Fire-resistant material with double-sided tape

Abstract

To provide a fire-resistant member that is less prone to deterioration of cohesive strength in laminated adhesive layers over time.SOLUTION: A fire-resistant member with a double-sided tape comprises a matrix polymer component, an inorganic compound, a softener, a fire-resistant layer containing a thermally expandable compound, and a double-sided tape, having adhesive layers on both sides of a support, disposed on one or both surfaces of the fire-resistant layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a fire-resistant member with double-sided tape. [Background technology]

[0002] As fire-resistant members having fire resistance and an adhesive layer, Patent Documents 1 and 2 are known which use a liquid additive-resistant adhesive layer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 034002 [Patent Document 2] Patent Publication No. 2017-145682 Summary of the Invention [Problem to be solved by the invention]

[0004] The adhesive layer described in the above patent document suppresses component migration to some extent by using a specific formulation. However, because the adhesive layer is laminated directly onto the fire-resistant material, the migration of low molecular weight substances from the fire-resistant material to the adhesive layer is not sufficiently suppressed, and there is an issue of a decrease in the cohesive strength of the laminated adhesive layer over time. Furthermore, when a base layer is provided, there is a problem that the fireproof material may be deteriorated by the solvent used when applying the base layer and the heat generated during drying.

[0005] An object of the present invention is to provide a fire-resistant member in which the cohesive strength of the laminated pressure-sensitive adhesive layer decreases little over time. [Means for solving the problem]

[0006] The present inventors have found that the above object can be achieved by providing a laminate including a layer of an adhesive and a layer of a fire-resistant material with a specific structure, and have thus completed the present invention.

[0007] That is, according to the present invention, the following inventions are provided. [1] A fire-resistant layer containing a matrix polymer component, an inorganic compound, a softener, and a thermally expandable compound; a double-sided tape having pressure-sensitive adhesive layers on both sides of a support, the double-sided tape being provided on one or both sides of the fire-resistant layer; A fire-resistant member with double-sided tape. [2] The fire-resistant member with double-sided tape according to [1], wherein the fire-resistant layer contains 20 to 600 parts by mass of the inorganic compound, 10 to 200 parts by mass of the softener, and 5 to 400 parts by mass of the thermally expandable compound, relative to 100 parts by mass of the matrix polymer component. [3] The fire-resistant member with double-sided tape according to [1] or [2], wherein the inorganic compound contains aluminum hydrogen phosphite. [4] The fire-resistant member with double-sided tape according to any one of [1] to [3], wherein the thermally expandable compound contains thermally expandable graphite. [5] The fire-resistant member with double-sided tape according to any one of [1] to [3], wherein the pressure-sensitive adhesive layer is a cross-linked acrylic pressure-sensitive adhesive. [6] The fire-resistant member with double-sided tape according to any one of [1] to [4], which is a sheet or a molded body. [7] A fire-resistant member with double-sided tape according to any one of [1] to [5], which is used for fire-resistant covering of building materials or steel frames. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a refractory member that exhibits little decrease in cohesive strength over time. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram showing an example of a fire-resistant member in which a double-sided tape is provided on one side of a fire-resistant layer. FIG. [Figure 2] 1 is a schematic diagram showing an example of a fire-resistant member in which double-sided tape is provided on both sides of a fire-resistant layer. FIG. [Figure 3] FIG. 10 is a diagram illustrating a method for producing a joint for a flexibility test. [Figure 4]FIG. 10 is a diagram illustrating the bending direction and angle θ of the joint for flexibility test. DETAILED DESCRIPTION OF THE INVENTION

[0010] Below, we will explain in detail the embodiment of the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0011] <Fire-resistant material with double-sided tape> The fireproof member of this embodiment is a fireproof member with double-sided tape having a fireproof layer (fireproof material) and double-sided tape (double-sided tape layer). As shown in FIG. 1, in a fireproof member with double-sided tape 1, the double-sided tape 5 may be provided on one side of the fireproof layer 3. The double-sided tape 5 is a double-sided tape having adhesive layers 7 (7a, 7b) on both sides of a support 9, which is a substrate. Also, as shown in FIG. 2, in a fireproof member with double-sided tape 10, the double-sided tape 15 (15a, 15b) is provided on both sides of the fireproof layer 13. The double-sided tape 15 (15a, 15b) is a double-sided tape having adhesive layers 17 (17aa, 17ab, 17ba, 17bb) on both sides of a support 19, which is a substrate. The double-sided tape may be provided on the fireproof layer via another layer, but is preferably provided directly on the fireproof layer (directly attached).

