JP7728306B2 - Fire-resistant material with double-sided tape - Google Patents

Description

The present invention relates to a fire-resistant member with double-sided tape.

Patent documents 1 and 2 are known examples of fire-resistant components that have both fire resistance and an adhesive layer, and use a liquid-additive-resistant adhesive layer.

International Publication No. 2017/034002 Patent Publication No. 2017-145682

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.

The object of the present invention is to provide a fire-resistant component in which the adhesive layer laminated thereon exhibits minimal loss of cohesive strength over time.

The inventors discovered that the above objectives could be achieved by creating a laminate containing a layer of adhesive and a fire-resistant material in a specific configuration, leading to the completion of the present invention.

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 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. [1]
[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 fireproof member with double-sided tape according to any one of [1] to [5], which is used for fireproof coating of building materials or steel frames.

The present invention makes it possible to provide a refractory component that exhibits minimal loss of cohesive strength over time.

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. 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. FIG. 10 is a diagram illustrating a method for producing a joint for a flexibility test. FIG. 10 is a diagram illustrating the bending direction and angle θ of the joint for flexibility test.

The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present invention is not limited to this embodiment, and various modifications are possible without departing from the spirit of the present invention.

<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. Note that the double-sided tape may be provided on the fireproof layer via another layer, but is preferably provided directly on (directly attached to) the fireproof layer.

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

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

<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.

Examples of thermoplastic resins include polyolefin resins such as polypropylene resin, polyethylene resin, poly(1-)butene resin, and polypentene resin, as well as synthetic resins such as 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 ethylene-vinyl acetate (EVA).

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.

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.

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.

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).

The polystyrene-based thermoplastic elastomer is preferably a block copolymer consisting of a polymer block primarily composed of a vinyl aromatic hydrocarbon and a polymer block primarily 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.

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.

One or more of these matrix polymer components can be used.

<Thermal 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.

Thermal expandable graphite is a crystalline compound that maintains the layered structure of graphite, and is made by treating powders of natural graphite, pyrolytic graphite, or other materials with inorganic acids such as sulfuric acid or nitric acid and strong oxidizing agents such as concentrated nitric acid or permanganate. When exposed to temperatures of around 200°C or higher, it thermally expands, for example, by more than 100 times. There are various types of powders of natural graphite, pyrolytic graphite, and other materials, including those that have been deoxidized and further neutralized, and all of these can be used.

The thermally expandable graphite used in the present invention preferably has an average aspect ratio of 20 or more. Thermally expandable graphite with an average aspect ratio of 20 or more can be sufficiently filled into the interior of the frame that constitutes the opening frame of building fixtures such as fire-resistant resin sashes, and can also be suitably used for covering steel frames.

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 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).

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 keeping the content of the thermally expandable compound within this range, it is possible to achieve both a high thermal expansion ratio and the shape stability of the fire-resistant material after thermal expansion.

<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 of two or more. From the viewpoint of dispersibility, the average particle size of the inorganic compound is preferably 1 to 100 μm as measured by laser diffraction.

<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.

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

Examples of phosphite compounds include aluminum phosphite, aluminum hydrogen phosphite, sodium phosphite, potassium phosphite, calcium phosphite, and zinc phosphite.

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

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

An example of a pyrophosphate compound is sodium pyrophosphate.

Examples of polyphosphate compounds include ammonium polyphosphate and melamine-modified ammonium polyphosphate.

The inorganic compound content is 20 to 600 parts by mass, preferably 80 to 470 parts by mass, and more preferably 140 to 340 parts by mass, per 100 parts by mass of the matrix polymer component. By keeping the inorganic compound content within this range, it is possible to achieve both flame retardancy and flexibility.

The inorganic compound preferably contains aluminum hydrogen phosphite. In this case, the thermally expandable compound contained in the fire-resistant material tends to have good shape stability after expansion.

<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, sebacic acid 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.

The softener content 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, per 100 parts by mass of the matrix polymer component. By keeping the softener content within this range, it is possible to achieve both flexibility and flame retardancy.

In this embodiment, the fire-resistant material of the present invention may contain vulcanizing agents and vulcanization accelerators used in ordinary rubber compounds, provided that the effects are not impaired. The vulcanizing agents and vulcanization accelerators improve the degree of crosslinking of vulcanizable rubber and increase 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 vulcanizing agents and vulcanization accelerators. In other words, the fire-resistant material of the present invention does not need to be vulcanized.

In this embodiment, antioxidants, processing aids, lubricants, organic fibers, tackifiers, and other agents typically used in rubber compounds may be used in combination, as long as their effects are not impaired.

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

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.

<Double-sided tape having pressure-sensitive adhesive layers on both sides of a 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.

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

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

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, Examples 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.

Examples of functional group-containing monomers include those containing hydroxyl groups, carboxyl groups, epoxy groups, amide groups, amino groups, and methylol groups.

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.

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.

Examples of functional group-containing monomers having epoxy groups include glycidyl (meth)acrylate.

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

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

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

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.

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

The adhesive strength and cohesive strength (holding power) of acrylic adhesives can be set to any desired value by using a crosslinking agent. Examples of such crosslinking agents include polyisocyanate compounds, polyepoxy compounds, polyaziridine compounds, and chelate compounds.

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.

Examples of polyepoxy compounds that can be used include ethylene glycol diglycidyl ether and terephthalic acid diglycidyl ester.

