JP2014180817A - Foam laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foam laminate that has excellent water cut-off performance, enables temporary fixing, and has excellent workability.SOLUTION: A foam laminate 1 is provided with: a foam layer 2 that is formed of a resin foam; and an adhesive layer 4 that is laminated on at least one surface of the foam layer 2. The adhesive layer 4 has a shear storage modulus at 25°C of 1.5×10Pa or more, and the adhesive strength of the adhesive layer 4 to an acrylic plate is from 0.05 N/25 mm to 4.0 N/25 mm (inclusive).

Description

  The present invention relates to a foam laminate. In detail, it is related with the foaming laminated body used suitably as a sealing material of various industrial products.

  Conventionally, resin foams such as EPDM foams obtained by foaming ethylene / propylene / diene rubber (hereinafter sometimes referred to as EPDM) are known as sealing materials for various industrial products.

  Such a resin foam is disposed between one member to be sealed and the other member, and then compressed through the member, so that the member is sealed with the resin foam.

  However, the resin foam single layer alone has a problem that the water stoppage at the seal portion (compressed resin foam) is insufficient.

  Therefore, in order to improve the water-stopping property, a water-stopping sealing material in which a polyester-based pressure-sensitive adhesive layer containing a polymer having a polycarbonate structure is laminated on one surface of a resin foam has been proposed (for example, see Patent Document 1). ).

  According to the waterproof seal material described in Patent Document 1, the waterproof property is improved.

Japanese Patent Laid-Open No. 11-35924

  However, the pressure-sensitive adhesive layer on the surface of the water sealing material described in Patent Document 1 does not have a tack force. Therefore, when the member to be sealed is placed on the surface of the water-stop sealing material and sealed, temporary fixing cannot be performed, and thus there is a problem that workability is inferior.

  An object of the present invention is to provide a foam laminate that has good water-stopping properties, can be temporarily fixed, and is excellent in workability.

In order to achieve the above object, a foam laminate of the present invention comprises a foam layer formed from a resin foam and a pressure-sensitive adhesive layer laminated on at least one surface of the foam layer. The shear storage modulus at 25 ° C. is 1.5 × 10 ⁵ Pa or more, and the adhesive force of the adhesive layer to the acrylic plate is 0.05 N / 25 mm or more and 4.0 N / 25 mm or less. Yes.

  Moreover, in the foaming laminated body of this invention, it is suitable for the said adhesive layer to contain an oligomer.

  In the foam laminate of the present invention, it is preferable that the oligomer has a number average molecular weight of 500 or more and 10,000 or less.

  In the foamed laminate of the present invention, it is preferable that the oligomer is a compound having a polyoxyalkylene unit.

  Moreover, in the foaming laminated body of this invention, it is suitable that the content rate of the said oligomer is 0.01 mass part or more and 20 mass parts or less with respect to 100 mass parts of adhesive layers.

  Moreover, in the foaming laminated body of this invention, it is suitable that the adhesive composition which forms the said adhesive layer contains a polymer.

  Moreover, in the foaming laminated body of this invention, it is suitable for the said adhesive composition to contain a crosslinking agent.

  In the foam laminate of the present invention, it is preferable that the resin foam contains a polyolefin foam, a urethane foam, or a rubber foam.

  In the foam laminate of the present invention, it is preferable that the rubber-based foam contains ethylene / propylene / diene rubber.

In the foamed laminate of the present invention, it is preferable that the 10% compression load is 0.1 N / cm ² or more and 2.0 N / cm ² or less.

The foam laminate of the present invention comprises a foam layer formed from a resin foam and an adhesive layer laminated on at least one surface of the foam layer, and the shear storage elastic modulus at 25 ° C. of the adhesive layer is 1.5 × 10 ⁵ Pa or more, and the adhesive strength of the adhesive layer to the acrylic plate is 0.05 N / 25 mm or more and 4.0 N / 25 mm or less. Therefore, the water stopping property is good. Moreover, since a foaming laminated body can be temporarily fixed to the member sealed, it is excellent in workability | operativity.

FIG. 1A is a process diagram for explaining an embodiment of a method for producing a foam laminate of the present invention, FIG. 1A is a process for preparing a foam layer, and FIG. 1B is a process for forming an undercoat layer on one surface of the foam layer. 1C is a step of disposing the pressure-sensitive adhesive layer laminated substrate and the foam layer, FIG. 1D is a step of laminating the pressure-sensitive adhesive layer and the foam layer (undercoat layer), and FIG. 1E is a foam laminate of the release substrate. The process of peeling from is shown.

  The foam laminate of the present invention comprises a foam layer formed from a resin foam and an adhesive layer laminated on at least one surface of the foam layer, and is used as a sealing material.

  Examples of the resin foam include foams such as polyolefin foam, urethane foam, and rubber foam.

  Examples of the polyolefin foam include foamed polyethylene and foamed polypropylene.

  Examples of the urethane foam include flexible urethane foam, rigid urethane foam, urethane-modified polyisocyanurate foam, and polyisocyanurate foam.

  In the present invention, a rubber foam is preferable.

  The rubber-based foam is obtained, for example, by foaming a rubber composition containing rubber, a foaming agent and a crosslinking agent.

  Examples of such rubber include olefin elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM), such as styrene-butadiene rubber (SBR), styrene-butadiene-styrene rubber (SBS). Styrene-isoprene-styrene rubber (SIS), styrene-ethylene-butadiene rubber, styrene-ethylene-butylene-styrene rubber (SEBS), styrene-isobutylene-styrene block rubber (SIBS), styrene-isoprene-propylene-styrene rubber, etc. Styrene elastomers such as butyl rubber, polyisobutylene rubber, polybutene, polyisoprene rubber, nitrile butadiene rubber (NBR), etc., such as chloroprene rubber, Vinyl chloride elastomer, such Rorosuruhon polyethylene rubber, e.g., natural rubber.

  The rubber contained in the resin foam is preferably an olefin-based elastomer, more preferably EPDM. By containing such rubber, even when the foamed laminate is compressed at a lower compression rate and the members are sealed, reliable water-stopping can be ensured.

  EPDM is a rubber obtained by copolymerization of ethylene, propylene and dienes. In addition to ethylene and propylene, dienes are further copolymerized to introduce unsaturated bonds and enable crosslinking with a crosslinking agent. It is said.

  Examples of dienes 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.

  If the diene is dicyclopentadiene, the degree of crosslinking can be improved.

  Moreover, as EPDM, Preferably, EPDM which has a long chain branch is mentioned.

  The method for introducing a long branched chain into EPDM is not particularly limited, and a known method is employed.

  If EPDM has long chain branching, the rubber composition can be foamed well.

  In the present invention, the content (diene content) of dienes in EPDM is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and for example, 20% by mass. % Or less, preferably 15% by mass or less. If the diene content is less than this, surface shrinkage of the EPDM foam obtained by foaming EPDM may occur. Moreover, when more than this, a crack may arise in an EPDM foam.

  Examples of the foaming agent include organic foaming agents and inorganic foaming agents.

