JP2013194072A - Fire-resistant adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technical means for changing various substrates into incombustible substrates to improve the fire-resistance thereof, which can easily impart such sufficiently high fire resistance as satisfying the accreditation criteria of fire-protecting materials in Building Standard Act as much as possible to the various substrates as low costs.SOLUTION: A fire-resistant adhesive tape 100 having a fire-resistant layer 10 and an adhesive layer 20, wherein the fire-resistant layer contains aluminum, and wherein a composite member obtained by adhering the fire-resistant adhesive tape to an adherend having a thickness of 0.1 mm-50 mm has a total calorific value of ≤8 MJ/m2 on heating combustion at a radiation strength of 50 kW/m2 for 20 min in a cone calorimeter test based on ASTM-E-1354.

Description

  The present invention relates to a fire resistant adhesive tape.

  Fire resistance is required for building ceiling materials, building floor materials, building wall materials, railcar ceiling materials, railcar floor materials, railcar wall materials, aircraft interior materials, marine materials, etc. There are many structural materials (fireproof partitions, etc.) that can be used. Since most of such structural materials include various base materials such as paper, wood board, and resin board, a technique for making the base material incombustible and improving fire resistance is required.

The outline of the certification standards for fire prevention materials in the Building Standards Law is as follows: (1) The total calorific value is 8 MJ / m ² or less in a 20-minute heating combustion at a radiation intensity of 50 kW / m ² by a cone calorimeter test, (2 The heat generation time exceeding 200 kW / m ² is less than 10 seconds, and (3) no cracking or penetration reaching the back surface occurs.

  Therefore, in light of the Building Standards Law, in providing fireproof materials, a technique for making the various base materials incombustible so as to satisfy the above-mentioned certification standards as much as possible is strongly required.

  However, no technology has been established that can easily impart sufficiently high fire resistance to various base materials at low cost so as to satisfy the above-mentioned certification standards as much as possible.

  In relation to the technology for making various base materials incombustible, a method using a flame-retardant resin sheet as a base material has been proposed. As a material for such a flame-retardant resin sheet, a halogen-based resin such as a fluorine-based resin or a vinyl chloride resin is used (Patent Document 1). However, the use of halogen-based resins has been restricted in recent years due to the problem of generating harmful gases and dioxins when incinerated.

  In addition, in connection with technologies for making various base materials incombustible, there has been proposed a method of adding a non-halogen flame retardant such as a phosphate ester or a metal hydrate to a resin used as a base material (Patent Document). 2). However, in this technique, it is necessary to add a large amount of flame retardant, and as a result, problems such as a decrease in transparency of the resin and a defect in appearance occur.

  Furthermore, the above conventional technique cannot be applied when the material of various base materials that are required to be nonflammable is other than resin (for example, wood or paper).

JP 2005-015620 A JP 2001-040172 A

  An object of the present invention is a technical means for improving the fire resistance by making various base materials incombustible, and the various base materials have sufficiently high fire resistance to satisfy the certification standards for fireproof materials in the Building Standard Law as much as possible. An object of the present invention is to provide technical means that can be easily applied at low cost.

  As a technical means that can easily impart fire resistance to various base materials at low cost, the present inventor pays attention to the technology of applying an adhesive tape to the base material, and as much as possible the certification standards for fireproof materials in the Building Standards Act. The present inventors have completed the present invention by examining an adhesive tape that can provide sufficiently high fire resistance to satisfy the requirements.

The fireproof adhesive tape of the present invention is
A fire resistant adhesive tape comprising a fire resistant layer and an adhesive layer,
The refractory layer includes aluminum.

In a preferred embodiment, a radiation intensity of 50 kW / m by a cone calorimeter test in accordance with ASTM-E-1354 of a composite member obtained by sticking the fireproof adhesive tape to an adherend having a thickness of 0.1 mm to 50 mm. the total amount of heat generated at 20 minute heating combustion in ² is 8 MJ / ^{m 2} or less.

In a preferred embodiment, a radiation intensity of 50 kW / m by a cone calorimeter test in accordance with ASTM-E-1354 of a composite member obtained by sticking the fireproof adhesive tape to an adherend having a thickness of 0.1 mm to 50 mm. ^The heat generation time exceeding 200 kW / m ² in 20-minute heat combustion at ² is less than 10 seconds.

In a preferred embodiment, a radiation intensity of 50 kW / m by a cone calorimeter test in accordance with ASTM-E-1354 of a composite member obtained by sticking the fireproof adhesive tape to an adherend having a thickness of 0.1 mm to 50 mm. ^No cracking or penetration reaching the back surface after 20 minutes of heat burning in ² .

  In preferable embodiment, the thickness of the said fireproof layer is 5 micrometers-300 micrometers.

  In a preferred embodiment, the refractory layer is any one of an aluminum foil, a laminate in which the aluminum foil is laminated, and a glass cloth aluminum foil.

  In preferable embodiment, the said adhesive layer contains an acrylic adhesive.

  In a preferred embodiment, the refractory layer partially has an opening.

  In preferable embodiment, the thickness of the said adhesive layer is 5 micrometers-2 mm.

  The fireproof treatment method of the present invention is performed using the fireproof adhesive tape of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, sufficiently high fire resistance which satisfy | fills the certification | criteria of the fire prevention material in a building standard method as much as possible can be easily provided to various base materials at low cost.

It is a schematic sectional drawing which shows preferable embodiment of the fireproof adhesive tape of this invention. It is a schematic sectional drawing which shows another preferable embodiment of the fireproof adhesive tape of this invention. It is the schematic which shows the surface of an example of the refractory layer which has an opening part partially.

≪Fireproof adhesive tape≫
The fire resistant adhesive tape of the present invention includes a fire resistant layer and an adhesive layer. The fireproof layer and the pressure-sensitive adhesive layer are preferably arranged in the outermost layer, respectively. The refractory layer may be only one layer or two or more layers. The pressure-sensitive adhesive layer may be only one layer or two or more layers.

  In the fire-resistant adhesive tape of the present invention, any appropriate other layer can be included between the fire-resistant layer and the adhesive layer as long as the effects of the present invention are not impaired. Such other layers may be only one layer or two or more layers. Examples of such other layers include an easy adhesion layer. By providing the easy-adhesion layer between the refractory layer and the pressure-sensitive adhesive layer, the adhesion between the refractory layer and the pressure-sensitive adhesive layer can be improved, which can contribute to the improvement of the effects of the present invention.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the fire-resistant adhesive tape of the present invention. In FIG. 1, the fireproof adhesive tape 100 of the present invention includes a fireproof layer 10 and an adhesive layer 20.

  FIG. 2 is a schematic cross-sectional view showing another preferred embodiment of the fire-resistant adhesive tape of the present invention. In FIG. 2, the fire resistant adhesive tape 100 of the present invention includes a fire resistant layer 10 and an adhesive layer 20, and has an easy-adhesion layer 30 between the fire resistant layer 10 and the adhesive layer 20.

The fire-resistant adhesive tape of the present invention has a radiation intensity of 50 kW / m ² according to a cone calorimeter test based on ASTM-E-1354 of a composite member obtained by sticking it to an adherend having a thickness of 0.1 mm to 50 mm. the total amount of heat generated in the heating combustion 10 minutes of in, preferably not more than 8 MJ / ^{m 2,} more preferably not more than 5 MJ / ^{m 2,} more preferably not more than 3 MJ / ^{m 2,} particularly preferably 1 MJ / m ² or less. The lower limit of the total calorific value is preferably as small as possible, and most preferably 0 MJ / m ² .