[0012] The fireproof member of this embodiment can be manufactured, for example, by bonding a sheet-like fireproof material and double-sided tape. The fireproof member may be a sheet or a molded body. The fireproof member is not limited to a sheet shape. The fireproof material (fireproof layer) and the double-sided tape can be shaped or deformed according to the shape of the structure to which the fireproof member is attached, and fireproof members of various shapes may be obtained.

[0013] <Fireproof layer> The fire-resistant layer contains a matrix polymer component, an inorganic compound, a softener, and a thermally expandable compound.

[0014] <Matrix polymer component> As the matrix polymer component, a wide variety of known resins can be used, including, for example, thermoplastic resins, thermosetting resins, elastomers, and combinations thereof.

[0015] Examples of thermoplastic resins include polyolefin resins such as polypropylene resin, polyethylene resin, poly(1-)butene resin, and polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate resin, polyphenylene ether resin, (meth)acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), novolac resin, polyurethane resin, polyisobutylene, polyvinyl acetate, and synthetic resins such as ethylene-vinyl acetate (EVA).

[0016] Examples of thermosetting resins include synthetic resins such as polyurethane, polyisocyanate, polyisocyanurate, phenolic resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide.

[0017] Examples of elastomers include rubber and thermoplastic elastomers. Thermoplastic elastomers are elastomers that soften and become fluid when heated, and can be distinguished from rubber, which does not have this property.

[0018] Examples of rubber include natural rubber, isoprene rubber, butylene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, chlorinated polyethylene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM), ethylene-vinyl acetate rubber, chloroprene rubber (CR), chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, crosslinkable rubber such as reclaimed rubber, silicone rubber, fluororubber, and urethane rubber.

[0019] Examples of thermoplastic elastomers include polyolefin thermoplastic elastomers (TPO), polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, polybutadiene thermoplastic elastomers, and polystyrene thermoplastic elastomers (TPS).

[0020] The polystyrene-based thermoplastic elastomer is preferably a block copolymer consisting of a polymer block mainly composed of a vinyl aromatic hydrocarbon and a polymer block mainly composed of a conjugated diene. Examples of vinyl aromatic hydrocarbons include styrene, p-methylstyrene, α-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and monobromostyrene, which may be used alone or in combination of two or more. Examples of conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene, which may be used alone or in combination of two or more.

[0021] Specific examples of polystyrene-based thermoplastic elastomers include styrene-butadiene-styrene (SBS) copolymer, styrene-isoprene-styrene (SIS) copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene-isoprene-hydrogenated styrene-isoprene-styrene (SEPS) copolymer, styrene-ethylene-propylene (SEP) copolymer, styrene-ethylene-propylene-styrene (SEPS) copolymer, styrene-ethylene-ethylene-propylene-styrene (SEEPS) copolymer, and styrene-butadiene copolymer. The styrene content of the styrene-based thermoplastic elastomer is, for example, 15% to 70% by mass, preferably 20% to 60% by mass. This content may be, for example, 5, 10, 15, 18, 20, 23, 25, 30, 31, 35, 40, 45, 50, 55, 60, 65, or 70% by mass, or may fall within a range between any two of the values ​​listed here.

[0022] These matrix polymer components can be used alone or in combination of two or more.

[0023] <Thermally expandable compound> The thermally expandable compound is not particularly limited as long as it expands when heated, and examples thereof include microspheres, melamine, azo compounds, nitroso compounds, hydrazine derivatives, bicarbonates, vermiculite, kaolin, mica, thermally expandable graphite, etc. Among these, thermally expandable graphite is preferred because of its low expansion initiation temperature, and the thermally expandable compound preferably contains thermally expandable graphite.

[0024] Thermally expandable graphite is a crystalline compound that maintains the layered structure of graphite and is produced by treating powders of natural graphite, pyrolytic graphite, or the like with an inorganic acid such as sulfuric acid or nitric acid and a strong oxidizing agent such as concentrated nitric acid or permanganate. When exposed to temperatures of about 200°C or higher, it thermally expands, for example, by 100 times or more. These powders of natural graphite, pyrolytic graphite, and the like are available in various varieties, including those that have been deoxidized and further neutralized, and any of these can be used.

[0025] The thermally expandable graphite used in the present invention preferably has an average aspect ratio of at least 20. When the thermally expandable graphite has an average aspect ratio of at least 20, it can be sufficiently filled into the interior of a frame that constitutes an opening frame of a fixture such as a fire-resistant resin sash, and can also be suitably used for covering steel frames.