  Examples of the organic foaming agent include azo foaming agents such as azodicarboxylic amide (ADCA), barium azodicarboxylate, azobisisobutyronitrile (AIBN), azocyclohexylnitrile, and azodiaminobenzene, such as N N-nitroso-based blowing agents such as N, N'-dinitrosopentamethylenetetramine (DTP), N, N'-dimethyl-N, N'-dinitrosoterephthalamide, trinitrosotrimethyltriamine, for example, 4,4'- Oxybis (benzenesulfonylhydrazide) (OBSH), paratoluenesulfonyl hydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 2,4-toluenedisulfonylhydrazide, p, p-bis (benzenesulfonylhydrazide) ether, benzene- 1,3-disulfo Hydrazide-based blowing agents such as nylhydrazide and allylbis (sulfonylhydrazide), for example, p-toluylenesulfonyl semicarbazide, semicarbazide-based blowing agents such as 4,4′-oxybis (benzenesulfonyl semicarbazide), such as trichloromonofluoromethane, dichloro Examples include fluorinated alkane-based blowing agents such as monofluoromethane, triazole-based blowing agents such as 5-morpholyl-1,2,3,4-thiatriazole, and other known organic foaming agents. Examples of the organic foaming agent include thermally expandable fine particles in which a heat-expandable substance is enclosed in a microcapsule. Examples of such thermally expandable particles include microspheres (trade name, Matsumoto). And commercial products such as those manufactured by Yushi Corporation.

  Examples of the inorganic foaming agent 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. Examples thereof include borohydride salts such as sodium borohydride, for example, azides, and other known inorganic foaming agents. These foaming agents may be used alone or in combination of two or more.

  Preferably, an organic foaming agent is mentioned, More preferably, an azo foaming agent is mentioned.

  The blending ratio of the foaming agent is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 10 parts by mass or more, and, for example, 50 parts by mass with respect to 100 parts by mass of rubber. Hereinafter, it is preferably 30 parts by mass or less.

Examples of the crosslinking agent include sulfur (S ₈ ) and sulfur compounds (for example, 4,4′-dithiodimorpholine and the like), selenium, magnesium oxide, lead monoxide, quinoid compounds (for example, p-quinonedioxime, p, p '-Dibenzoylquinonedioxime, poly-p-dinitrosobenzene, etc.), polyamine, nitroso compounds (eg, p-dinitrosobenzene, etc.), organic peroxides (eg, dicumyl peroxide, dimethyldi (t-butyl) Peroxy) hexane, 1,1-di (t-butylperoxy) cyclohexane, α, α′-di (t-butylperoxy) diisopropylbenzene), resin (eg, alkylphenol-formaldehyde resin, melamine-formaldehyde condensation) Products), ammonium salts (such as ammonium benzoate) Is mentioned.

  These crosslinking agents can be used alone or in combination of two or more.

Preferably, the sulfur (S ₈₎ and sulfur compounds, quinoid compound, and an organic peroxide. In particular, from the viewpoint of ensuring excellent mechanical strength and foamability, sulfur and sulfur compounds are preferable. In addition, a quinoid compound is preferably used from the viewpoint that the sulfur atom content ratio can be reduced, corrosion resistance is reduced, and excellent foamability can be secured. From the viewpoint of being able to obtain a resin foam with high foaming and excellent flexibility, for example, from the viewpoint of improving the adhesion to the object to be sealed, the step following ability, preferably an organic peroxide is mentioned. It is done.

  The blending ratio of the crosslinking agent is, for example, 0.05 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of rubber. It is 20 parts by mass or less, more preferably 10 parts by mass or less.

  In the present invention, more preferably, a quinoid compound and an organic peroxide are used in combination as a crosslinking agent. If the quinoid compound and the organic peroxide are used in combination, the crosslinking on the surface of the resin foam can be sufficiently ensured.

  In the case where the quinoid compound and the organic peroxide are used in combination, the mixing ratio of the organic peroxide is, for example, 1 part by mass or more, preferably 10 parts by mass or more with respect to 100 parts by mass of the quinoid compound. Yes, for example, 100 parts by mass or less, preferably 50 parts by mass or less.

  The rubber composition preferably contains a foaming aid and a crosslinking aid.

  Examples of foaming aids include urea foaming aids, salicylic acid foaming aids, benzoic acid foaming aids, metal oxides (eg, zinc oxide) and the like. Preferably, urea-based foaming aids and metal oxides are used. These foaming aids may be used alone or in combination of two or more.

  The blending ratio of the foaming aid is, for example, 0.5 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 with respect to 100 parts by mass of rubber. It is as follows.

  Examples of the crosslinking aid include thiazoles (eg, dibenzothiazyl disulfide, 2-mercaptobenzothiazole, etc.), thioureas (eg, diethylthiourea, trimethylthiourea, dibutylthiourea, etc.), dithiocarbamic acids (eg, dimethyldithiocarbamic acid). Sodium, sodium diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibenzyldithiocarbamate, etc.), guanidines (eg diphenylguanidine, di-o-tolylguanidine etc.), sulfenamides (eg benzothiazyl) -2-diethylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide, etc.), thiurams (for example, tetramethylthiura) Monosulfide, tetramethylthiuram disulfide, tetrabenzylthiuram disulfide, etc.), xanthates (eg, sodium isopropylxanthate, zinc isopropylxanthate), aldehyde ammonia (eg, acetaldehyde ammonia, hexamethylenetetramine, etc.), aldehyde amines (For example, n-butyraldehyde aniline, butyraldehyde monobutylamine, etc.) etc. are mentioned. Among these, thiazoles, thioureas, dithiocarbamic acids, and thiurams are preferable.

  Moreover, alcohols etc. are mentioned as a crosslinking adjuvant. Examples of alcohols include monohydric alcohols such as ethanol, dihydric alcohols such as ethylene glycol, trihydric alcohols such as glycerin, polyols such as polyethylene glycol and polypropylene glycol (polyoxyethylene glycol), and the like. It is done. As the alcohol, a polyol is preferable. In addition, the number average molecular weight of a polyol is 200 or more, for example, Preferably, it is 300 or more, for example, is 10,000 or less, Preferably, it is 5000 or less.

  These crosslinking aids can be used alone or in combination of two or more.

  When sulfur and a sulfur compound are used as the crosslinking agent, the crosslinking aid is preferably a thiazole, thiourea, dithiocarbamic acid from the viewpoint of ensuring a good foam shape and flexibility of the resin foam. Thiurams are used.

  When a quinoid compound is used as the crosslinking agent, from the viewpoint of corrosiveness, the crosslinking aid is preferably an alcohol, more preferably a polyol. In particular, when a derivative of p-quinonedioxime is used as the quinoid compound, polyethylene glycol is preferably used. If polyethylene glycol is used as the polyol, the rubber composition can be cross-linked satisfactorily and excellent foamability can be ensured.

  The blending ratio of the crosslinking aid is, for example, 0.01 parts by mass or more, preferably 0.02 parts by mass or more, more preferably 0.06 parts by mass or more with respect to 100 parts by mass of rubber. 20 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

  Further, the rubber composition can appropriately contain a lubricant (processing aid), a pigment, a filler, a flame retardant, a softening agent and the like as necessary.