The fire-resistant adhesive tape of the present invention has a radiation intensity of 50 kW / m ² according to a cone calorimeter test based on ASTM-E-1354 of a composite member obtained by sticking it to an adherend having a thickness of 0.1 mm to 50 mm. the total amount of heat generated at 20 minutes heating combustion in, preferably not more than 8 MJ / ^{m 2,} more preferably not more than 5 MJ / ^{m 2,} more preferably not more than 3 MJ / ^{m 2,} particularly preferably 1 MJ / m ² or less. The lower limit of the total calorific value is preferably as small as possible, and most preferably 0 MJ / m ² .

Refractory adhesive tape of the present invention, any of the gross calorific value of the gross calorific value and heat combustion above 20 minutes of heating burning the 10 minutes, preferably 8 MJ / m ² or less, more preferably 5 MJ / m ² or less, still more preferably not more than 3 MJ / ^{m 2,} particularly preferably not more than 1 MJ / ^{m 2.}

The fire-resistant adhesive tape of the present invention has a radiation intensity of 50 kW / m ² according to a cone calorimeter test based on ASTM-E-1354 of a composite member obtained by sticking it to an adherend having a thickness of 0.1 mm to 50 mm. The exothermic time of more than 200 kW / m ² in the 10-minute heating combustion at 10 is preferably less than 10 seconds, more preferably less than 5 seconds, even more preferably less than 3 seconds, and particularly preferably less than 1 second. is there. The lower limit of the heat generation time is preferably as small as possible, and most preferably 0 seconds.

The fire-resistant adhesive tape of the present invention has a radiation intensity of 50 kW / m ² according to a cone calorimeter test based on ASTM-E-1354 of a composite member obtained by sticking it to an adherend having a thickness of 0.1 mm to 50 mm. The exothermic time of more than 200 kW / m ² in the 20-minute heat combustion at is preferably less than 10 seconds, more preferably less than 5 seconds, even more preferably less than 3 seconds, and particularly preferably less than 1 second. is there. The lower limit of the heat generation time is preferably as small as possible, and most preferably 0 seconds.

Refractory adhesive tape of the present invention, any of the heating time of more than 200 kW / ^{m 2} in the heat generating time and heating combustion above 20 minutes greater than 200 kW / ^{m 2} in the heat combustion above 10 minutes, preferably less than 10 seconds More preferably, it is less than 5 seconds, More preferably, it is less than 3 seconds, Most preferably, it is less than 1 second.

The fire-resistant adhesive tape of the present invention has a radiation intensity of 50 kW / m ² according to a cone calorimeter test based on ASTM-E-1354 of a composite member obtained by sticking it to an adherend having a thickness of 0.1 mm to 50 mm. After the 20-minute heating and burning, preferably cracks and penetrations that reach the back side harmful to fire prevention occur but do not disappear. More preferably, cracks and penetrations that reach the back side harmful to fire protection do not occur.

  Any appropriate adherend may be selected as the adherend having a thickness of 0.1 mm to 50 mm. Examples of such adherends include paperboard, wood board, plywood (veneer board), MDF board (hollow fiber board), SPF material (wood deck material), polycarbonate sheet, polyolefin sheet, acrylic resin sheet, polystyrene sheet, Styrofoam, these laminated bodies, etc. are mentioned.

  Details of the corn calorimeter test will be described later.

  In the fireproof adhesive tape of the present invention, the fireproof layer contains aluminum. As such a refractory layer, preferably, an aluminum foil, a laminate in which an aluminum foil is laminated, or a glass cloth aluminum foil is used. Examples of the laminate in which the aluminum foil is laminated include, for example, a laminate of an aluminum foil and a polyolefin layer, a laminate of an aluminum foil and a polyester layer, a laminate of an aluminum foil and a nitrocellulose layer, and an aluminum foil and paper. A laminate, a laminate of an aluminum foil and another metal foil, and the like can be given.

  The fire-resistant pressure-sensitive adhesive tape of the present invention has a fire-resistant layer as described above, so that it can be easily produced at low cost on various base materials with sufficiently high fire resistance that satisfies the certification standards for fire-proof materials in the Building Standard Law as much as possible. Can be granted.

  The thickness of the refractory layer is preferably 5 μm to 300 μm.

  When the refractory layer is an aluminum foil, the thickness of the refractory layer is more preferably 5 μm to 200 μm, still more preferably 5 μm to 100 μm, and particularly preferably 5 μm to 80 μm. When the refractory layer is aluminum foil, the thickness of the refractory layer falls within the above range, so that the refractory pressure-sensitive adhesive tape of the present invention further satisfies the certification standards for fireproof materials in the Building Standard Law as much as possible. Sufficiently high fire resistance can be easily imparted to various substrates at low cost.

  When the fireproof layer is a laminate in which an aluminum foil is laminated, the thickness of the fireproof layer is more preferably 10 μm to 200 μm, still more preferably 30 μm to 170 μm, and particularly preferably 50 μm to 150 μm. When the fire-resistant layer is a laminate in which aluminum foil is laminated, the fire-resistant adhesive tape of the present invention further meets the certification standards for fire-proof materials in the Building Standards Law by keeping the thickness of the fire-resistant layer within the above range. Sufficiently high fire resistance that satisfies as much as possible can be easily imparted to various base materials at low cost.

  When the fireproof layer is a glass cloth aluminum foil, the thickness of the fireproof layer is more preferably 50 μm to 300 μm, still more preferably 100 μm to 300 μm, and particularly preferably 150 μm to 300 μm. When the fire-resistant layer is a glass cloth aluminum foil, the fire-resistant adhesive tape of the present invention further satisfies the certification standards for fire-resistant materials in the Building Standard Act as much as possible by keeping the thickness of the fire-resistant layer within the above range. Such sufficiently high fire resistance can be easily imparted to various substrates at low cost.

  The refractory layer may partially have an opening. When the refractory layer partially has an opening, for example, when the timber is used as an adherend to which the refractory adhesive tape of the present invention is applied to impart fire resistance, the humidity of the timber can be adjusted. Become.

  FIG. 3 is a schematic view showing the surface of an example of a refractory layer partially having an opening. In FIG. 3, the refractory layer 10 has a plurality of apertures 40. The size and number of the opening portions 40 can be appropriately selected according to the required fire resistance, the humidity control level of the wood, and the like. The ratio of the open portion in the entire surface of the fireproof layer (including the open portion) is preferably 10% or less. Arbitrary appropriate hole-opening methods can be selected as a method of providing a hole part in a fireproof layer.

  The thickness of the pressure-sensitive adhesive layer can be appropriately set according to the purpose as long as the effects of the present invention are not impaired. The thickness of the pressure-sensitive adhesive layer is preferably 5 μm to 2 mm, more preferably 10 μm to 1.2 mm, still more preferably 25 μm to 1.0 mm, and particularly preferably 50 μm to 0.8 mm. By keeping the thickness of the pressure-sensitive adhesive layer within the above range, the fire-resistant pressure-sensitive adhesive tape of the present invention has various base materials with sufficiently high fire resistance to satisfy the certification standards for fire-proof materials in the Building Standard Law as much as possible. Can be easily applied at low cost.

  The pressure-sensitive adhesive layer contains a polymer component. The content of the polymer component in the pressure-sensitive adhesive layer is preferably 20% by weight to 100% by weight, more preferably 30% by weight to 100% by weight, and still more preferably based on the solid content of the pressure-sensitive adhesive layer. Is 40% to 100% by weight, particularly preferably 50% to 100% by weight. When the content ratio of the polymer component in the pressure-sensitive adhesive layer is within the above range, an effect that it is hardly peeled off from the adherend even when exposed to a high temperature atmosphere such as a fire can be exhibited.