[0026] The average aspect ratio is the ratio of the average diameter in the horizontal direction to the thickness in the vertical direction. Since the thermally expandable graphite used in the present invention is generally flat, the vertical direction can be considered to be the thickness direction and the horizontal direction the diameter direction, and therefore the aspect ratio is the value obtained by dividing the maximum horizontal dimension by the thickness in the vertical direction. The aspect ratios of a sufficiently large number of graphite pieces, i.e., 10 or more pieces, are then measured, and the average value is taken as the average aspect ratio. The average particle size of the thermally expandable graphite can also be determined as the average value of the maximum horizontal dimension. The maximum horizontal dimension and thickness of the thermally expandable graphite can be measured using, for example, a field emission scanning electron microscope (FE-SEM).

[0027] The content of the thermally expandable compound is 5 to 400 parts by mass, preferably 35 to 300 parts by mass, and more preferably 65 to 200 parts by mass, per 100 parts by mass of the matrix polymer component. By having the content of the thermally expandable compound in this range, it is possible to achieve both a high thermal expansion ratio and shape stability of the fire-resistant material after thermal expansion.

[0028] <Inorganic compounds> Examples of inorganic compounds include metal oxides such as alumina, aluminosilicate, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, aluminum hydroxide, and ferrites; hydrated inorganic substances such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; calcium salts such as calcium sulfate and calcium silicate; and glass. Examples of suitable inorganic fillers include beads, silica-based baluns, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon baluns, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, zinc borate, various magnetic powders, fly ash, inorganic hollow fillers, pearlite, obsidian, perlite, colophonite, diatomaceous earth, dewatered sludge, boron, sodium tetraborate hydrate (borax), glass fiber, silica, clay minerals, and inorganic phosphorus compounds. These may be used alone or in combination. From the standpoint of dispersibility, the average particle size of the inorganic compound is preferably 1 to 100 μm as measured by laser diffraction.

[0029] <Inorganic phosphorus compounds> The inorganic phosphorus-based compound includes at least one of a phosphoric acid-based compound, a phosphorous acid-based compound, a hypophosphorous acid-based compound, a metaphosphate-based compound, a pyrophosphate-based compound, and a polyphosphate-based compound.

[0030] Examples of phosphate compounds include monoaluminum phosphate, monosodium phosphate, monopotassium phosphate, monocalcium phosphate, monozinc phosphate, dialuminum phosphate, disodium phosphate, dipotassium phosphate, dicalcium phosphate, dizinc phosphate, trialuminum phosphate, trisodium phosphate, tripotassium phosphate, tricalcium phosphate, trizinc phosphate, trimagnesium phosphate, monoammonium phosphate, diammonium phosphate, tricalcium phosphate, and aluminum phosphate.

[0031] Examples of the phosphite compounds include aluminum phosphite, aluminum hydrogen phosphite, sodium phosphite, potassium phosphite, calcium phosphite, and zinc phosphite.

[0032] Examples of hypophosphite compounds include aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and zinc hypophosphite.

[0033] Examples of metaphosphate compounds include aluminum metaphosphate, sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, zinc metaphosphate, and sodium hexametaphosphate.

[0034] An example of the pyrophosphate compound is sodium pyrophosphate.

[0035] Examples of polyphosphate compounds include ammonium polyphosphate and melamine-modified ammonium polyphosphate.

[0036] The content of the inorganic compound is 20 to 600 parts by mass, preferably 80 to 470 parts by mass, and more preferably 140 to 340 parts by mass, relative to 100 parts by mass of the matrix polymer component. By keeping the content of the inorganic compound within this range, both flame retardancy and flexibility can be achieved.

[0037] The inorganic compound preferably contains aluminum hydrogen phosphite, which tends to improve shape stability after expansion of the thermally expandable compound contained in the fireproof material.

[0038] <Softener> The softener is not particularly limited, but examples thereof include rapeseed oil, cottonseed oil, palm oil, coconut oil, peanut oil, tall oil, pine tar, process oil (paraffinic oil, naphthenic oil, and aromatic process oil), carboxylic acid ester plasticizers (phthalic acid esters, adipic acid esters, sebacate esters, maleic acid esters, fumaric acid esters, trimellitic acid esters, citrate esters, oleic acid esters, ricinoleic acid esters, stearic acid esters, glycolic acid esters, etc.), and phosphate ester plasticizers (tritolyl phosphate, triisopropylphenyl phosphate, etc.). One softener may be used alone, or two or more may be used in combination.