  Examples of the lubricant include stearic acid and esters thereof, stearic compounds such as zinc stearate, and paraffin. These lubricants may be used alone or in combination of two or more. The blending ratio of the lubricant 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 rubber. It is.

  Examples of the pigment include carbon black. These pigments may be used alone or in combination of two or more. The blending 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 the rubber.

  Examples of the filler 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 may be used alone or in combination of two or more. The blending ratio of the filler is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and for example, 300 parts by mass or less, relative to 100 parts by mass of rubber. Preferably, it is 200 mass parts or less.

  Examples of the flame retardant include hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. These flame retardants may be used alone or in combination of two or more. The blending ratio of the flame retardant is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, for example, 200 parts by mass or less, preferably 100 parts by mass of rubber. 150 parts by mass or less, more preferably 100 parts by mass or less.

  Examples of the softener include petroleum oils (for example, paraffinic process oil (such as paraffin oil), naphthenic process oil, drying oils and animal and vegetable oils (such as linseed oil), aroma-based process oil, etc.) , Asphalts, 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, alkyls Sulfonic acid esters, etc.) and thickeners. Preferably, petroleum oils and asphalts are used, and paraffinic process oils are more preferable. These softeners may be used alone or in combination of two or more. The blending ratio of the softening agent is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and for example, 300 parts by mass or less, preferably 200 parts by mass or less with respect to 100 parts by mass of rubber. .

  Furthermore, the rubber composition can be used, for example, as a plasticizer, an antioxidant, an antioxidant, a colorant, an antifungal agent, in a range that does not affect the excellent effect of the obtained resin foam depending on its purpose and use. Known additives such as non-rubber polymers can be appropriately contained.

  The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer contains, for example, a polymer.

  Examples of the polymer include rubber-based polymers and non-rubber-based polymers.

  Examples of the rubber-based polymer include synthetic rubbers such as thermoplastic elastomers and thermosetting elastomers.

  For example, as the thermoplastic elastomer, olefin-based elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM), for example, styrene-butadiene rubber (SBR), styrene-butadiene-styrene rubber (SBS), Styrene-isoprene-styrene rubber (SIS), styrene-ethylene-butadiene rubber, styrene-ethylene-butylene-styrene rubber (SEBS), styrene-isobutylene-styrene block rubber (SIBS), styrene-isoprene-propylene-styrene rubber, etc. Styrenic elastomers such as butyl rubber, polyisobutylene rubber, polybutene, polyisoprene rubber, nitrile butadiene rubber (NBR), etc. butyl elastomers such as chloroprene Beam, such as a vinyl chloride elastomer, such as chlorosulfonated polyethylene rubber.

  Examples of the thermosetting elastomer include silicone rubber, fluorine rubber, acrylic rubber, and polyamide rubber.

  The rubber polymer is preferably a thermoplastic elastomer, more preferably a styrene elastomer or a butyl elastomer, and still more preferably polyisobutylene or SIBS.

  The weight average molecular weight is, for example, 30,000 or more, preferably 50,000 or more, more preferably 100,000 or more, and, for example, 5 million or less, preferably 3 million or less, more preferably 1 million or less. It is. Within this range, the pressure-sensitive adhesive layer can sufficiently exhibit adhesive strength. The weight average molecular weight is measured in terms of polystyrene using gel permeation chromatography.

  The non-rubber type is preferably an acrylic polymer. When the pressure-sensitive adhesive composition contains an acrylic polymer, the weather resistance is good.

  The acrylic polymer is a copolymer obtained by polymerization of a monomer containing a (meth) acrylic acid alkyl ester, and preferably a (meth) acrylic acid alkyl ester and a hydroxyl group-containing (meth) acrylic acid alkyl ester And a copolymer obtained by polymerization of a monomer containing.

  The (meth) acrylic acid alkyl ester is a methacrylic acid alkyl ester and / or an acrylic acid alkyl ester. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) Examples include hexyl acrylate, 2-ethylhexyl (meth) acrylate, and nonyl (meth) acrylate, and linear or branched (meth) acrylic acid alkyl esters having 1 to 10 carbon atoms are preferred, The alkyl moiety includes a linear or branched (meth) acrylic acid alkyl ester having 1 to 8 carbon atoms.

  The (meth) acrylic acid alkyl ester containing a hydroxyl group is a methacrylic acid alkyl ester and / or an acrylic acid alkyl ester containing a hydroxy group, for example, hydroxyethyl (meth) acrylate, hydroxy (meth) acrylate. Examples thereof include linear or branched hydroxyl group-containing (meth) acrylic acid alkyl esters having an alkyl moiety of 1 to 10 carbon atoms, such as butyl, and preferably an alkyl moiety having a linear or branched structure of 1 to 4 carbon atoms. Examples thereof include branched hydroxyl group-containing (meth) acrylic acid alkyl esters.

  The content ratio of the (meth) acrylic acid alkyl ester containing a hydroxyl group is, for example, 0.1 parts by mass or more, preferably 1 mass with respect to 100 parts by mass of the (meth) acrylic acid alkyl ester not containing a hydroxyl group. Part or more, for example, 10 parts by mass or less, preferably 5 parts by mass or less.

  The acrylic polymer can be obtained, for example, by publicly known radical polymerization of the above monomer.

  The weight average molecular weight of the acrylic polymer is, for example, 100,000 or more, preferably 200,000 or more, and for example, 2 million or less.

  The glass transition temperature of the acrylic polymer is, for example, 0 ° C. or lower and −50 ° C. or higher.

  When the pressure-sensitive adhesive composition contains a non-rubber polymer, it preferably contains a crosslinking agent.

  Examples of the crosslinking agent include isocyanate-based crosslinking agents such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, and polyhydric alcohol adducts thereof (trimethylolpropane adduct). It is done.

  As a content rate of a crosslinking agent, it is 0.1 mass part or more with respect to 100 mass parts of polymers, Preferably, it is 1 mass part or more, for example, 10 mass parts or less, Preferably, it is 5 mass parts. It is as follows.

  When the pressure-sensitive adhesive composition contains a crosslinking agent, it can also contain a crosslinking catalyst, if necessary.

  Examples of the crosslinking catalyst include known organometallic catalysts such as dibutyltin dilaurate and dioctyltin dilaurate.

  The content ratio of the crosslinking catalyst is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and, for example, 5 parts by mass or less, preferably 1 part with respect to 100 parts by mass of the polymer. It is below mass parts.

  The pressure-sensitive adhesive composition preferably contains a peeling aid.

  Examples of the peeling aid include oligomers.

  The number average molecular weight of the oligomer is, for example, 300 or more, preferably 500 or more, for example, 10,000 or less, preferably 7000 or less. When the molecular weight is within this range, the pressure-sensitive adhesive layer can have an appropriate adhesive strength, and is excellent in water-stopping, positioning, reworkability, low contamination, and the like. The number average molecular weight is measured in terms of polystyrene using gel permeation chromatography.

  Specific examples of such oligomers include compounds having polyoxyalkylene units, polyolefins, and acrylic oligomers.