  As the polymer component in the pressure-sensitive adhesive layer, any appropriate polymer component can be adopted as long as it is a polymer component capable of expressing adhesiveness. The polymer component in the pressure-sensitive adhesive layer may be only one kind or two or more kinds. As such a polymer component, any appropriate pressure-sensitive adhesive can be selected as long as the effects of the present invention are not impaired.

  Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives. Among these, from the viewpoint of easy adjustment of the adhesive properties, low cost, etc., preferably, an acrylic adhesive, a rubber adhesive, and the like, more preferably in consideration of stability such as weather resistance An acrylic pressure-sensitive adhesive can be mentioned.

  As the acrylic polymer, any appropriate acrylic polymer capable of exhibiting adhesiveness can be adopted. The acrylic polymer can be preferably formed from a monomer component essentially comprising an acrylic monomer. The content of the acrylic monomer in the total monomers that can be used to form the acrylic polymer is preferably 50% to 100% by weight, more preferably 55% to 98% by weight, and even more preferably. It is 60 to 95% by weight, particularly preferably 65 to 93% by weight. Only one type of acrylic monomer may be used, or two or more types may be used.

  As an acryl-type monomer, Preferably, the (meth) acrylic-acid alkylester which has an alkyl group is mentioned. Only one (meth) acrylic acid alkyl ester having an alkyl group may be used, or two or more may be used in combination. “(Meth) acryl” means “acryl” and / or “methacryl”.

  Examples of (meth) acrylic acid alkyl ester having an alkyl group include (meth) acrylic acid alkyl ester having a linear or branched alkyl group, (meth) acrylic acid alkyl ester having a cyclic alkyl group, and the like. Is mentioned. In addition, the (meth) acrylic acid alkyl ester here means monofunctional (meth) acrylic acid alkyl ester.

  Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, ( (Meth) acrylic acid decyl, (meth) acrylic acid isodecyl, (meth) a Undecyl silylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl ester having 1 to 20 carbon atoms, such as octadecyl acid, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate. Among these, Preferably, it is a (meth) acrylic acid alkyl ester having 2 to 14 carbon atoms in the alkyl group, and more preferably a (meth) acrylic acid alkyl ester having 2 to 10 carbon atoms in the alkyl group. .

  Examples of the (meth) acrylic acid alkyl ester having a cyclic alkyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

  A polyfunctional monomer can be used as a monomer component that can form an acrylic polymer. Any appropriate multifunctional monomer can be adopted as the multifunctional monomer. By employing a polyfunctional monomer, a crosslinked structure can be imparted to the acrylic polymer. Only 1 type may be used for a polyfunctional monomer and it may use 2 or more types together.

  Examples of the polyfunctional monomer include 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and (poly) ethylene glycol. Di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester Acrylate, urethane acrylate, 4-hydroxybutyl acrylate glycidyl ether, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol (meth) acrylate, 2-hydroxyethyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl ether 2-isocyanatoethyl acrylate, isocyanate ethyl (meth) acrylate, isocyanate (meth) acrylate, triglycidyl isocyanurate, (meth) acrylic acid, monohydroxyethyl phthalate (Meth) acrylate, hexahydroxyphthalate monohydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, 1,4-butanediol diglycidyl Ether, 1,2-ethanediol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenyl Methane triisocyanate, methyl triisocyanate silane, tetraisocyanate silane, polyisocyanate, oxalic acid, Ronic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, 1,2,3-propanetricarboxylic acid, ethylene glycol, diethylene glycol, propylene glycol, dipropylene Glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2,4-butanetriol, polyoxypropylenetriol, trimethylolethane, tri Methylolpropane, aminomethanol, 2-aminoethanol, 3-amino-1-propanol, diethanolamine, triethanolamine, N, N-di-n-butylethanolamine, ethylenediamine, hexamethylenediamine, tolylene Mines, hydrogenated tolylenediamine, diphenylmethanediamine, hydrogenated diphenylmethanediamine, tolidineamine, naphthalenediamine, isophoronediamine, xylenediamine, hydrogenated xylenediamine, vinylamine, 2- (2-thienyl) vinylamine, 1- (allyloxy) vinylamine , Allyl alcohol, 1,3-butadiene monoepoxide, 1-vinyl-3,4-epoxycyclohexane and the like. Among these, acrylate-based polyfunctional monomers are preferable because of high reactivity, and 1,9-nonanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate are more preferable. 4-hydroxybutyl acrylate glycidyl ether.

  As a monomer component capable of forming an acrylic polymer, a polar group-containing monomer can be used. Any appropriate polar group-containing monomer can be adopted as the polar group-containing monomer. By adopting the polar group-containing monomer, it becomes possible to improve the cohesive strength of the acrylic polymer or to improve the adhesive strength of the acrylic polymer. Only 1 type may be used for a polar group containing monomer, and it may use 2 or more types together.

  Examples of polar group-containing monomers include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and other carboxyl group-containing monomers or anhydrides thereof (such as maleic anhydride); (meth) acrylic Hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate, vinyl alcohol, allyl alcohol, etc .; (meth) acrylamide, N, N-dimethyl Amide group-containing monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; aminoethyl (meth) acrylate, (meth) acrylic acid Zimechi Amino group-containing monomers such as aminoethyl and t-butylaminoethyl (meth) acrylate; Glycidyl group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; Cyano groups such as acrylonitrile and methacrylonitrile Containing monomer: N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, N- Heterocycle-containing vinyl monomers such as vinyl oxazole; (meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; monomers containing sulfonic acid groups such as sodium vinyl sulfonate ; 2-phosphoric acid group-containing monomers such as hydroxyethyl acryloyl phosphate; and the like; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; cyclohexyl maleimide, imide group-containing monomers such as isopropyl maleimide. The polar group-containing monomer is preferably a carboxyl group-containing monomer or an anhydride thereof, and more preferably acrylic acid.

  As a monomer component capable of forming an acrylic polymer, other copolymerizable monomers can be used. Any appropriate other copolymerizable monomer can be adopted as the other copolymerizable monomer. By employing other copolymerizable monomers, it becomes possible to improve the cohesive strength of the acrylic polymer or to improve the adhesive strength of the acrylic polymer. Other copolymerizable monomers may be used alone or in combination of two or more.

  Other copolymerizable monomers include, for example, (meth) acrylic acid alkyl esters such as (meth) acrylic acid esters having an aromatic hydrocarbon group such as phenyl (meth) acrylate; vinyl such as vinyl acetate and vinyl propionate Esters; aromatic vinyl compounds such as styrene and vinyltoluene; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; methoxyethyl (meth) acrylate, (meth) (Meth) acrylic acid alkoxyalkyl monomers such as ethoxyethyl acrylate; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphate group-containing monomers such as 2-hydroxyethylacryloyl phosphate; cyclohexyl Maleimide, imide group-containing monomers such as isopropyl maleimide; fluorine-containing (meth) acrylate; 2-methacryloyloxy isocyanate group-containing monomers such as acryloyloxyethyl isocyanate silicon atom-containing (meth) acrylate; and the like.

  The weight average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably 400,000 to 3,000,000. The weight average molecular weight of the acrylic polymer can be determined by a gel permeation chromatography method (GPC method).

  The polymer component in the pressure-sensitive adhesive layer may have a crosslinked structure. When the polymer component in the pressure-sensitive adhesive layer has a crosslinked structure, the pressure-sensitive adhesive layer can exhibit very excellent heat resistance.