[0039] The content of the softener is preferably 10 to 200 parts by mass, more preferably 40 to 170 parts by mass, and even more preferably 70 to 140 parts by mass, relative to 100 parts by mass of the matrix polymer component. By keeping the content of the softener within this range, both flexibility and flame retardancy can be achieved.

[0040] In this embodiment, a vulcanizing agent and a vulcanization accelerator used in ordinary rubber compounds may be contained within a range that does not impair the effects. The vulcanizing agent and the vulcanization accelerator improve the degree of crosslinking of vulcanizable rubber and improve the strength of the rubber itself. The strength of rubber can be evaluated by hardness. However, the fire-resistant material of the present invention does not need to contain a vulcanizing agent and a vulcanization accelerator. In other words, the fire-resistant material of the present invention does not need to be vulcanized.

[0041] In this embodiment, antioxidants, processing aids, lubricants, organic fibers, tackifiers, and the like that are used in ordinary rubber compounds may be used in combination within the range that does not impair the effects of the rubber composition.

[0042] The fire-resistant layer (fire-resistant material) of this embodiment can be obtained by kneading the above-mentioned components using a known kneading device such as a Banbury mixer, a kneader mixer, or a two-roll mill, and then molding the mixture into a sheet using a conventionally known molding method such as press molding, roll molding, extrusion molding, or calendar molding.

[0043] The thickness of the resulting fire-resistant layer is not particularly limited, but is preferably 0.1 to 20 mm, and particularly preferably 0.5 to 10 mm.

[0044] <Double-sided tape having adhesive layers on both sides of the support> The double-sided tape used in this embodiment is composed of a support and an adhesive, and has adhesive layers on both sides of the support, which is a substrate. Conventionally known adhesives can be used as the adhesive, such as rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, and urethane-based adhesives, or combinations thereof. In one embodiment, the adhesive layer is preferably a crosslinked acrylic adhesive. When the acrylic adhesive is an acrylic adhesive crosslinked with an isocyanate compound or the like, migration of low-molecular-weight substances from the fire-resistant material to the adhesive layer is suppressed, and the decrease in cohesive strength of the laminated adhesive layer over time can be suppressed.

[0045] <Rubber-based adhesive> Examples of rubber-based adhesives include natural rubber-based adhesives, styrene-based thermoplastic elastomer-based adhesives, and butyl rubber-based adhesives.

[0046] <Acrylic adhesive> Examples of the acrylic adhesive include an acrylic adhesive containing an acrylic ester as a main component. Typically, an acrylic copolymer is obtained by mixing a (meth)acrylic ester-based monomer component, a functional group-containing monomer, and a polymerization initiator, and polymerizing the monomer component.

[0047] Examples of (meth)acrylic acid ester monomers include butyl (meth)acrylate, 2-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tridecyl (meth)acrylate, and methyl (meth)acrylate. Examples of the acrylates include sil(meth)acrylate, myristyl(meth)acrylate, cetyl(meth)acrylate, stearyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentanyl(meth)acrylate, benzyl(meth)acrylate, methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate, butoxymethyl(meth)acrylate, and ethoxy-n-propyl(meth)acrylate.

[0048] Examples of functional group-containing monomers include those having a hydroxyl group, a carboxyl group, an epoxy group, an amide group, an amino group, a methylol group, and the like.

[0049] Examples of functional group-containing monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxyvinyl ether.

[0050] Examples of functional group-containing monomers having a carboxyl group include (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamido-N-glycolic acid, and cinnamic acid.

[0051] Examples of functional group-containing monomers having an epoxy group include glycidyl (meth)acrylate.

[0052] Examples of functional group-containing monomers having an amide group include (meth)acrylamide.

[0053] Examples of functional group-containing monomers having an amino group include N,N-dimethylaminoethyl (meth)acrylate and Nt-butylaminoethyl (meth)acrylate.

[0054] Examples of functional group-containing monomers having a methylol group include N-methylol (meth)acrylamide.

[0055] Other copolymerizable monomers include, for example, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, vinyl acetate, and styrene.

[0056] The polymerization initiator is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, etc. These may be used alone or in combination.

[0057] The adhesive strength and cohesive strength (holding force) of acrylic pressure-sensitive adhesives can be set to any desired values ​​by using a crosslinking agent, such as a polyisocyanate compound, a polyepoxy compound, a polyaziridine compound, or a chelate compound.

[0058] Examples of polyisocyanate compounds include aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates. Specific examples include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and adducts thereof.

[0059] Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether and terephthalic acid diglycidyl ester.

[0060] Examples of polyvalent aziridine compounds that can be used include tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, tris[1-(2-methyl)-aziridinyl]phosphine oxide, and hexa[1-(2-methyl)-aziridinyl]triphosphatriazine.