  Examples of the compound having a polyoxyalkylene unit include polyoxypropylene glyceryl ether and polyoxyethylene polyoxypropylene block polymer. In addition, for example, compounds containing phosphorus such as polyoxyethylene stearyl ether phosphoric acid are also included.

  Examples of the polyolefin include polypropylene and polyethylene.

  The acrylic oligomer is a copolymer obtained by polymerization of a monomer containing a (meth) acrylic acid alkyl ester. Examples of the (meth) acrylic acid alkyl ester include the same acrylic polymer as described above.

  Preferably, a (meth) acrylic acid alkyl ester having two or more alkyl groups is used in combination as a monomer. More specifically, a combination of an alkyl alkyl acrylate ester having 2 to 6 carbon atoms (particularly 2 to 4 carbon atoms) and an acid alkyl ester having an alkyl moiety having 7 to 12 carbon atoms (particularly 7 to 8 carbon atoms). Is mentioned. When using them together, the content of the alkyl alkyl acrylate ester having 7 to 12 carbon atoms relative to 100 parts by mass of the alkyl alkyl acrylate ester having 2 to 6 carbon atoms is, for example, preferably 1 part by mass or more. Is 10 parts by mass or more, more preferably 100 parts by mass or more, and for example, 500 parts by mass or less, preferably 300 parts by mass or less.

  Moreover, as an oligomer, Preferably, the compound which has a polyoxyalkylene unit is mentioned. In particular, among compounds having a polyoxyalkylene unit, a compound containing phosphorus is preferable. Specific examples include polyoxyethylene stearyl ether phosphoric acid.

  By containing such a peeling aid, the adhesive strength can be in a good range, and the foamed laminate can be sufficiently temporarily attached to the member to be sealed, and also has good water-stopping properties. be able to.

  The content of the peeling aid is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the polymer. For example, it is 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 2 parts by mass or less.

  The pressure-sensitive adhesive layer may contain other additives as necessary within a range not impairing the effects of the present invention.

  Then, with reference to FIG. 1, the manufacturing method of the foaming laminated body 1 is demonstrated.

  The production method of the foam laminate 1 includes, for example, a foam layer preparation step for preparing (manufacturing) the foam layer (resin foam) 2, an undercoat step for forming the undercoat layer 3 on one surface of the foam layer 2, and a release substrate 5. An adhesive layer laminated substrate 6 formed by laminating an adhesive layer 4 and a foaming layer 2 on which an undercoat layer 3 is disposed, and an adhesive layer laminated substrate 6 (adhesive layer 4 side). ) And the foamed layer 2 (undercoat layer 3 side), and a peeling step of peeling the release substrate 5 from the foamed laminate 1.

  In the foam layer preparation step, a known or commercially available foam is prepared. Or the foaming layer which is a rubber-type foam can also be prepared by making a rubber composition foam.

  When preparing a foamed layer made of a rubber-based foam, the components of the rubber composition described above are blended and kneaded using a kneader, a mixer, a mixing roll, or the like, whereby the rubber composition is used as an admixture. Prepare (preparation step).

  In the preparation step, kneading can be performed while appropriately heating. In the preparation step, for example, components other than the cross-linking agent, the cross-linking aid, the foaming agent and the foaming aid are first kneaded to prepare the primary mixture, and then the cross-linking agent and the cross-linking aid are added to the primary mixture. A rubber composition (secondary mixture) can also be prepared by adding an agent, a foaming agent and a foaming aid and kneading. Moreover, when preparing a primary blend, a part of crosslinking adjuvant can also be mix | blended.

  Then, the prepared rubber composition (mixture) is extruded into a sheet or the like using an extruder (molding process), and the extruded rubber composition is heated and foamed (foaming process). .

  The foaming composition is appropriately selected depending on 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 circulation oven, for example, 40 to 200 ° C. After preheating at 60 to 160 ° C., for example, for 1 to 60 minutes, preferably 5 to 40 minutes, for example, 450 ° C. or less, preferably 100 to 350 ° C., more preferably 120 to 250 It is heated at, for example, 5 to 80 minutes, preferably 15 to 50 minutes.

  According to such a method for producing a resin foam (rubber-based foam), a resin foam that can suppress the corrosion of the member and can seal the member with good adhesion and step following ability is easily and efficiently produced. be able to.

  Moreover, the prepared rubber composition can be extruded into a sheet shape (molding step) while being heated using an extruder, and the rubber composition can be continuously crosslinked and foamed (foaming step).

  Thereby, a rubber composition is bridge | crosslinked while foaming, and the foaming layer (rubber-type foam) 2 can be obtained (FIG. 1A).

  The thickness of the foamed layer 2 is, for example, 0.1 mm or more, preferably 1 mm or more, more preferably 5 mm or more, and for example, 50 mm or less, preferably 45 mm or less, more preferably 30 mm or less. .

  The foamed layer 2 has an open cell structure (open cell ratio 100%) or a semi-continuous semi-closed cell structure (open cell ratio 0% exceeding 100%, preferably open cell ratio 50 to 95%). If the foamed layer 2 is an open-cell structure or a semi-continuous semi-closed cell structure, the flexibility can be improved, and consequently the sealing property of the resin foam between the members can be improved.

  The cell diameter of the foamed layer 2 is, for example, 50 μm or more, preferably 100 μm or more, more preferably 200 μm or more, for example, 1200 μm or less, preferably 1000 μm or less, more preferably 800 μm or less.

  The volume expansion ratio (density ratio before and after foaming) of the foam layer 2 is, for example, 2 times or more, preferably 5 times or more, and usually 30 times or less.

  Next, as shown in FIG. 1B, an undercoat layer 3 is formed on one surface (upper surface) of the foam layer 2 (undercoat step).

  The undercoat layer 3 is formed, for example, by applying and drying the undercoat liquid on the surface of the foamed layer 2 by a known method such as an applicator.

  The undercoat liquid may be, for example, a solvent-based undercoat liquid obtained by dissolving or dispersing rubber in a solvent, or may be a solventless undercoat liquid obtained by softening rubber to form a liquid.

  Such rubber includes natural rubber and synthetic rubber. Examples of the synthetic rubber include the same ones as described above.

  Preferred examples include polyisobutylene, polybutene, polyisoprene, and the like, and more preferred is a combined use of polyisobutylene and polybutene.

  When polyisobutylene and polybutene are used in combination, the content of polybutene is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, and, for example, 200 parts by mass with respect to 100 parts by mass of polyisobutylene. Hereinafter, it is preferably 150 parts by mass or less.

  The rubber used in the undercoat liquid is preferably a rubber having a weight average molecular weight of, for example, 10,000 or more, preferably 20,000 or more, and, for example, 200,000 or less, preferably 100,000 or less. It is done. Alternatively, a rubber having a number average molecular weight of, for example, 500 or more, preferably 1000 or more, and 5000 or less, preferably 3000 or less is mentioned. In particular, when a rubber having an average molecular weight in the above range is used in combination, the foam layer 2 and the pressure-sensitive adhesive layer 4 can be more reliably fixed.