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.

Examples of chelating compounds that can be used include ethyl acetoacetate aluminum diisopropylate and aluminum tris(ethyl acetoacetate).

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

The thickness of the resulting adhesive layer is not particularly limited, but is preferably 5 to 200 μm, particularly 10 to 150 μm, and even more preferably 15 to 100 μm. If the thickness is above the lower limit, the adhesive properties will be stable, and if it is below the upper limit, adhesive residue is less likely to occur.

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

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)), etc.), 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.

To improve adhesion between the support and the adhesive layer, the support may be subjected to corona treatment or electron beam treatment. Furthermore, a base layer made of polyester resin, polyolefin resin, acrylic resin, epoxy resin, amide resin, urethane resin, or melamine resin may also be provided.

By providing a support, migration of low molecular weight substances from the fire-resistant material layer to the adhesive layer can be effectively prevented.

<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.

The present invention will be explained in more detail below using examples, but the present invention is not limited to these.

Details of the ingredients in the tables (Tables 1 to 5) are as follows. The content of each ingredient in the tables is expressed in parts by mass.

<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: "jER806" manufactured by Mitsubishi Chemical Corporation
Epoxy resin curing agent: "FL052" manufactured by Mitsubishi Chemical Corporation
- Thermoplastic polyolefin elastomer (TPO): "Milastomer 4010NS" manufactured by Mitsui Chemicals, Inc.
- Thermoplastic polystyrene elastomer (TPS): "TEFABLOCK" manufactured by Mitsubishi Chemical Corporation
-Butyl rubber: "BUTYL268" manufactured by JSR Corporation
・EPDM rubber: "EPT3092M" manufactured by Mitsui Chemicals, Inc.
- Chloroprene rubber (CR): "S-40V" manufactured by Denka Co., Ltd.
[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]
-Thermal expandable graphite: "SS-3" manufactured by Air Water Chemical Co., Ltd.

<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: "No. 5000NS" manufactured by Nitto Denko Corporation (total thickness 160 μm, acrylic adhesive, support is nonwoven fabric 70 μm)
Tape 2: "W-503" manufactured by Furutoh Industries Co., Ltd. (total thickness 1 mm, butyl rubber adhesive, support is polyethylene film 210 μm)

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

(1) Production of refractory component samples of Examples 1 to 42 and Comparative Examples 1 and 2 [Example 1]

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 further pressed in a hot press to obtain a sheet-like EPDM rubber-based fire-resistant material having a thickness of 2 mm.

Preparation of 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 placed in a reactor equipped with a thermometer, a stirrer, and a cooling tube, and the inside of the reactor was replaced with nitrogen. Then, the reactor was heated to start 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.
To this acrylic copolymer solution, 3 parts by weight of a trimethylolpropane-modified xylylene diisocyanate crosslinking agent (manufactured by Soken Chemical & Engineering Co., Ltd., product name "TD-75") was added in terms of solid content, and the mixture was stirred to obtain a solution of an acrylic copolymer containing the crosslinking agent.
This solution of the acrylic copolymer containing the crosslinking agent was coated on a 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.

- Preparation of Fire-Resistant Member The prepared double-sided tape was attached to one side of a 2 mm thick EPDM rubber-based fire-resistant material to prepare a fire-resistant member.

[Example 2]
A fire-resistant member was produced in the same manner as in Example 1, except that in the pressure-sensitive 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 Company, Inc., product name "Tetrad C").

[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.

[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.

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

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

[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.

[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.

[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.

[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 changed to 21 parts by weight.

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

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

[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.

[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.

[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.

[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).

[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).

[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.

[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).

[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 refractory member was produced in the same manner as in Example 1.

[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.

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

[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.

The test performance evaluation method for each sample is described below.

<Flexibility>
Two 1 mm thick, 25 mm wide, and 100 mm long SUS plates were prepared and placed side by side with a 3 mm gap 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 surface to 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 an angle of 180 degrees ○: Cracks occur at an angle of 150 degrees or more and less than 180 degrees △: Cracks occur at an angle of 120 degrees or more and less than 150 degrees ×: Cracks occur at an angle less than 120 degrees

<Thermal expansion>
A test piece of the fireproof 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 actually 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

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

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

<Cohesiveness (retention 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 was measured.
◎: Misalignment is less than 2 mm ○: Misalignment is 2 mm or more but less than 4 mm △: Misalignment is 4 mm or more but less than 6 mm ×: Misalignment is 6 mm or more

<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 2 mm or more but less than 4 mm △: Misalignment is 4 mm or more but less than 6 mm ×: Misalignment is 6 mm or more

<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 rate of 300 mm/min.
◎: Adhesive strength is 6N/20mm or more ○: Adhesive strength is 4N/20mm or more and less than 6N/20mm △: Adhesive strength is 2N/20mm or more and less than 4N/20mm ×: Adhesive strength is less than 2N/20mm

1, 10: Fire-resistant member with double-sided tape 3, 13: Fire-resistant layer 5, 15 (15a, 15b): Double-sided tape 7 (7a, 7b), 17 (17aa, 17ab, 17ba, 17bb): Pressure-sensitive adhesive layer 9, 19 (19a, 19b): Support

Claims (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,
The fire-resistant member with double-sided tape, wherein the inorganic compound contains aluminum hydrogen phosphite. 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. 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.