[0061] As the chelate compound, for example, ethyl acetoacetate aluminum diisopropylate, aluminum tris(ethyl acetoacetate), etc. may be used.

[0062] The preferred amount of the crosslinking agent added is 0.1 to 20 parts by mass per 100 parts by mass of the acrylic copolymer. If the amount is less than 0.1 part by mass, the composition will be too soft, resulting in problems with retention when attached to a structure. If the amount is more than 20 parts by mass, the composition will be too hard, resulting in poor wetting and spreading (adhesion) to the structure.

[0063] The thickness of the resulting pressure-sensitive adhesive layer is not particularly limited, but is preferably 5 to 200 μm, particularly 10 to 150 μm, and further preferably 15 to 100 μm. If the thickness is equal to or greater than the lower limit, the adhesive properties are stable, and if the thickness is equal to or less than the upper limit, adhesive residue is less likely to occur.

[0064] The support of the double-sided tape used in the present invention may be, for example, a nonwoven fabric such as rayon or polyester, Japanese paper, plastic film, or metal foil.

[0065] Examples of plastic films include materials containing one or more polymers such as polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, etc.), polyphenylene sulfide, polyimide, polyetherimide, aromatic polyether ketone (polyether ketone (PEK), polyether ether ketone (PEEK)), polyamide (nylon, aramid, etc.), polyacetate, polyurethane, polyvinyl acetate, ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, fluororesin (polytetrafluoroethylene, etc.), cellophane, vinylon, polyvinyl alcohol, acrylic resin, polycarbonate, polystyrene, and various rubbers.

[0066] In order to improve the adhesion between the support and the pressure-sensitive adhesive layer, the support may be subjected to a corona treatment or an electron beam treatment. Also, an underlayer made of a polyester resin, a polyolefin resin, an acrylic resin, an epoxy resin, an amide resin, a urethane resin, a melamine resin, or the like may be provided.

[0067] By providing a support, migration of low molecular weight substances from the fire-resistant material layer to the pressure-sensitive adhesive layer can be efficiently prevented.

[0068] <Application> The fire-resistant member of this embodiment can be used for various purposes, for example, as a fire-resistant covering for building fixtures or steel frames, etc. Furthermore, a sealing material according to one embodiment of the present invention is a sealing material for building fixtures or a fire-resistant covering material for steel frames, etc., made of the fire-resistant member. [Example]

[0069] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0070] Details of the components in the tables (Tables 1 to 5) are as follows: The unit of content of each component in the tables is "parts by mass."

[0071] <Refractory material layer> [Matrix polymer component] Polyvinyl chloride (PVC): "TH-1000" manufactured by Taiyo PVC Co., Ltd. Ethylene vinyl acetate copolymer (EVA): "Evaflex EV460" manufactured by Mitsui Dow Polychemicals Co., Ltd. Epoxy resin: Mitsubishi Chemical Corporation "jER806" Epoxy resin hardener: Mitsubishi Chemical Corporation "FL052" Thermoplastic polyolefin elastomer (TPO): "Milastomer 4010NS" manufactured by Mitsui Chemicals, Inc. Thermoplastic polystyrene elastomer (TPS): "TEFABLOCK" manufactured by Mitsubishi Chemical Corporation Butyl rubber: JSR Corporation "BUTYL268" EPDM rubber: Mitsui Chemicals "EPT3092M" Chloroprene rubber (CR): Denka Company Limited "S-40V" [Inorganic compounds] Calcium carbonate (Ca carbonate): "TA-004" manufactured by Chichibu Lime Industry Co., Ltd. Aluminum hydrogen phosphite (Al hydrogen phosphite): "NSF" manufactured by Taihei Chemical Industry Co., Ltd. [Softener] Process oil: Idemitsu Kosan Co., Ltd. "AH-16" [Thermal expandable compound] Thermally expandable graphite: "SS-3" manufactured by Air Water Chemical Co., Ltd.