  Examples of the solvent include water, for example, ketones such as acetone and methyl ethyl ketone (MEK), aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, esters such as ethyl acetate, and N, N-dimethylformamide. And amides.

  The undercoat liquid can also contain other known additives.

  The solid content in the solvent-based undercoat liquid is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

  A drying temperature is 60 degreeC or more, for example, Preferably, it is 70 degreeC or more, for example, is 150 degrees C or less, Preferably, it is 120 degrees C or less.

  The drying time is, for example, 10 seconds or more, preferably 30 seconds or more, and for example, 30 minutes or less, preferably 10 minutes or less.

  The thickness of the undercoat layer 3 thus obtained is, for example, 3 μm or more, preferably 5 μm or more, and for example, 100 μm or less, preferably 50 μm or less.

  Next, as shown in FIG. 1C, the pressure-sensitive adhesive layer laminated substrate 6 and the foamed layer 2 are disposed to face each other (arrangement step). Then, as shown to FIG. 1D, the adhesive layer laminated base material 6 is laminated | stacked on the foaming layer 2 (lamination process).

  In this arrangement step, first, an adhesive layer laminated substrate 6 in which the adhesive layer 4 is laminated on one surface of the release substrate 5 is prepared.

  The pressure-sensitive adhesive layer laminated substrate 6 is obtained by applying and drying a pressure-sensitive adhesive solution containing a pressure-sensitive adhesive composition and a solvent on one surface of the release substrate 5 by a known method such as an applicator.

  Examples of the solvent include the same solvents as those described above for the undercoat liquid.

  The solid content in the pressure-sensitive adhesive solution is, for example, 3% by mass or more, preferably 5% by mass or more, for example, 95% by mass or less, preferably 90% by mass or less.

  Examples of the release substrate 5 include a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, and paper. These are subjected to mold release treatment on the surface with, for example, a fluorine release agent, a long-chain alkyl acrylate release agent, a silicone release agent, or the like.

  A drying temperature is 60 degreeC or more, for example, Preferably, it is 70 degreeC or more, for example, is 150 degrees C or less, Preferably, it is 120 degrees C or less. The same temperature is obtained when the pressure-sensitive adhesive composition contains a non-rubber polymer and a crosslinking agent.

  The drying time is, for example, 10 seconds or more, preferably 30 seconds or more, and for example, 30 minutes or less, preferably 10 minutes or less.

  The thickness of the pressure-sensitive adhesive layer 4 thus obtained is, for example, 1 μm or more, preferably 5 μm or more, more preferably 10 or more μm, and for example, 100 μm or less, preferably 50 μm or less, more preferably Is 30 μm or less.

Moreover, the shear storage elastic modulus in 25 degreeC of the adhesive layer 4 is 1.5 * 10 < ⁵ > Pa or more, Preferably, it is 2.0 * 10 < ⁵ > Pa or more, More preferably, it is 2.5 * 10 < ⁵ > Pa. That's it. Moreover, it is 7.0 * 10 < ⁵ > Pa or less, Preferably, it is 6.0 * 10 < ⁵ > Pa or less, More preferably, it is 5.0 * 10 < ⁵ > Pa or less.

  When the shear storage modulus is within the above range, the water-stop property of the foamed laminate is good. In addition, temporary fixing to the member is possible, and workability is excellent.

  Details of the method for measuring the shear storage modulus will be described later in Examples.

  Then, the pressure-sensitive adhesive layer laminated substrate 6 and the foamed layer 2 are arranged so that the pressure-sensitive adhesive layer 4 and the undercoat layer 3 face each other with an interval (FIG. 1C).

  Next, as shown in FIG. 1D, the pressure-sensitive adhesive layer laminated substrate 6 is laminated on the foam layer 2 (lamination step). Specifically, the pressure-sensitive adhesive layer 4 and the undercoat layer 3 are brought into contact with each other.

  At this time, the pressure-sensitive adhesive layer laminated substrate 6 and / or the foamed layer 2 are pressed and heated as necessary.

  Thereby, the laminated body by which the undercoat layer 3, the adhesive layer 4, and the peeling base material 5 were laminated | stacked in order on the foaming layer 2 is obtained.

  Subsequently, the peeling base material 5 is peeled from the foaming laminated body 1 (peeling process). That is, the peeling base material 5 is peeled off from the surface of the pressure-sensitive adhesive layer 4 as indicated by arrows and phantom lines in FIG. 1D.

  Thereby, as shown to FIG. 1E, the foaming laminated body 1 by which the undercoat layer 3 and the adhesive layer 4 were laminated | stacked in order on the foaming layer 2 is obtained.

  The total thickness of the foamed laminate 1 thus obtained is, for example, 1 mm or more, preferably 3 mm or more, and for example, 50 mm or less, preferably 30 mm or less.

The apparent density (according to JIS K 6767 (1999)) of the foamed laminate 1 is, for example, 0.50 g / cm ³ or less, preferably 0.2 g / cm ³ or less, usually 0.01 g / cm ³ or more. It is. According to such a foam laminate 1, excellent foamability can be ensured, and the member can be satisfactorily sealed.

  Moreover, when not using sulfur and a sulfur compound as a crosslinking agent, the content rate of the sulfur atom in the foaming laminated body 1 is 1000 ppm or less on a mass basis, Preferably, it is 800 ppm or less, More preferably, it is 500 ppm or less. When the sulfur atom content ratio is within the above range, corrosion to the member to be sealed can be reliably reduced by the sulfur contained in the foam laminate 1. The sulfur atom content is calculated based on the measurement result of fluorescent X-ray measurement using an XRF apparatus (ZXS100e manufactured by Rigaku).

Content of the foam laminate 1 in the sulfur _{S 8,} for example, 100 ppm or less, preferably 50 ppm or less, more preferably 10ppm or less. The content ratio of sulfur S ₈ can be measured by gel permeation gas chromatography (GPC).

10% compressive load value of the foam laminate 1 (JIS K equivalent to 6767 (1999).), For example, 0.1 N / cm ² or more, preferably, 0.15 N / cm ² or more, more preferably, 0. and a 2N / cm ² or more, and is, for example, 2.0 N / cm ² or less, preferably, 1.5 N / cm ² or less, more preferably 1.0 N / cm ² or less.

The 50% compression load value (according to JIS K 6767 (1999)) of the foamed laminate 1 is, for example, 0.05 N / cm ² or more, preferably 0.1 N / cm ² or more, more preferably 0.00. and at 15N / cm ² or more, and is, for example, 2.0 N / cm ² or less, preferably, 1.5 N / cm ² or less, more preferably 1.0 N / cm ² or less.

The tensile strength of the foamed laminate 1 (maximum load in a tensile test according to JIS K 6767 (1999)) is, for example, 1.0 N / cm ² or more and 2.0 N / cm ² or more. 0 N / cm ² or less, preferably 30.0 N / cm ² or less.

  Further, the elongation percentage (according to JIS K 6767 (1999)) of the foam laminate 1 is, for example, 10% or more, preferably 150% or more, and, for example, 1500% or less, preferably 1000%. It is as follows.