  The crosslinked structure can be constructed by any appropriate method. The cross-linked structure is preferably constructed by including a cross-linkable monomer in all monomer components constituting the polymer component. In this case, the content ratio of the crosslinkable monomer in all the monomer components constituting the polymer component is preferably 2.0% by weight to 60% by weight, more preferably 3.0% by weight to 57% by weight. More preferably, the content is 5.0% to 55% by weight, particularly preferably 7.0% to 53% by weight, and most preferably 8.0% to 50% by weight. When the content ratio of the crosslinkable monomer is within the above range, the pressure-sensitive adhesive layer can exhibit much more excellent heat resistance.

  The crosslinkable monomer may be only one type or two or more types.

  As the crosslinkable monomer, any appropriate crosslinkable monomer can be adopted as long as it is a monomer capable of constructing a crosslinked structure. Such a crosslinkable monomer is preferably a crosslinkable monomer having at least one functional group selected from an acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a vinyl group, and an amino group. Specific examples of such a crosslinkable monomer include the aforementioned polyfunctional monomer.

  The polymer component in the pressure-sensitive adhesive layer may contain an antioxidant. When the polymer component in the pressure-sensitive adhesive layer contains an antioxidant, the pressure-sensitive adhesive layer can exhibit very excellent heat resistance.

  The content of the antioxidant in the pressure-sensitive adhesive layer is preferably 0.1% by weight to 10% by weight, more preferably 0.3% by weight to 8% by weight, based on the solid content of the pressure-sensitive adhesive layer. More preferably, it is 0.5 to 6% by weight, and particularly preferably 0.7 to 5% by weight. When the content ratio of the antioxidant falls within the above range, the pressure-sensitive adhesive layer can exhibit much more excellent heat resistance. The antioxidant may be only one kind or two or more kinds.

  Any appropriate antioxidant can be adopted as the antioxidant. As such an antioxidant, Preferably, at least 1 sort (s) chosen from a phenolic antioxidant, an amine antioxidant, an aminoether antioxidant, and a phosphorus antioxidant is mentioned.

Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4 -N-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL-α-tocopherol, steari monocyclic phenolic compounds such as β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4, 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-) -T-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis [3- (3-t-butyl-4-hydride) Xyl-5-methylphenyl) propionate], triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl); ) Isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate Tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4- Tricyclic phenolic compounds such as hydroxybenzyl) benzene; tetracyclic [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] tetracyclic phenolic compounds such as methane; bis (3,5-di -T-butyl-4-hydroxybenzylphosphonate ethyl) phosphorus-containing phenol compounds such as calcium and bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) nickel;

  Examples of amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2, Polycondensate of 6,6-tetramethylpiperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [ {6- (1,1,3 3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6 , 6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6 , 6-Tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-pepyridyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-butyl malonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5, 5-tetramethylpiperazinone (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl- 4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl -3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6 , 6-Pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1, 2,3,4-butanetetracarbo Sylate, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6 Chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine And 1,2-dibromoethane condensate, N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl and the like.

  Examples of amino ether antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1- Propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-pentyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-he Tyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-nonyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-dodecyloxy-2,2,6, 6-tetramethyl-4-piperidyl) sebacate and the like.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite. , Cyclic neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl Tris (dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite, tris Such as 2,4-di -t- butyl-phenyl) phosphite.

  The pressure-sensitive adhesive layer may contain sinterable particles.

  The content ratio of the sinterable particles in the pressure-sensitive adhesive layer is preferably 1% by weight to 80% by weight, more preferably 5% by weight to 70% by weight, based on the solid content of the pressure-sensitive adhesive layer. More preferably, it is 10 weight%-60 weight%, Most preferably, it is 15 weight%-50 weight%. When the content ratio of the sinterable particles in the pressure-sensitive adhesive layer is within the above range, the effect that it is hardly peeled off from the adherend even when exposed to a high-temperature atmosphere such as a fire can be sufficiently exhibited.

  The sinterable particles in the pressure-sensitive adhesive layer preferably include two or more types of sinterable particles having different yield points. When the sinterable particles in the pressure-sensitive adhesive layer contain two or more types of sinterable particles having different yield points, the pressure-sensitive adhesive layer can exhibit very excellent heat resistance.

  The yield point of the sinterable particles in the pressure-sensitive adhesive layer is preferably 250 ° C to 800 ° C, more preferably 250 ° C to 700 ° C, still more preferably 250 ° C to 600 ° C, and particularly preferably 250. C. to 500.degree. When the yield point of the sinterable particles in the pressure-sensitive adhesive layer falls within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high-temperature atmosphere such as in a fire can be sufficiently exhibited.

  Among the two or more types of sinterable particles having different yield points, the yield point of the sinterable particles having the lowest yield point is preferably 250 ° C to 800 ° C, more preferably 250 ° C to 700 ° C. More preferably, it is 250 to 600 ° C, and particularly preferably 250 to 500 ° C. When the yield point of the sinterable particles having the lowest yield point falls within the above range, the pressure-sensitive adhesive layer can exhibit much more excellent heat resistance.

  Arbitrary appropriate sinterability particles can be adopted as sinterability particles in an adhesive layer. Such sinterable particles are preferably inorganic particles having sinterability, and more preferably, silicic acid, boric acid, borosilicate, aluminum oxide, calcium oxide, sodium oxide, lithium oxide, phosphorus oxide. Sinterable particles formed from at least one component selected from By adopting such sinterable particles, the effect that it is very difficult to peel off from the adherend even when exposed to a high temperature atmosphere such as in a fire can be sufficiently exhibited.

  The average particle size of the sinterable particles in the pressure-sensitive adhesive layer is preferably 0.1 μm to 1000 μm, more preferably 0.5 μm to 500 μm, still more preferably 1 μm to 300 μm, and particularly preferably 2 μm to 150 μm. When the average particle diameter of the sinterable particles in the pressure-sensitive adhesive layer falls within the above range, the effect that it is hardly peeled off from the adherend even when exposed to a high-temperature atmosphere such as in a fire can be sufficiently exhibited.

  The pressure-sensitive adhesive layer may contain any appropriate fine particles as long as the effects of the present invention are not impaired. Such fine particles may be only one type or two or more types.

  Examples of the fine particles that can be contained in the pressure-sensitive adhesive layer include metal particles such as copper, nickel, aluminum, chromium, iron, and stainless steel and metal oxide particles thereof; carbide particles such as silicon carbide, boron carbide, and nitrogen carbide; aluminum nitride Nitride particles such as silicon nitride and boron nitride; ceramic particles typified by oxides such as alumina and zirconium; inorganic fine particles such as calcium carbide, aluminum hydroxide, glass and silica; natural raw material particles such as volcanic shirasu and sand And polymer particles such as polystyrene, polymethyl methacrylate, phenol resin, benzoguanamine resin, urea resin, silicone resin, nylon, polyester, polyurethane, polyethylene, polypropylene, polyamide, polyimide, and the like.

  As fine particles that can be contained in the pressure-sensitive adhesive layer, hollow inorganic microspheres or hollow organic microspheres may be employed. Specifically, as the hollow inorganic microspheres, for example, glass hollow balloons such as hollow glass balloons; hollow balloons made of metal compounds such as hollow alumina balloons; porcelain hollow balloons such as hollow ceramic balloons; Etc. Examples of the hollow organic microspheres include resin hollow balloons such as hollow acrylic balloons and hollow vinylidene chloride balloons.