[0072] <Adhesive layer> Butyl acrylate (BA): "Butyl acrylate" manufactured by Mitsubishi Chemical Corporation 2-Hydroxyethyl acrylate (HA): "2-Hydroxyethyl acrylate" manufactured by Tokyo Chemical Industry Co., Ltd. Acrylic acid (AA): "Acrylic acid" manufactured by Mitsubishi Chemical Corporation Azobisisobutyronitrile: 2,2'-azodiisobutyronitrile manufactured by Tokyo Chemical Industry Co., Ltd. Trimethylolpropane-modified xylylene diisocyanate crosslinking agent (NCO): "TD-75" manufactured by Soken Chemical & Engineering Co., Ltd. Epoxy crosslinking agent: "Tetrad C" manufactured by Mitsubishi Gas Chemical Co., Ltd. Polyethylene terephthalate film: Toyobo Co., Ltd. "E5200" 0.025 mm thick <Double-sided tape> Tape 1: Nitto Denko Corporation "No. 5000NS" (total thickness 160 μm, acrylic adhesive, backing is nonwoven fabric 70 μm) Tape 2: Furutokogyo Co., Ltd. "W-503" (total thickness 1 mm, butyl rubber adhesive, backing is polyethylene film 210 μm)

[0073] <Various evaluations> The fire-resistant members with double-sided tape of the examples and comparative examples were subjected to the following various evaluations, and the results are shown in Tables 1 to 5.

[0074] (1) Production of Fireproof Member Samples of Examples 1 to 42 and Comparative Examples 1 and 2 [Example 1]

[0075] -Fireproofing material production The components shown in the table were kneaded for 2 minutes at 120°C using a 3-liter kneader mixer to obtain a composition. The obtained composition was then pressed in a hot press to obtain a sheet-like EPDM rubber-based fire-resistant material with a thickness of 2 mm.

[0076] ·Preparing double-sided tape 95 parts by weight of butyl acrylate, 5 parts by weight of 2-hydroxyethyl acrylate, and 80 parts by weight of ethyl acetate were added to a reactor equipped with a thermometer, a stirrer, and a condenser, and the inside of the reactor was replaced with nitrogen. Then, the reactor was heated to initiate reflux. Subsequently, 0.1 parts by weight of azobisisobutyronitrile was added as a polymerization initiator to the reactor, and the mixture was refluxed for 5 hours to obtain a solution of an acrylic copolymer. This acrylic copolymer solution was mixed with 3 parts by weight of a trimethylolpropane-modified xylylene diisocyanate crosslinking agent (manufactured by Soken Chemical & Engineering Co., Ltd., product name "TD-75") in terms of solid content, and the mixture was stirred to obtain a solution of acrylic copolymer containing the crosslinking agent. This solution of the acrylic copolymer containing the crosslinking agent was coated on release paper and dried to obtain a 0.05 mm thick adhesive layer, which was then attached to both sides of a 0.025 mm thick polyethylene terephthalate support and cured at 40°C for 3 days to obtain a double-sided tape.

[0077] -Production of fire-resistant materials The prepared double-sided tape was attached to one side of a 2 mm thick EPDM rubber-based fire-resistant material to form a fire-resistant member.

[0078] [Example 2] A fire-resistant member was produced in the same manner as in Example 1, except that in the adhesive layer, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were used instead of 95 parts by weight of butyl acrylate and 5 parts by weight of 2-hydroxyethyl acrylate, and the crosslinking agent was an epoxy-based crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Inc., product name "Tetrad C").

[0079] [Example 3] A fire-resistant member was produced in the same manner as in Example 1, except that "No. 5000NS" manufactured by Nitto Denko Corporation (total thickness 160 μm, acrylic adhesive, support is nonwoven fabric 70 μm) was used as the double-sided tape.

[0080] [Example 4] A fire-resistant member was produced in the same manner as in Example 1, except that "W-503" manufactured by Furuto Industries Co., Ltd. (total thickness 1 mm, butyl rubber adhesive, support: polyethylene film 210 μm) was used as the double-sided tape.

[0081] [Example 5] A fire-resistant member was produced in the same manner as in Example 1, except that no crosslinking agent was used.

[0082] [Example 6] A fire-resistant member was produced in the same manner as in Example 2, except that no crosslinking agent was used.

[0083] [Example 7] A fire-resistant member was produced in the same manner as in Example 1, except that the amount of the crosslinking agent was 0.05 parts by weight.

[0084] [Example 8] A fire-resistant member was produced in the same manner as in Example 1, except that the amount of the crosslinking agent was 0.1 parts by weight.

[0085] [Example 9] A fire-resistant member was produced in the same manner as in Example 1, except that the amount of the crosslinking agent was 19 parts by weight.

[0086] [Example 10] A fire-resistant member was produced in the same manner as in Example 1, except that the amount of the crosslinking agent was 21 parts by weight.

[0087] [Comparative Example 1] A fire-resistant material was produced in the same manner as in Example 1, except that no support was used.

[0088] Comparative Example 2 A fire-resistant material was produced in the same manner as in Example 2, except that no support was used.