  The adhesive strength with respect to the acrylic plate on the pressure-sensitive adhesive layer 4 side is, for example, 0.05 N / 25 mm or more, preferably 0.4 N in the initial stage (that is, when contacting the adherend for the first time after the foamed laminate 1 is manufactured). / 25 mm or more, more preferably 1 N / 25 mm or more, more preferably 3.0 N / 25 mm or more, and for example, 4.0 N / 25 mm or less and 3.5 N / 25 mm or less. In addition, the measuring method of adhesive force is mentioned later in an Example. When the adhesive strength is less than the above lower limit, the foam laminate becomes slippery with respect to the member, cannot be temporarily fixed, and is inferior in workability. On the other hand, if the adhesive strength exceeds the above upper limit, the adhesive strength becomes too strong, and when the foam laminate is peeled off from the member after temporarily fixing, a part of the foam laminate (adhesive layer) is formed on the surface of the member. The problem of remaining is caused.

  The foamed laminate 1 can prevent water leakage by compression of, for example, 50% or less, preferably 30% or less, more preferably 10% or less in the U-shaped water-stop test (initial stage). In the U-shaped water-stopping test (re-adhesion after peeling), for example, water leakage can be prevented by compression of 50% or less, preferably 30% or less, more preferably 10% or less. The measuring method of the U-shaped water-stopping test will be described later in Examples.

And this foaming laminated body 1 is equipped with the foaming layer 2 formed from a resin foam, and the adhesive layer 4 laminated | stacked on the at least one surface of the foaming layer 2, The shear storage in 25 degreeC of the adhesive layer 4 The elastic modulus is 1.5 × 10 ⁵ Pa or more, and the adhesive force of the adhesive layer 4 to the acrylic plate is 0.05 N / 25 mm or more and 4.0 N / 25 mm or less.

  Therefore, when the foaming laminated body 1 is arrange | positioned between the members to be sealed and the space between the members is sealed, the water-stopping property is good.

  Further, since the pressure-sensitive adhesive layer 4 has an appropriate tack force (fine tack), the foamed laminate 1 can be temporarily fixed to a member to be sealed. As a result, workability is excellent.

  Further, when the pressure-sensitive adhesive layer 4 contains an oligomer, and when the oligomer is a specific oligomer, the water-stopping property and workability are further improved.

  Moreover, when the adhesive layer 4 contains a polymer and a crosslinking agent, the water-stopping property is further improved.

  Moreover, when a resin foam contains a polyolefin foam, a urethane foam, or a rubber-type foam, water-stop is still more excellent.

  Further, when the rubber-based foam is ethylene / propylene / diene rubber, even when the foamed laminate 1 is compressed at a lower compression ratio and the members are sealed, the water-stopping property can be surely exhibited. . In other words, since the members can be sealed with a lower compressive load, the load applied to the members (and hence the deformation of the members) can be reduced.

Moreover, when the 10% compressive load of the foam laminate 1 is 0.1 N / cm ² or more and 2.0 N / cm ² or less, the foam laminate can be laminated on the member at a lower pressure. Such a load can be reliably reduced.

The foamed laminate 1 is not particularly limited, and seals gaps of various members for the purposes of vibration suppression, sound absorption, sound insulation, dust prevention, heat insulation, loosening, water tightness, etc., for example, vibration insulation, sound absorption material, sound insulation It can be used as a material, a dustproof material, a heat insulating material, a buffer material, a waterstop material, and the like. More specifically, a gap between a car casing and a part (for example, a taillight), an electric / electric equipment casing and a part (for example,
It can be used for a gap with an engine control unit (ECU) or the like.

  In the embodiment of FIG. 1, the undercoat layer 3 is laminated on one surface of the foam layer 3, and the adhesive layer 4 is laminated on the surface of the undercoat layer 3. The pressure-sensitive adhesive layer can be directly laminated on the foam layer without laminating the undercoat layer 3.

  From the viewpoint of surely laminating the foam layer 2 on the pressure-sensitive adhesive layer 4, the undercoat layer 3 is preferably provided on the foam layer 2.

  Further, in the embodiment of FIG. 1, as shown in FIG. 1E, the peeling substrate 5 is peeled from the pressure-sensitive adhesive layer 4, but if necessary, the peeling substrate 5 is laminated until actually used. You can also keep it.

  Further, in the embodiment of FIG. 1, the pressure-sensitive adhesive layer 4 is formed only on one surface of the foam layer 2, but for example, the pressure-sensitive adhesive layer 4 can be formed on one surface and the other surface of the foam layer 2. . Alternatively, the pressure-sensitive adhesive layer 4 can be formed on one surface of the foam layer 2, and a commercially available or known double-sided adhesive tape can be formed on the other surface of the foam layer 2.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to an Example and a comparative example at all. Moreover, the numerical value of the Example shown below can be substituted for the numerical value (namely, upper limit or lower limit value) described in said embodiment.

(Production Example 1)
In the compounding prescription shown in Table 1, each component was compounded and kneaded with a 3 L pressure kneader and a 10 inch mixing roll to prepare a rubber composition.

  Next, the rubber composition was extruded into a sheet having a thickness of about 8 mm using a single screw extruder (45 mmφ) to produce a rubber composition sheet.

  The rubber composition sheet was preheated at 140 ° C. for 20 minutes in a hot air circulating oven. Thereafter, the temperature was raised to 170 ° C. in a hot-air circulation oven over 10 minutes, and the rubber composition sheet was heated at 170 ° C. for 10 minutes to be foamed to obtain a foamed layer (EPDM foam). The thickness was 30 mm.

(Production Example 2)
An EPDM foam was obtained in the same manner as in Production Example 1, except that the formulation shown in Table 1 was changed. The thickness was 30 mm.

(Production Example 3)
20 parts by mass of polyisobutylene (“Opanol B50”, manufactured by BASF, weight average molecular weight 500,000) and 20 parts by mass of polybutene (“300H”, manufactured by Idemitsu Kosan Co., Ltd., number average molecular weight 1330) are blended in 60 parts by mass of toluene. Thus, an undercoat liquid was prepared.

  The prepared undercoat liquid was applied to one side of the EPDM obtained in Production Example 1 with an applicator, and the undercoat liquid was dried at 80 ° C. for 3 minutes, and an undercoat layer (thickness 15 μm) was formed on one side of the EPDM foam. ) Was formed.

(Production Example 4)
An undercoat layer (thickness: 15 μm) was formed on one surface of the EPDM foam in the same manner as in Production Example 3, except that the EPDM foam of Production Example 2 was used instead of the EPDM foam of Production Example 1.

(Preparation Example 1)
In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 50 parts by weight of 2-ethylhexyl acrylate, 50 parts by weight of ethyl acrylate, 5 parts by weight of methyl methacrylate, 4 parts by weight of hydroxyethyl acrylate Then, 0.2 parts by weight of dibenzoyl peroxide (manufactured by NOF Corporation, Niper BW) as a polymerization initiator and toluene were charged, and nitrogen gas was introduced while gently stirring, followed by substitution with nitrogen, and then the liquid temperature in the flask was adjusted. The polymerization reaction was carried out for 10 hours while maintaining the temperature at around 60 ° C. to prepare an acrylic polymer solution (solid content 50% by weight). This acrylic polymer had a weight average molecular weight of 300,000 and Tg of −43 ° C.