  Examples of commercially available hollow glass balloons include trade names “Glass Micro Balloon” (manufactured by Fuji Silysia Co., Ltd.); trade names “Cell Star Z-25”, “Cell Star Z-27”, “Cell Star CZ-31T”, and “Cell Star Z-”. 36 ”“ Cell Star Z-39 ”“ Cell Star T-36 ”“ Cell Star SX-39 ”“ Cell Star PZ-6000 ”(manufactured by Tokai Kogyo Co., Ltd.); trade name“ Syracx Fine Balloon ”(manufactured by Fine Balloon Co., Ltd.) And so on.

  A solid glass balloon may be employed as the fine particles that can be contained in the pressure-sensitive adhesive layer. As a commercial product of a solid glass balloon, for example, trade name “Sunsphere NP-100” (manufactured by Asahi Glass Co., Ltd.); trade names “micro glass beads EMB-20” “glass beads EGB-210” (Potters Ballotini) Etc.);

  Among the fine particles that can be contained in the pressure-sensitive adhesive layer, hollow inorganic microspheres and hollow organic microspheres are preferable from the viewpoint of the efficiency and weight of polymerization by active energy rays (particularly, ultraviolet rays).

  The surface of the fine particles that can be contained in the pressure-sensitive adhesive layer may be subjected to various surface treatments (for example, a low surface tension treatment with a silicone compound or a fluorine compound).

  The particle size (average particle size) of the fine particles that can be contained in the pressure-sensitive adhesive layer is not particularly limited, but for example, is preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm, and further preferably 10 μm to 100 μm. is there.

Any appropriate specific gravity can be adopted as the specific gravity (true density) of the fine particles that can be contained in the pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired. Such specific gravity, preferably ^{0.01g / cm 3 ~1.8g / cm 3} , more preferably ^{0.02g / cm 3 ~1.5g / cm 3} . When the specific gravity of the fine particles that can be contained in the pressure-sensitive adhesive layer is greater than 0.01 g / cm ^3, when the fine particles are blended with the polymer component and mixed, the fine particles are unlikely to float, and the fine particles are easily dispersed uniformly. Further, cracking of the fine particles can be suppressed. When the specific gravity of the fine particles that can be contained in the pressure-sensitive adhesive layer is less than 1.8 g / cm ³ , there is little influence on the transmittance of active energy rays (particularly ultraviolet rays), that is, the efficiency of the photocuring reaction. The weight of the fireproof adhesive tape does not become too large and the workability is good.

  As a blending amount of the fine particles that can be contained in the pressure-sensitive adhesive layer, any appropriate blending amount can be adopted as long as the effects of the present invention are not impaired. Such a blending amount is preferably 5% by volume (volume%) to 50% by volume (volume%), more preferably 10% by volume (volume%) to 50% with respect to the total volume of the pressure-sensitive adhesive layer. It is volume% (volume%), and more preferably 15 volume% (volume%) to 40 volume% (volume%). When the blending amount is within the above range, the effects of adhesion strength and shear strength at room temperature by adding fine particles are sufficiently exhibited.

  The pressure-sensitive adhesive layer may contain any appropriate other component as long as the effects of the present invention are not impaired. Such other components may contain only 1 type, and may contain 2 or more types.

  Other components include, for example, other polymer components, softeners, anti-aging agents, curing agents, plasticizers, fillers, thermal polymerization initiators, photopolymerization initiators, ultraviolet absorbers, light stabilizers, colorants ( Pigments and dyes), solvents (organic solvents), surfactants (eg, ionic surfactants, silicone surfactants, fluorosurfactants, etc.), crosslinking agents (eg, polyisocyanate crosslinking agents, silicones) System crosslinking agents, epoxy crosslinking agents, alkyl etherified melamine crosslinking agents, etc.). In addition, a thermal polymerization initiator and a photoinitiator may be contained in the material for forming a polymer component.

  Any appropriate thermal polymerization initiator can be adopted as the thermal polymerization initiator. Examples of such thermal polymerization initiators include peroxide polymerization initiators such as hydrogen peroxide, benzoyl peroxide, and t-butyl peroxide; 2,2′-azobis-2-methylpropioaminate 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-N, N′-dimethyleneisobutylaminate, 2,2′-azobisisobutyronitrile, 2,2 And azo polymerization initiators such as' -azobis-2-methyl-N- (2-hydroxyethyl) propionamide; Only one type of thermal polymerization initiator may be used, or two or more types may be used in combination. Such a thermal polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent. Examples of such a reducing agent include ionized salts such as sulfites, hydrogen sulfites, iron, copper, and cobalt salts; amines such as triethanolamine; reducing sugars such as aldose and ketose;

  The content of the thermal polymerization initiator in the pressure-sensitive adhesive layer is preferably 5 parts by weight or less, more preferably 0.01 parts by weight with respect to the monomer component used to form the polymer component of the pressure-sensitive adhesive layer. -5 parts by weight, more preferably 0.05-3 parts by weight.

  Arbitrary appropriate photoinitiators can be employ | adopted as a photoinitiator. Examples of such photopolymerization initiators include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime systems. Examples include photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators. Only 1 type may be used for a photoinitiator and it may use 2 or more types together.

  Examples of the ketal photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, trade name “Irgacure 651” (manufactured by Ciba Specialty Chemicals), etc.). It is done. Examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone (for example, trade name “Irgacure 184” (manufactured by Ciba Specialty Chemicals), etc.), 2,2-diethoxyacetophenone, 2,2- Examples include dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, and 4- (t-butyl) dichloroacetophenone. Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the acylphosphine oxide photopolymerization initiator include trade name “Lucirin TPO” (manufactured by BASF). Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. . Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzyl photopolymerization initiator include benzyl. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

  The content ratio of the photopolymerization initiator in the pressure-sensitive adhesive layer is preferably 5 parts by weight or less, more preferably 0.01 parts by weight with respect to the monomer component used to form the polymer component of the pressure-sensitive adhesive layer. -5 parts by weight, more preferably 0.05-3 parts by weight.

  The pressure-sensitive adhesive layer is mainly composed of an acrylic polymer obtained by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method or a UV polymerization method. It can be prepared by adding various additives such as a rust inhibitor such as a benzotriazole and a filler. In addition, the adhesive layer may have a resin film, a nonwoven fabric, cloth, etc. in the adhesive layer.

  The refractory adhesive tape of the present invention is a refractory adhesive tape including a refractory layer and an adhesive layer, and the refractory layer can be formed on the adherend by adhering it to the adherend with an adhesive. As a result, there is no need to use a solvent during construction as in the case of bonding aluminum foil using an adhesive, so the work environment is good, and the drying time of the adhesive is unnecessary, so a fireproof layer can be easily formed on the adherend. In addition, the thickness of the pressure-sensitive adhesive can be made constant rather than applying an adhesive, and the design is excellent. Moreover, the position correction by re-sticking is also attained by using an adhesive. Furthermore, since the pressure-sensitive adhesive is a flexible viscoelastic body, it can be expected that the adhesive reliability with respect to vibration and impact is higher than when the adhesive is bonded.

≪Method for manufacturing fire-resistant adhesive tape≫
The fire-resistant adhesive tape of the present invention can be produced by any appropriate method. The fire-resistant pressure-sensitive adhesive tape of the present invention is preferably formed by laminating a fire-resistant layer and a pressure-sensitive adhesive layer, or by forming a pressure-sensitive adhesive layer by laminating a material for forming a pressure-sensitive adhesive layer and a fire-resistant layer and then curing reaction And a method of manufacturing the same.