[0089] [Example 11] A fire-resistant member was produced in the same manner as in Example 1, except that the matrix polymer component of the fire-resistant material layer was changed to PVC, a thermoplastic resin.

[0090] [Example 12] A fire-resistant member was produced in the same manner as in Example 1, except that the matrix polymer component of the fire-resistant material layer was changed to EVA, a thermoplastic resin.

[0091] [Example 13] A fire-resistant member was produced in the same manner as in Example 1, except that the matrix polymer component of the fire-resistant material layer was a thermosetting epoxy resin.

[0092] [Example 14] A fire-resistant member was produced in the same manner as in Example 1, except that the matrix polymer component of the fire-resistant material layer was changed to a polyolefin-based thermoplastic elastomer (TPO).

[0093] [Example 15] A fire-resistant member was produced in the same manner as in Example 1, except that the matrix polymer component of the fire-resistant material layer was a polystyrene-based thermoplastic elastomer (TPS).

[0094] [Example 16] A fire-resistant member was produced in the same manner as in Example 1, except that the matrix polymer component of the fire-resistant material layer was changed to a rubber-based butyl rubber.

[0095] [Example 17] A fire-resistant member was produced in the same manner as in Example 1, except that the matrix polymer component of the fire-resistant material layer was changed to a rubber-based chloroprene rubber (CR).

[0096] [Examples 18 to 24] The inorganic compound of the fireproof material layer is calcium carbonate, and the blending amount is 20 to 600 parts by mass. A fire-resistant member was produced in the same manner as in Example 1.

[0097] [Examples 25 to 30] A fireproof member was produced in the same manner as in Example 1, except that aluminum hydrogen phosphite was used as the inorganic compound in the fireproof material layer and the blending amount thereof was set to 20 to 600 parts by mass.

[0098] [Examples 31 to 36] A fireproof member was produced in the same manner as in Example 1, except that process oil was used as the softener for the fireproof material layer and the blending amount thereof was set to 10 to 200 parts by mass.

[0099] [Examples 37 to 42] A fire-resistant member was produced in the same manner as in Example 1, except that thermally expandable graphite was used as the thermally expandable compound for the fire-resistant material layer and the blending amount thereof was set to 5 to 400 parts by mass.

[0100] The test methods for evaluating the performance of each sample are described below.

[0101] <Flexibility> Two SUS plates, each 1 mm thick, 25 mm wide, and 100 mm long, were prepared and placed side by side, with a 3 mm gap between them in the longitudinal direction. A 10 mm wide, 100 mm long fireproof member with double-sided tape was attached to each plate to create a bonded structure (Figure 3). The bonded structure was bent in the opposite direction to the side on which the test piece was attached, and the angle θ at which a crack appeared in the fireproof layer of the test piece was measured (Figure 4). The flexibility was evaluated according to the following criteria. The larger the angle at which the crack appeared, the better the flexibility. ◎: No cracks even at a 180 degree angle ○: Cracks occur at angles of 150 degrees or more and less than 180 degrees △: Cracks occur at angles of 120 degrees or more and less than 150 degrees ×: Cracks occur at angles less than 120 degrees

[0102] <Thermal expansion> A test piece of fire-resistant material (before being attached with double-sided tape) measuring 2 mm in thickness, 30 mm in width, and 30 mm in length was heat-treated at 300°C for 0.5 hours, and its expansion ratio was measured. Specifically, the volume after heat treatment was divided by the volume before heat treatment to calculate the volume expansion ratio, and the thermal expandability was evaluated according to the following criteria. The volume was calculated by measuring the thickness, width, and length. ◎: Volume expansion ratio is 6 times or more ○: Volume expansion ratio is 4 times or more but less than 6 times △: Volume expansion ratio is 2 times or more but less than 4 times ×: Volume expansion ratio is less than 2 times

[0103] <Shape stability> After evaluating the thermal expansion properties, the strength (three-point bending fracture strength) of the thermally expanded test piece was measured at fracture under conditions of a compression rate of 50 mm / min using a three-point bending test jig (top push side tip R1 mm and width 80 mm, bottom two-point support side R1 mm, width 80 mm, distance between supports 20 mm).The shape stability after thermal expansion was then evaluated according to the following criteria. ◎: Three-point bending breaking strength of 2.0N or more ○: Three-point bending breaking strength is 1.5N or more and less than 2.0N △: Three-point bending breaking strength is 1N or more but less than 1.5N ×: Three-point bending breaking strength less than 1N