Example 1
In the compounding quantity as described in the compounding prescription shown in Table 1, each component was mix | blended and the adhesive composition was prepared.

  10 parts by weight of the prepared pressure-sensitive adhesive composition and 90 parts by weight of toluene were mixed to prepare a pressure-sensitive adhesive solution.

  This pressure-sensitive adhesive solution is applied to the surface of a release substrate (“MRF # 38”, manufactured by Mitsubishi Plastics) with an applicator and heated at 80 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 15 μm. Thus, a pressure-sensitive adhesive layer-forming substrate was produced.

  The pressure-sensitive adhesive layer side of the obtained pressure-sensitive adhesive layer-forming substrate was brought into contact with the surface of the EPDM foam undercoat layer obtained in Example 3, and then the release substrate was peeled from the pressure-sensitive adhesive layer. Thereby, the foaming laminated body of Example 1 was manufactured.

(Examples 2 to 10)
Except having changed the compounding prescription of an adhesive layer into the compounding prescription shown in Table 2, it carried out similarly to Example 1, and manufactured the foaming layered product of each example.

(Examples 11 to 18)
The foamed laminate of each example was manufactured in the same manner as in Example 1 except that the formulation of the pressure-sensitive adhesive layer was changed to the formulation shown in Table 3 and the EPDM foam of Production Example 2 was used.

(Comparative Example 1)
The EPDM foam of Production Example 1 was used as the foam laminate of Comparative Example 1.

(Comparative Examples 2 to 4)
Except having changed the compounding prescription of an adhesive layer into the compounding prescription shown in Table 2, it carried out similarly to Example 1, and manufactured the foaming layered product of each comparative example.

(Comparative Example 5)
The EPDM foam of Production Example 2 was used as the foam laminate of Comparative Example 5.

(Comparative Example 6)
The foamed laminate of Comparative Example 6 was produced in the same manner as in Example 1 except that the formulation of the adhesive layer was changed to the formulation shown in Table 3 and the EPDM foam of Production Example 2 was used.
(2) Physical property measurement About the foaming laminated body obtained by each Example and each comparative example, a part of surface of the foaming layer was shaved and the total thickness of the foaming laminated body was 10 mm. Each physical property of the foamed laminate (10 mm) was measured by the following method. The results are shown in Table 2 and Table 3.

A) Apparent density Measured according to JIS K 6767 (1999). Specifically, the weight of the foam laminate (10 mm) was measured, and the weight per unit volume (apparent density) was calculated.

B) 10% compressive load value Measured according to JIS K 6767 (1999). Specifically, a compression load value 10 seconds after the foamed laminate (10 mm) was compressed 10% at a compression speed of 10 mm / min was measured using a compression tester.

C) 50% compressive load value Measured according to JIS K 6767 (1999). Specifically, the compression load value was measured 10 seconds after the foamed laminate (10 mm) was compressed 50% at a compression rate of 10 mm / min using a compression tester.

D) Tensile strength and elongation The measurement was performed according to JIS K 6767 (1999). Specifically, a dumbbell No. 1 was used to punch out a foam laminate (10 mm) to obtain a measurement sample. Using a tensile tester, the measurement sample was pulled at a pulling speed of 500 mm / min, and the load (tensile strength) and elongation rate when the measurement sample was cut at the dumbbell-shaped parallel portion were measured.

E) Sulfur atom content (fluorescence X-ray measurement)
The foamed laminate was cut into an appropriate size, and four sheets were stacked to perform fluorescent X-ray measurement (XRF) (measurement diameter: 30 mmφ). The XRF equipment and conditions are described below.

XRF equipment: Rigaku ZXS100e
X-ray source: Vertical Rh tube Analysis area: 30mmφ
Analytical element range: B to U
Further, the quantification was calculated based on the ratio of sulfur element in all the detected elements.

F) Sulfur S ₈ content (GPC measurement)
Based on the measurement result of gel permeation chromatography (GPC), sulfur S ₈
The content ratio of was calculated. Procedures, conditions and equipment are described below.

(Procedure 1)
The foamed laminate was cut into small pieces, and a sample having an average maximum length of 5 mm was produced. Next, 300 mg of EPDM foam was weighed, and then 10 ml of THF (tetrahydrofuran) was added using a whole pipette and allowed to stand overnight.

  The THF solution was filtered through a 0.45 μm membrane filter, and the filtrate was measured by gel permeation chromatography.

(Procedure 2)
Separately, sulfur _{S 8} was dissolved in THF, and adjusted to a concentration 1000 [mu] g / ml, was allowed to stand overnight in THF. Thereafter, the THF solution was filtered through a 0.45 μm membrane filter.

  The filtrate was diluted to a predetermined concentration to prepare a standard solution, this standard solution was subjected to gel permeation chromatography measurement, and a calibration curve was created from the obtained peak area value.

(Procedure 3)
The calibration curve method based on the calibration curve prepared by the procedure 2, seeking mass of sulfur S ₈ in the sample in step 1, by dividing by the mass of the sample (300 mg) to this, the content ratio of sulfur S ₈ in a sample Was calculated.

<Measurement equipment and measurement conditions>
GPC equipment: TOSOH HLC-8120GPC
Column: TSKgel Super HZ2000 / HZ2000 / HZ1000 / HZ1000
Column size: 6.0 mm I.D. D. × 150mm
Eluent: THF
Flow rate: 0.6ml / min
Detector: UV (280 nm)
Column temperature: 40 ° C
Injection volume: 20 μl
Detection limit: 10ppm
G) Adhesive strength with respect to acrylic plate A foam laminate (10 mm) was cut into a width of 25 mm and a length of 150 mm to obtain a sample for evaluation.

  In an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH, the pressure-sensitive adhesive layer surface of the sample for evaluation was attached to an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite L) by one reciprocation of a 2 kg roller. After curing at 23 ° C. for 30 minutes, the adhesive strength was measured using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) at a peeling angle of 180 degrees and a pulling speed of 10 m / min.

G) Shear storage elastic modulus The shear storage elastic modulus G ′ in the pressure-sensitive adhesive layer of the foam laminate (10 mm) was measured using a dynamic viscoelasticity measuring device (“ARES”, manufactured by TA Instruments) under the following measurement conditions. Based on.

Mode: Torsion mode Measurement temperature range: -70 ° C to 150 ° C
Temperature increase rate: 5 ° C / min
Measurement frequency: 1Hz
I) Temporary fastening test The foam laminate (10 mm) was brought into contact with a member (acrylic plate: manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite L), and the foam laminate was pressed at 0.02 MPa, and then the member was 90 °. A temporary fixing test was performed by tilting.

  At this time, the case where the foam laminate did not fall off from the member and could be easily peeled was evaluated as ◯, the case where the foam laminate fell off from the member was evaluated as A, and the foam laminate was displaced from the member. Although it did not fall, it evaluated as B when a part of foaming laminated body remained at the time of peeling.