  As one method for producing the pressure-sensitive adhesive layer, for example, a polymerizable composition containing a monomer component used for forming a polymer component and any other appropriate component (such as a tackifier or a crosslinking agent) The method of coating on a suitable base material (separator etc.) and drying and manufacturing is mentioned. Further, as another method for producing the pressure-sensitive adhesive layer, for example, a polymerizable syrup is obtained by partially polymerizing a polymerizable composition containing a monomer component used for forming a polymer component and any appropriate photopolymerization initiator. Prepare and add sinterable particles, etc. to the polymerizable syrup as needed to disperse it uniformly, and then coat it on any appropriate substrate (separator, etc.) and photopolymerize it by irradiating it with light. The method of (curing) is mentioned.

  Arbitrary appropriate conditions can be employ | adopted about conditions, such as a light source in the case of light irradiation, irradiation energy, an irradiation method, and irradiation time.

  Examples of active energy rays used for light irradiation include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron rays, and ultraviolet rays. Preferably it is an ultraviolet-ray.

  Examples of irradiation with active energy rays include irradiation with a black light lamp, a chemical lamp, a high-pressure mercury lamp, a metal halide lamp, and the like.

  Heating may be performed during the polymerization. Any appropriate heating method can be adopted as the heating method. Examples of the heating method include a heating method using an electric heater, a heating method using electromagnetic waves such as infrared rays, and the like.

  The fire-resistant adhesive tape of the present invention can be produced by laminating a fire-resistant layer on the adhesive layer obtained by the production method as described above by any appropriate method.

≪Fireproofing method≫
By using the fire-resistant adhesive tape of the present invention, a ceiling material for buildings, a floor material for buildings, a wall material for buildings, a ceiling material for railway vehicles, a floor material for rail vehicles, a wall material for rail vehicles, an interior for aircraft Various base materials such as paper, wood board, resin board and the like employed for structural materials (fireproof partitions, etc.) that require fire resistance, such as materials and marine materials, can be made nonflammable to improve fire resistance. That is, the fireproofing treatment method of the present invention is performed using the fireproof adhesive tape of the present invention.

  According to the fire-resistant treatment method of the present invention, sufficiently high fire resistance that satisfies the certification standards for fire-proof materials in the Building Standards Act as much as possible can be easily applied to various base materials such as paper, wood board and resin board at low cost. Can be granted. The fireproof treatment method of the present invention is particularly effective for combustible substrates.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all.

  The separators and cover separators used in each of the following examples are each a biaxially stretched polyethylene terephthalate film with a thickness of 38 μm (trade name “MRN38”, manufactured by Mitsubishi Chemical Polyester Film Co. ).

[Synthesis Example 1] (Preparation of photopolymerizable syrup (A))
As monomer components, 2-ethylhexyl acrylate: 90 parts by weight, acrylic acid: 10 parts by weight, photopolymerization initiator (trade name “Irgacure 651”, manufactured by BASF): 0.05 part by weight, and photopolymerization initiator (trade name) "Irgacure 184" (manufactured by BASF): Nitrogen gas after stirring 0.05 parts by weight in a four-necked separable flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube until uniform Was carried out for 1 hour to remove dissolved oxygen. Thereafter, ultraviolet light was irradiated from the outside of the flask with a black light lamp to polymerize, and when the viscosity reached an appropriate level, the lamp was turned off and nitrogen blowing was stopped to partially polymerize at a polymerization rate of 3.5%. A photopolymerizable syrup (A) as a composition was prepared.

[Synthesis Example 2] (Preparation of pressure-sensitive adhesive composition (A))
A polymerization vessel was charged with 95 parts by weight of n-butyl acrylate, 5 parts by weight of acrylic acid, and 150 parts by weight of toluene, and purged with nitrogen at room temperature for 1 hour. Thereafter, the temperature was raised to 60 ° C., 0.22 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator was added, polymerization was conducted at 63 ° C. for 7 hours, and the weight average molecular weight was 500,000 An acrylic polymer copolymer solution was obtained. In this copolymer solution, a xylene formaldehyde tackifier resin having a hydroxyl group as a tackifier resin with respect to 100 parts by weight of the solid content of the copolymer (trade name “Nikanol H-80”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) : 30 parts by weight and a hydroxy compound containing a nitrogen atom as a hydroxy compound (trade name “EDP-300”, manufactured by Asahi Denka Co., Ltd., polyhydroxyalkylamine compound): 0.05 part by weight, isocyanate compound (trade name) “Coronate L” (manufactured by Nippon Polyurethane Industry Co., Ltd.): 4 parts by weight were added and mixed well to obtain an adhesive composition (A) (solid content 40%).

[Synthesis Example 3] (Preparation of pressure-sensitive adhesive layer (A))
Acrylic polymer (acrylic polymer obtained by polymerization using 2-ethylhexyl acrylate: 70 parts by weight, butyl acrylate: 30 parts by weight, acrylic acid: 2 parts by weight): polymerization with respect to 100 parts by weight Rosin resin (trade name “Pencel D125”, manufactured by Arakawa Chemical Co., Ltd.): 30 parts by weight are added, and further, an isocyanate-based crosslinking agent (trade name “Coronate L”, manufactured by Nippon Polyurethane Industry Co., Ltd.): 2 parts by weight. The adhesive composition was prepared by addition.
The prepared pressure-sensitive adhesive composition was applied to the separator release surface and dried to obtain a pressure-sensitive adhesive layer (A) having a thickness of 50 μm formed on the separator.

[Synthesis Example 4] (Preparation of pressure-sensitive adhesive layer (B))
Photopolymerizable syrup obtained in Synthesis Example 1 (A): 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, and phosphate frit (manufactured by Takara Standard Co., Ltd., VY0144) , Yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper to obtain a frit dispersion syrup. The obtained frit-dispersed syrup was applied onto the release-treated surface of the separator so as to have a thickness of 150 μm after curing. It was bonded onto the coated surface so that the peeled surface of the cover separator was in contact. Next, using a black light lamp (“Black Light” manufactured by Toshiba Corporation) as a light source, ultraviolet light having an illuminance of 5 mW / cm ² was irradiated for 5 minutes to cure the frit dispersion syrup. Thereafter, the cover separator was peeled off to obtain a pressure-sensitive adhesive layer (B) having a thickness of 150 μm, one side of which was covered with the separator.

[Synthesis Example 5] (Preparation of pressure-sensitive adhesive layer (C))
After adding 0.08 parts by weight of 1,6-hexanediol diacrylate (HDDA) to 100 parts by weight of the photopolymerizable syrup (A) obtained in Synthesis Example 1, hollow glass balloons (average particle size of 40 μm, product) The name “Fuji Balloon H-40” manufactured by Fuji Silysia Chemical Co., Ltd. is added to 12.5 parts by weight with respect to 100 parts by weight of the photopolymerizable syrup (A), and a photopolymerization initiator (trade name “Irgacure 651” is added. “Made by BASF): 0.04 part by weight was added to obtain a pressure-sensitive adhesive composition containing hollow inorganic fine particles. The pressure-sensitive adhesive composition was applied to the separator release surface. It was bonded onto the coated surface so that the peeled surface of the cover separator was in contact. Next, a black light lamp (“Black Light” manufactured by Toshiba Corporation) was used as a light source, and ultraviolet rays with an illuminance of 5 mW / cm ² were irradiated from both sides for 3 minutes to be cured. Thereafter, the cover separator was peeled off to obtain a pressure-sensitive adhesive layer (C) having a thickness of 1200 μm, one side of which was covered with the separator.

