Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/02—Inorganic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/027—Thermal properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • E—FIXED CONSTRUCTIONS
  • E04—BUILDING
  • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
  • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
  • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
  • E04B1/92—Protection against other undesired influences or dangers
  • E04B1/94—Protection against other undesired influences or dangers against fire
• • E—FIXED CONSTRUCTIONS
  • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
  • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
  • E06B5/00—Doors, windows, or like closures for special purposes; Border constructions therefor
  • E06B5/10—Doors, windows, or like closures for special purposes; Border constructions therefor for protection against air-raid or other war-like action; for other protective purposes
  • E06B5/16—Fireproof doors or similar closures; Adaptations of fixed constructions therefor
  • E06B5/164—Sealing arrangements between the door or window and its frame, e.g. intumescent seals specially adapted therefor

Definitions

• the present invention relates to a thermally expandable fire-resistant sheet.
• fireproof materials are used in fire prevention equipment such as doors and windows.
• fireproof materials include fireproof sheets made of resin mixed with inorganic fillers and thermally expandable graphite (see, for example, Patent Document 1).
• Such fireproof sheets expand when heated, and the combustion residue forms a fireproof insulation layer, thereby achieving fireproof insulation performance.
• fireproof sheets are placed in the gaps between doors and windows and the frames that surround them, such as door frames and window frames, and in the event of a fire, the sheet expands in the thickness direction to close the gap and prevent the fire from spreading.
• an object of the present invention is to provide a heat-expandable fire-resistant sheet that has a low expansion initiation temperature, has a good appearance, and is long.
• a heat-expandable fire-resistant sheet that contains a matrix component and heat-expandable graphite, has an expansion start temperature of 160°C or less, and is a rolled body with a length of 1 m or more, and have completed the present invention. That is, the present invention provides the following [1] to [8].
• the present invention provides a heat-expandable fire-resistant sheet that has a low expansion start temperature, a good appearance, and is long.
• the thermally expandable fire-resistant sheet of the present invention contains a matrix component and thermally expandable graphite, and has an expansion start temperature of 160°C or less, an average thickness of 0.5 mm or more, a thickness variation of 10% or less of the average thickness, and is a rolled body having a length of 1 m or more.
• the thermally expandable fire-resistant sheet of the present invention will be described in detail below.
• the thermally expandable fire-resistant resin sheet of the present invention contains a matrix component in which thermally expandable graphite, as well as a thermally expandable inorganic material other than thermally expandable graphite and an inorganic filler, which are blended as necessary, are dispersed.
• the matrix component is not particularly limited, and may be a thermoplastic resin, a thermosetting resin, a rubber, etc.
• the matrix component may be formed of one kind of component, or may be formed of a plurality of components.
• Thermoplastic resins include polyvinyl chloride resin, polypropylene resin, polyethylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, vinyl acetate copolymer resin, fluororesin, phenolic resin, polycarbonate resin, acrylic resin, polystyrene resin, polyacrylonitrile resin, etc.
• Thermosetting resins include polyurethane resin, phenolic resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, polyimide, etc.
• Rubber includes natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), styrene-based thermoplastic elastomer, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluororubber, urethane rubber, etc.
• the matrix component is preferably a resin for extrusion molding, a dry-solidifying adhesive, a moisture-curing reaction type adhesive, a hot-melt adhesive, or a thermosetting reaction type adhesive.
• the matrix component is one of these specific resin components, it is easy to obtain a long heat-expandable fire-resistant sheet with a length of 1 m or more, with a good appearance.
• the resin for extrusion molding is a resin that can be used to obtain a heat-expandable fireproof sheet by extrusion molding.
• the resin for extrusion molding as a matrix component in a heat-expandable composition for obtaining a heat-expandable fireproof sheet
• the heat-expandable composition can be extrusion molded to obtain a heat-expandable fireproof sheet.
• the resin for extrusion molding examples include thermoplastic resins and rubbers, which are as described above.