J) Water-stop test (initial)
Test by pasting a double-sided tape (acrylic double-sided tape, manufactured by Nitto Denko Corporation) on the foamed layer side of the foamed laminate (10 mm), and then punching it into a U-shape (foamed laminate width 10 mm, total length 300 mm) A piece was made. Next, the test piece was sandwiched between the acrylic plate and the stainless steel plate from the thickness direction of the test piece so that the open end of the test piece (the open end in the U-shape) was directed upward. At this time, it was sandwiched so that the pressure-sensitive adhesive layer was in contact with the acrylic plate and the double-sided tape was in contact with the stainless steel plate. Next, the acrylic plate and the stainless steel plate were pressed in the thickness direction of the test piece so that the test piece was compressed by 10% in thickness.

  Then, with the test piece compressed to 10%, water is poured into the U-shaped inside of the test piece so that the water level from the inner lower end of the test piece is 100 mm, and whether there is water leakage after 24 hours. confirmed. And the case where water leak was not able to be confirmed was evaluated as "with water stop (10%)", and the case where water leak was confirmed was evaluated as "without water stop (10%)".

  Subsequently, when it was evaluated as “no water-stop”, the compression ratio (%) was increased stepwise, and at the compression ratio at that stage, the presence or absence of water leakage was confirmed by the same confirmation method as described above.

  The measurement was continued up to the compression ratio at the stage where “water-stopping” was evaluated. Tables 2 and 3 show the compression ratio at that stage.

  In Tables 1 to 3, numbers indicate parts by mass unless otherwise specified.

Details such as abbreviations shown in Tables 1 to 3 are described below.
EPDM (A): EPT3045 (Mitsui Chemicals, diene 5-ethylidene-2-norbornene) content 4.7 mass%)
EPDM (B): EP-24 (manufactured by JSR, diene 5-ethylidene-2-norbornene) content 4.5% by mass)
EPDM (C): EPT8030M (manufactured by Mitsui Chemicals, long chain branching content, diene (5-ethylidene-2-norbornene) content 9.5% by mass)
ADCA: Azodicarbonamide AC # LQ, foaming agent, urea-based compound made by Eiwa Kasei Kogyo Co., Ltd .: Cell paste K5, foaming aid, made by Eiwa Kasei Kogyo Co., Ltd. Zinc oxide: 2 types of zinc oxide, foaming aid, Mitsui Metal Mining Sulfur manufactured: Alphagran S-50EN, cross-linking agent, Tochi Co., Ltd. p, p'-dibenzoylquinone dioxime: Barnock DGM, cross-linking agent, Ouchi Shinsei Chemical Co., Ltd. α, α'-di (t-butyl Peroxy) diisopropylbenzene: perbutyl P-40MB, 1 minute half-life temperature: 175 ° C, cross-linking agent, polyethylene glycol manufactured by NOF Corporation: PEG 4000S, number average molecular weight 3400, cross-linking aid, 2-mercaptobenzo manufactured by Sanyo Chemical Industries Thiazole: Noxeller M, crosslinking aid, manufactured by Ouchi Shinsei Chemical Co., Ltd. N, N'-dibutylthiourea: Noxeller BUR, crosslinking aid, Ouchi emerging chemical Zinc Dibenzyldithiocarbamate: Noxeller ZTC, crosslinking aid, Tetrabenzylthiuram disulfide: Noxeller TBzTD, crosslinking aid manufactured by Ouchi Shinsei Chemical Co., Ltd. Stearic acid: Powdered stearic acid sakura, lubricant, NOF Corporation Paraffin: Parapere 130, Lubricant, Taniguchi Oil Co., Ltd.
Carbon black: Asahi # 50, pigment, Asahi Carbon Co. calcium carbonate: N heavy calcium carbonate, filler, Maruo Calcium Magnesium hydroxide: Kisuma 5A, flame retardant, Kyowa Chemical Industries aluminum hydroxide: Hydrite H-32, Flame Retardant, Showa Denko Asphalt: Trumble Base Asfalt, Owens Corning Paraffin Oil (A): Diana Process Oil PW-90, Idemitsu Kosan Paraffin Oil (B): Diana Process Oil PW- 380, Idemitsu Kosan Co., Ltd. acrylic polymer: The acrylic polymer prepared in Preparation Example 1 (in terms of solid content) was used.
Polyisobutylene: PIB-B150, manufactured by BASF, weight average molecular weight 2 million styrene-isobutylene-styrene block copolymer: SIBS 102T, manufactured by Kaneka Corporation, weight average molecular weight 100,000 phosphorus-containing oligomer: Phosphanol RL-210, poly Oxyethylene stearyl ether phosphoric acid, acrylic oligomer manufactured by Toho Chemical Industries: Modaflow, copolymer of ethyl acrylate (30 parts by mass) and 2-ethylhexyl acrylate (70 parts by mass), number average molecular weight 6300, manufactured by Monsanto Polypropylene (Mn400): Sannix PP-400, number average molecular weight 400, manufactured by Sanyo Chemical Industries,
Polypropylene (Mn1000): Sannix PP-1000, number average molecular weight 1000, polyoxypropylene glyceryl ether manufactured by Sanyo Chemical Industries, Ltd .: Sannix PP-3000, number average molecular weight 3000, polyoxyethylene polyoxypropylene block manufactured by Sanyo Chemical Industries Polymer: New Pole PE64, number average molecular weight 3000, dioctyltin dilaurate manufactured by Sanyo Chemical Industries, Ltd .: cross-linking catalyst, tolylene diisocyanate TMP manufactured by Tokyo Fine Chemical Co., Ltd .: Tolylene diisocyanate trimethylolpropane addition product, cross-linking agent, manufactured by Nippon Polyurethane

1 Foam laminate 2 Foam layer 4 Adhesive layer

Claims (10)

A foam layer formed from a resin foam;
An adhesive layer laminated on at least one surface of the foam layer,
The adhesive layer has a shear storage modulus at 25 ° C. of 1.5 × 10 ⁵ Pa or more,
The foamed laminate is characterized in that the adhesive strength of the adhesive layer to the acrylic plate is 0.05 N / 25 mm or more and 4.0 N / 25 mm or less.   The foamed laminate according to claim 1, wherein the pressure-sensitive adhesive layer contains an oligomer.   The number average molecular weight of the said oligomer is 500-10000, The foaming laminated body of Claim 2 characterized by the above-mentioned.   The foamed laminate according to claim 2 or 3, wherein the oligomer is a compound having a polyoxyalkylene unit.   5. The foamed laminate according to claim 2, wherein a content ratio of the oligomer is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the pressure-sensitive adhesive layer. .   The foamed laminate according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer contains a polymer.   The foamed laminate according to claim 6, wherein the pressure-sensitive adhesive composition contains a crosslinking agent.   The foamed laminate according to any one of claims 1 to 7, wherein the resin foam contains a polyolefin foam, a urethane foam, or a rubber foam.   The foam laminate according to claim 8, wherein the rubber-based foam contains ethylene / propylene / diene rubber. The foamed laminate according to any one of claims 1 to 9, wherein a 10% compressive load is 0.1 N / cm ² or more and 2.0 N / cm ² or less.

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