[Synthesis Example 6] (Preparation of pressure-sensitive adhesive layer (D))
In some cases, a silicone release agent is applied to both surfaces of a high-quality paper (glassine paper, density 70 g / m ² , thickness 130 μm) that has been laminated with polyethylene on both sides, and is referred to as a release liner (“release liner A”). The pressure-sensitive adhesive composition (A) obtained in Synthesis Example 2 was applied to one side of the release liner A so that the thickness after drying was 80 μm, and the temperature was 110 ° C. for 3 minutes. It dried and formed the adhesive layer D1, and produced the release liner A in which the adhesive layer D1 was formed. The release liner A on which the pressure-sensitive adhesive layer D1 is formed is coated on one side of a basis weight rayon pulp nonwoven fabric (trade name “MR base paper (basis weight 14 g / m ² )”, manufactured by Miki Special Paper Co., Ltd.). The adhesive layer A with a nonwoven fabric was obtained by overlapping and bonding in a form in which D1 was in contact.
The pressure-sensitive adhesive composition (A) obtained in Synthesis Example 2 is formed on one side of another release liner (sometimes referred to as “release liner B”). Then, coating was performed so that the thickness after drying was 80 μm, and drying was performed at a temperature of 110 ° C. for 3 minutes to form a pressure-sensitive adhesive layer D2. Thus, a release liner B on which the pressure-sensitive adhesive layer D2 was formed was produced. The release liner B on which the pressure-sensitive adhesive layer D2 is formed is laminated and bonded in a form in which the nonwoven fabric surface of the pressure-sensitive adhesive layer A with the nonwoven fabric and the pressure-sensitive adhesive layer D2 are in contact with each other. A pressure-sensitive adhesive layer (D) having a thickness of 160 μm covered with a release liner A having a thickness of 130 μm was prepared.

[Example 1]
On the aluminum sheet (thickness: 50 μm), the pressure-sensitive adhesive layer (A) having a separator on one side obtained in Synthesis Example 3 was bonded with a hand roller, and then the separator was peeled off to obtain an aluminum having a thickness of 100 μm. A base material pressure-sensitive adhesive sheet (1) was produced.

[Example 2]
On the aluminum sheet (thickness: 12 μm), the pressure-sensitive adhesive layer (D) obtained by synthesizing Example 6 with one side covered with release liner A was bonded with a hand roller, and then release liner A was peeled off. An aluminum substrate pressure-sensitive adhesive sheet (2) having a thickness of 172 μm was produced.

Example 3
On the aluminum sheet (thickness: 12 μm), the pressure-sensitive adhesive layer (B) having a separator on one side obtained in Synthesis Example 4 was bonded with a hand roller, and then the separator was peeled off to obtain an aluminum having a thickness of 162 μm. A base material pressure-sensitive adhesive sheet (3) was produced.

Example 4
On the aluminum sheet (thickness: 12 μm), the pressure-sensitive adhesive layer (C) having a separator on one side obtained in Synthesis Example 5 was bonded with a hand roller, and then the separator was peeled off to obtain aluminum having a thickness of 1212 μm. A base material pressure-sensitive adhesive sheet (4) was produced.

Example 5
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded onto a veneer plate (thickness: 2.3 mm) with a hand roller to obtain a composite member (1). This composite member (1) was used for evaluation.

Example 6
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded to a veneer plate (thickness: 5.5 mm) with a hand roller to obtain a composite member (2). This composite member (2) was used for evaluation.

Example 7
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded to an MDF plate (medium density fiber plate) (thickness: 9 mm) with a hand roller to obtain a composite member (3). This composite member (3) was used for evaluation.

Example 8
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded to a polycarbonate plate (thickness: 2 mm, trade name “PC1600”, manufactured by Takiron Co., Ltd.) with a hand roller to obtain a composite member (4). It was. This composite member (4) was used for evaluation.

Example 9
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded to a polycarbonate sheet (thickness: 0.5 mm, trade name “POLICA ACE ECG101S”, manufactured by Sumitomo Bakelite Co., Ltd.) with a hand roller, and a composite member ( 5) was obtained. This composite member (5) was used for evaluation.

Example 10
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was pasted on a polypropylene plate (thickness: 2 mm, trade name “Kobe poly sheet polypropylene plate PP-N-AN”, manufactured by Shin-Kobe Electric Machinery Co., Ltd.) with a hand roller. In addition, a composite member (6) was obtained. This composite member (6) was used for evaluation.

Example 11
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded to an acrylic plate (thickness: 2 mm, trade name “Acrylite 001”, manufactured by Mitsubishi Rayon Co., Ltd.) with a hand roller, and a composite member (7 ) This composite member (7) was used for evaluation.

Example 12
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded onto an SPF material (thickness: 19 mm) with a hand roller to obtain a composite member (8). This composite member (8) was used for evaluation.

Example 13
The aluminum substrate pressure-sensitive adhesive sheet (1) obtained in Example 1 was bonded onto an SPF material (thickness: 38 mm) with a hand roller to obtain a composite member (9). This composite member (9) was used for evaluation.

Example 14
The aluminum substrate pressure-sensitive adhesive sheet (2) obtained in Example 2 was bonded onto a veneer plate (thickness: 2.3 mm) with a hand roller to obtain a composite member (10). This composite member (10) was used for evaluation.

Example 15
The aluminum substrate pressure-sensitive adhesive sheet (3) obtained in Example 3 was bonded onto a veneer plate (thickness: 2.3 mm) with a hand roller to obtain a composite member (11). This composite member (11) was used for evaluation.

Example 16
The aluminum substrate pressure-sensitive adhesive sheet (4) obtained in Example 4 was bonded onto a veneer plate (thickness: 2.3 mm) with a hand roller to obtain a composite member (12). This composite member (12) was used for evaluation.

Example 17
Two aluminum base adhesive sheets (thickness: 110 μm, width: 50 mm, trade name “aluminum craft tape J3200”, manufactured by Nitoms Co., Ltd.) are laminated on a veneer plate (thickness: 2.3 mm) with a hand roller without any gap. A composite member (13) was obtained. This composite member (13) was used for evaluation.

Example 18
Two aluminum base adhesive sheets (thickness: 110 μm, width: 50 mm, trade name “Aluminum Kraft Tape J3200”, manufactured by Nitoms Co., Ltd.) are laminated on a veneer plate (thickness: 5.5 mm) with a hand roller without any gap. A composite member (14) was obtained. This composite member (14) was subjected to evaluation.

Example 19
Kenyama (trade name “Chiyoshi Kenyama Daikaku No. 14”, manufactured by Fujiwara Sangyo Co., Ltd.) was pressed against the aluminum base adhesive sheet (1) obtained in Example 1, and the diameter was 0.4 mm at intervals of 3.5 mm. The aluminum base material adhesive sheet which has a hole part was obtained. The aluminum substrate pressure-sensitive adhesive sheet having the aperture was bonded to a veneer plate (thickness: 2.3 mm) with a hand roller to obtain a composite member (15). This composite member (15) was used for evaluation.

Example 20
Kenyama (trade name “Chiyoshi Kenyama Daikaku No. 14”, manufactured by Fujiwara Sangyo Co., Ltd.) was pressed against the aluminum base adhesive sheet (1) obtained in Example 1, and the diameter was 0.4 mm at intervals of 3.5 mm. The aluminum base material adhesive sheet which has a hole part was obtained. The aluminum substrate pressure-sensitive adhesive sheet having the aperture was bonded to a veneer plate (thickness: 5.5 mm) with a hand roller to obtain a composite member (16). This composite member (16) was used for evaluation.

[Comparative Example 1]
A single veneer plate (thickness: 2.3 mm) was used for evaluation.

[Comparative Example 2]
A veneer plate (thickness: 5.5 mm) alone was used for evaluation.

[Comparative Example 3]
A single MDF plate (thickness: 9 mm) was used for evaluation.