• the resin for extrusion molding is preferably rubber, and in particular, at least one selected from the group consisting of chloroprene rubber, styrene-butadiene rubber, and styrene-based thermoplastic elastomers is preferred.
• styrene-based thermoplastic elastomer examples include styrene-butadiene-styrene (SBS), polystyrene-poly(ethylene-propylene) (SEP), polystyrene-poly(ethylene-butylene)-polystyrene (SEBS), polystyrene-poly(ethylene-propylene)-polystyrene (SEPS), polystyrene-poly(ethylene-ethylene/propylene)-polystyrene (SEEPS), styrene-isoprene-styrene (SIS), etc.
• SBS or SEP are preferred.
• the dry-solidification type adhesive examples include a solvent-based adhesive, an emulsion-based adhesive, and a synthetic rubber latex-based adhesive.
• the thermally expandable composition for obtaining the thermally expandable fireproof sheet is in a liquid state, so that the load during kneading is reduced and the deterioration of the thermally expandable graphite can be suppressed. Therefore, the generation of gas caused by the deterioration of the thermally expandable graphite is suppressed, and a long thermally expandable fireproof sheet with good appearance can be obtained.
• the solvent-based adhesive exists as a solid in the heat-expandable fire-resistant sheet, but is dissolved in an organic solvent in the heat-expandable composition for obtaining the heat-expandable fire-resistant sheet. Therefore, when the solvent-based adhesive is used, the heat-expandable composition contains an organic solvent. In addition, the heat-expandable composition can be solidified by volatilizing the organic solvent.
• the solvent-based adhesive include vinyl acetate resin-based, vinyl acetate copolymer resin-based, rubber-based, acrylic resin-based, polyester-based, silicone resin-based, etc.
• the silicone resin-based adhesive is preferably a non-modified silicone resin-based adhesive.
• examples of vinyl acetate copolymer resins include copolymers of vinyl acetate and monomers copolymerizable with vinyl acetate (e.g., ⁇ -olefins, (meth)acrylic acid esters, etc.), such as vinyl acetate-(meth)acrylic acid ester copolymers.
• the (meth)acrylic acid is a concept that includes both acrylic acid and methacrylic acid.
• the rubbers include chloroprene, butadiene, styrene-butadiene, butadiene-acrylonitrile, isobutylene-isoprene, ethylene-propylene, etc., with chloroprene being preferred.
• chloroprene, acrylic resin-based, or silicone resin-based (non-modified) adhesives are preferred.
• the emulsion type adhesive exists as a solid in the heat-expandable fire-resistant sheet, but is dispersed in a dispersion medium, preferably water, in the heat-expandable composition for obtaining the heat-expandable fire-resistant sheet.
• a dispersion medium such as water.
• emulsion-type adhesives include vinyl acetate resin-based, vinyl acetate copolymer resin-based, acrylic resin-based, aqueous polymer-isocyanate-based, and polyurethane-based adhesives, with vinyl acetate copolymer resin-based and polyurethane-based adhesives being preferred.
• the synthetic rubber latex adhesive exists as a solid in the heat-expandable fire-resistant sheet, but is dispersed in a dispersion medium, preferably water, in the heat-expandable composition for obtaining the heat-expandable fire-resistant sheet.
• a synthetic rubber latex adhesive is used, the heat-expandable composition contains a dispersion medium such as water.
• synthetic rubber latex adhesives include chloroprene, butadiene, styrene-butadiene, butadiene-acrylonitrile, isobutylene-isoprene, and ethylene-propylene, with chloroprene being preferred.
• the thermally expandable composition will contain water or an organic solvent.
• the solid content of the thermally expandable composition is, for example, 10 to 90% by mass, and preferably 30 to 70% by mass.
• the moisture-curing adhesive is an adhesive that cures with moisture in the air.
• the thermally expandable composition containing the moisture-curing adhesive can be cured with moisture and kneaded at low temperatures, which makes it particularly easy to reduce the load during kneading and effectively suppresses the deterioration of the thermally expandable graphite. Therefore, the generation of gas caused by the deterioration of the thermally expandable graphite is suppressed, and a long thermally expandable fireproof sheet with an extremely good appearance can be obtained.