[0104] <Flame retardancy> The oxygen index of the test piece of fire-resistant material (before being attached with double-sided tape) was measured using a combustion tester (ON-1 model, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K6269, and the flame retardancy was judged according to the following criteria. Note that the higher the oxygen index, the higher the flame retardancy. ◎: Oxygen index is 55 or higher ○: Oxygen index is 50 or more and less than 55 △: Oxygen index is 45 or more but less than 50 ×: Oxygen index less than 45

[0105] <Cohesiveness (holding force)> The holding power was measured in accordance with JIS Z 0237. Specifically, the fireproof members with double-sided tape of the examples and comparative examples were left standing in an atmosphere at 40°C for one day, and then attached to a stainless steel test plate with a width of 20 mm and a length of 20 mm, and left in an atmosphere at 21°C with a load of 1 kg applied, and the distance (mm) of displacement from the original position after one hour had passed was measured. ◎: Misalignment is less than 2 mm ○: Misalignment is 2mm or more and less than 4mm △: Misalignment is 4mm or more and less than 6mm ×: Misalignment is 6mm or more

[0106] <Aggregation over time (retention over time)> The holding power was measured in accordance with JIS Z 0237. Specifically, the fireproof members with double-sided tape of the examples and comparative examples were left standing in an atmosphere at 40°C for 7 days, and then attached to a stainless steel test plate with a width of 20 mm and a length of 20 mm, and left in an atmosphere at 21°C with a load of 1 kg applied, and the distance (mm) of displacement from the original position after 1 hour was measured. ◎: Misalignment is less than 2 mm ○: Misalignment is 2mm or more and less than 4mm △: Misalignment is 4mm or more and less than 6mm ×: Misalignment is 6mm or more

[0107] <Adhesiveness (adhesive strength)> The adhesive strength was measured in accordance with JIS Z 0237. Specifically, the fire-resistant members with double-sided tape of the Examples and Comparative Examples were left standing in an atmosphere at 40°C for one day, then attached to a stainless steel test plate with a width of 20 mm and a length of 150 mm, pressed back and forth once with a 1 kg rubber roll, and then left in an atmosphere at 21°C for 20 minutes. The adhesive strength was measured by peeling in a 180-degree direction at a speed of 300 mm / min. ◎: Adhesive strength is 6N / 20mm or more ○: Adhesive strength is 4N / 20mm or more, less than 6N / 20mm △: Adhesive strength is 2N / 20mm or more, less than 4N / 20mm ×: Adhesive strength is less than 2N / 20mm

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3]

[0111] [Table 4]

[0112] [Table 5] [Explanation of symbols]

[0113] 1, 10: Fireproof material with double-sided tape 3, 13: Fireproof layer 5, 15 (15a, 15b): double-sided tape 7(7a, 7b), 17(17aa, 17ab, 17ba, 17bb):Adhesive layer 9, 19 (19a, 19b): Support

Claims

1. a fire-resistant layer containing a matrix polymer component, an inorganic compound, a softener, and a thermally expandable compound; a double-sided tape having pressure-sensitive adhesive layers on both sides of a support, the double-sided tape being provided on one or both sides of the fire-resistant layer; and the fire-resistant layer contains 70 to 140 parts by mass of the softener relative to 100 parts by mass of the matrix polymer component; the pressure-sensitive adhesive layer is a butyl rubber-based pressure-sensitive adhesive or an acrylic-based pressure-sensitive adhesive, The fire-resistant member with double-sided tape, wherein the inorganic compound contains aluminum hydrogen phosphite.

2. a fire-resistant layer containing a matrix polymer component, an inorganic compound, a softener, and a thermally expandable compound; a double-sided tape having pressure-sensitive adhesive layers on both sides of a support, the double-sided tape being provided on one or both sides of the fire-resistant layer; and the fire-resistant layer contains 70 to 140 parts by mass of the softener relative to 100 parts by mass of the matrix polymer component; The fire-resistant member with double-sided tape, wherein the pressure-sensitive adhesive layer is a cross-linked acrylic pressure-sensitive adhesive.

3. a fire-resistant layer containing a matrix polymer component, an inorganic compound, a softener, and a thermally expandable compound; a double-sided tape having pressure-sensitive adhesive layers on both sides of a support, the double-sided tape being provided on one or both sides of the fire-resistant layer; and the fire-resistant layer contains 70 to 140 parts by mass of the softener relative to 100 parts by mass of the matrix polymer component; the pressure-sensitive adhesive layer is a butyl rubber-based pressure-sensitive adhesive or an acrylic-based pressure-sensitive adhesive, Fire-resistant material with double-sided tape used for fire-resistant covering of building materials or steel frames.

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