[Comparative Example 4]
A polycarbonate plate (thickness: 2 mm, trade name “PC1600”, manufactured by Takiron Co., Ltd.) alone was used for evaluation.

[Comparative Example 5]
A polycarbonate sheet (thickness: 0.5 mm, trade name “POLICA ACE ECG101S”, manufactured by Sumitomo Bakelite Co., Ltd.) alone was used for evaluation.

[Comparative Example 6]
A polypropylene plate (thickness: 2 mm, trade name “Kobe poly sheet polypropylene plate PP-N-AN”, manufactured by Shin-Kobe Electric Machinery Co., Ltd.) alone was used for evaluation.

[Comparative Example 7]
A single acrylic plate (thickness: 2 mm, trade name “Acrylite 001”, manufactured by Mitsubishi Rayon Co., Ltd.) was used for evaluation.

[Comparative Example 8]
The pressure-sensitive adhesive layer (A) obtained in Synthesis Example 3 was bonded to the PET surface of aluminum-deposited PET (thickness: 25 μm, trade name “Metal Me 25S”, manufactured by Toray Industries, Inc.) with a hand roller, and then a separator was attached. It peeled off and the aluminum base adhesive sheet (5) with a thickness of 88 micrometers was obtained. This aluminum substrate pressure-sensitive adhesive sheet (5) was bonded to a veneer plate (thickness: 2.3 mm) with a hand roller to obtain a composite member (17) having an aluminum deposited layer on the surface. This composite member (17) was used for evaluation.

[Comparative Example 9]
An SPF material (thickness: 19 mm) alone was used for evaluation.

[Comparative Example 10]
An SPF material (thickness: 38 mm) alone was used for evaluation.

[Total calorific value and heat generation time by corn calorimeter test]
A plane square test piece having a side of 99 mm was cut out from the evaluation object (composite member obtained in the example and various members prepared in the comparative example), and this test piece was subjected to a combustion test (ASTM E 1354). Using a corn calorimeter, the test piece was burned by irradiation with 50 kW / m ² of heat rays. The total calorific value (MJ / m ² ) and the exothermic time (seconds) exceeding 200 kW / m ² were measured when 10 minutes and 20 minutes elapsed when the test piece was heated and burned for 20 minutes.

(Criteria)
(1) Total calorific value A: Total calorific value for 20 minutes is 8 MJ / m ² or less.
○: The total calorific value for 20 minutes exceeds 8 MJ / m ^2, and the total calorific value for 10 minutes is 8 MJ / m ² or less.
X: The total calorific value for 10 minutes exceeds 8 MJ / m ² .
(2) Heat generation time exceeding 200 kW / m ^{2 A} : Heat generation time (second) exceeding 200 kW / m ² in 20 minutes is less than 10 seconds.
○: Heat generation time (second) exceeding 200 kW / m ² in 20 minutes is 10 seconds or more, and heat generation time (second) exceeding 200 kW / m ² in 10 minutes is less than 10 seconds.
X: Exothermic time (second) exceeding 200 kW / m ² in 10 minutes is 10 seconds or more.
(3) Crack / penetration ○: No crack or penetration harmful to fire prevention.
Δ: Cracks and penetrations harmful to fire prevention.
X: Disappearance.

  The fire-resistant adhesive tape of the present invention is a general building material such as a wooden house such as a conventional shaft construction method or a frame wall construction method, a reinforced concrete construction, a light steel construction or a heavy steel construction, a prefabrication construction construction, etc. Residential buildings, super high-rise apartments, high-rise apartments, low-rise apartments, apartment buildings such as apartments, coffee shops, restaurants, office buildings, department stores, supermarkets, indoor parking lots, movie theaters, hotels, various sports facilities, gymnasiums, concert halls, domes Type baseball stadium, soccer field, indoor soccer field, indoor pool, factory building and other large buildings and public facilities exterior wall materials, exterior wall finish materials, interior wall materials, interior wall finish materials, wall insulation materials, ceiling materials, ceiling finish materials Roofing materials, flooring materials, flooring materials, partition materials, bathroom wall materials, flooring materials and ceiling materials and finishing materials, kitchen wall materials, flooring materials and ceiling materials These finishing materials, toilet wall materials, floor materials, ceiling materials and finishing materials, pillar materials, column protection materials, interior materials and surface finishing materials for various doors such as toilets, interiors, entrances, and walls, partition materials It can be suitably used for curtains, especially wall materials and ceiling materials for kitchens, partitioning of clean rooms, and the like. In addition, interior materials or surface finishing materials of fire prevention equipment such as exhaust ducts, fire doors and fire shutters, furniture surface finishing materials such as tables, door surface finishing materials, window glass surface finishing materials, furniture surface finishing materials such as tables, It can be used for anti-scattering materials and surface finishing materials such as window glass, mirrors and tiles, surface finishing materials for signboards and electronic signage, and roll screens. Also, body protection materials for ships, aircraft, automobiles, railway vehicles, internal and external wall materials, ceiling materials, roofing materials, flooring materials, partition materials, surface protection materials for printed materials affixed inside and outside railway vehicles, inkjet media It can be used for surface protection materials for materials, other external protection materials and internal protection materials for solar cells, battery protection materials such as lithium ion batteries, and electrical / electronic equipment members such as partitions inside electrical equipment. Furthermore, it can also be used as an ashtray peripheral tool, a surface finishing material of a trash can, a front panel of a pachinko machine, or a casing protective material.

DESCRIPTION OF SYMBOLS 10 Fireproof layer 20 Adhesive layer 30 Easy-adhesion layer 40 Opening part 100 Fireproof adhesive tape

Claims (10)

A fire resistant adhesive tape comprising a fire resistant layer and an adhesive layer,
The refractory layer comprises aluminum;
Fire resistant adhesive tape. Heating for 20 minutes at a radiation intensity of 50 kW / m ² by a cone calorimeter test according to ASTM-E-1354 of a composite member obtained by sticking the fire resistant adhesive tape to an adherend having a thickness of 0.1 mm to 50 mm. The fireproof adhesive tape according to claim 1, wherein the total calorific value in combustion is 8 MJ / m ² or less. Heating for 20 minutes at a radiation intensity of 50 kW / m ² by a cone calorimeter test according to ASTM-E-1354 of a composite member obtained by sticking the fire resistant adhesive tape to an adherend having a thickness of 0.1 mm to 50 mm. heating time of more than 200 kW / ^{m 2} in the combustion is less than 10 seconds, refractory adhesive tape according to claim 1 or 2. Heating for 20 minutes at a radiation intensity of 50 kW / m ² by a cone calorimeter test according to ASTM-E-1354 of a composite member obtained by sticking the fire resistant adhesive tape to an adherend having a thickness of 0.1 mm to 50 mm. The fire resistant adhesive tape according to any one of claims 1 to 3, wherein no crack or penetration reaching the back surface occurs after combustion.   The fireproof adhesive tape according to any one of claims 1 to 4, wherein the fireproof layer has a thickness of 5 µm to 300 µm.   The fireproof adhesive tape according to any one of claims 1 to 5, wherein the fireproof layer is any one of an aluminum foil, a laminate in which the aluminum foil is laminated, and a glass cloth aluminum foil.   The fire-resistant adhesive tape in any one of Claim 1 to 6 in which the said adhesive layer contains an acrylic adhesive.   The fireproof adhesive tape according to any one of claims 1 to 7, wherein the fireproof layer partially has an opening.   The fireproof adhesive tape according to any one of claims 1 to 8, wherein the pressure-sensitive adhesive layer has a thickness of 5 µm to 2 mm.   The fireproof processing method performed using the fireproof adhesive tape in any one of Claim 1-9.

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