組成物およびその用途
WO2007072885A1 (fr) * 2005-12-21 2007-06-28 Sekisui Chemical Co., Ltd. Feuille de caoutchouc cellulaire etanche, stratifie, et materiau d'etancheite etanche a l'eau/hermetique a l'eau utilisant la feuille ou le stratifie
JP2009242624A (ja) * 2008-03-31 2009-10-22 Sekisui Chem Co Ltd シール材
JP2010199538A (ja) * 2009-01-28 2010-09-09 Sekisui Chem Co Ltd 太陽電池モジュール用止水テープ
JP2012214624A (ja) * 2011-03-31 2012-11-08 Sekisui Chem Co Ltd 発泡体、該発泡体を用いたシール材、及び該発泡体の製造方法
WO2012157709A1 (fr) * 2011-05-18 2012-11-22 三井化学株式会社 Copolymère de propylène et composition à base d'un copolymère de propylène, moulage et mousse en contenant et procédés de production desdits moulages et mousses
WO2015125917A1 (fr) * 2014-02-20 2015-08-27 積水化学工業株式会社 Feuille d'étanchéité en mousse à cellules fermées ayant une couche d'adhérence

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031810A (ja) * 1999-07-23 2001-02-06 Mitsui Chemicals Inc 架橋可能なゴム組成物およびその用途
WO2007072885A1 (fr) * 2005-12-21 2007-06-28 Sekisui Chemical Co., Ltd. Feuille de caoutchouc cellulaire etanche, stratifie, et materiau d'etancheite etanche a l'eau/hermetique a l'eau utilisant la feuille ou le stratifie
JP2009242624A (ja) * 2008-03-31 2009-10-22 Sekisui Chem Co Ltd シール材
JP2010199538A (ja) * 2009-01-28 2010-09-09 Sekisui Chem Co Ltd 太陽電池モジュール用止水テープ
JP2012214624A (ja) * 2011-03-31 2012-11-08 Sekisui Chem Co Ltd 発泡体、該発泡体を用いたシール材、及び該発泡体の製造方法
WO2012157709A1 (fr) * 2011-05-18 2012-11-22 三井化学株式会社 Copolymère de propylène et composition à base d'un copolymère de propylène, moulage et mousse en contenant et procédés de production desdits moulages et mousses
WO2015125917A1 (fr) * 2014-02-20 2015-08-27 積水化学工業株式会社 Feuille d'étanchéité en mousse à cellules fermées ayant une couche d'adhérence

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