• moisture-curing adhesives include cyanoacrylate-based, modified silicone resin-based, and silylated urethane-based adhesives, with modified silicone resin-based and silylated urethane-based adhesives being preferred, and modified silicone resin-based adhesives being more preferred.
• a silicone-modified resin-based moisture-curing reaction adhesive is a polymer having a crosslinkable silyl group (a crosslinkable silyl group-containing polymer).
• the crosslinkable silyl group-containing polymer is preferably at least one selected from the group consisting of crosslinkable silyl group-containing polyoxyalkylene polymers, crosslinkable silyl group-containing acrylic polymers, and crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymers.
• the modified silicone resin-based moisture-curing reaction adhesive is a compound that does not have a urethane bond or a urea bond in the main chain, unlike the silylated urethane-based adhesive described below.
• polyoxyalkylene polymer containing a crosslinkable silyl group a polymer containing a crosslinkable silyl group in the molecule and having a polyoxyalkylene in the main chain is preferred, and a polymer having a polyoxyalkylene in the main chain and containing a crosslinkable silyl group at the end of the main chain is more preferred.
• the polyoxyalkylene is preferably polyoxypropylene.
• crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer a polymer containing a crosslinkable silyl group in the molecule and having a (meth)acrylic-modified polyoxyalkylene in the main chain skeleton is preferred, and a polymer having a (meth)acrylic-modified polyoxyalkylene in the main chain skeleton and containing a crosslinkable silyl group at the main chain end is more preferred.
• the (meth)acrylic-modified polyoxyalkylene is preferably a (meth)acrylic-modified polyoxypropylene.
• crosslinkable silyl group-containing acrylic polymers include polymers that have an acrylic polymer in the main chain skeleton and have one or more crosslinkable silyl groups in the molecule.
• the acrylic polymer may be any conventionally known polymer, and is not particularly limited as long as it is an acrylic polymer obtained by polymerizing or copolymerizing one or more acrylic monomers selected from (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylonitrile, (meth)acrylamide, etc.
• the crosslinkable silyl group examples include a group in which one or more reactive groups are bonded to a silicon atom.
• the reactive group is a group selected from halogen atom, hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group, mercapto group, ketoxime group, alkenyloxy group and aminooxy group, and when there are multiple reactive groups, the reactive groups may be the same or different groups.
• the reactive group is preferably an alkoxy group, and more preferably a methoxy group.
• the crosslinkable silyl group is preferably an alkoxysilyl group.
• the alkoxysilyl group includes trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group, dialkoxysilyl groups such as dimethoxymethylsilyl group and diethoxymethylsilyl group, and monoalkoxysilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group.
• trialkoxysilyl group or dialkoxysilyl group is preferred, and trimethoxysilyl group or dimethoxymethylsilyl group is more preferred.
• the silylated urethane-based moisture-curing adhesive is a polymer having at least one of a urethane bond and a urea bond in the main chain and a crosslinkable silyl group.
• the crosslinkable silyl group is preferably at the end of the main chain.
• the crosslinkable silyl group is the same as that described for the modified silicone resin-based moisture-curing adhesive.
• the main chain of the silylated urethane moisture-curing adhesive preferably has a polyoxyalkylene skeleton and at least one of a urethane bond and a urea bond, and the polyoxyalkylene is preferably polyoxypropylene.
• the moisture-curing reactive adhesive is preferably cured by a curing catalyst.
• the curing catalyst include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester maleate), tin octoate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate) oxide, dibutyltin oxybisethoxysilicate, and organic tin compounds such as 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, and organic titanium compounds such as tetra-n-butoxy titanate
• a hot melt adhesive is an adhesive that does not have fluidity at room temperature, but becomes fluid when heated, and is sometimes called a hot melt adhesive. In addition, the heated hot melt adhesive solidifies when cooled again.
• a hot melt adhesive is used in a heat-expandable composition for obtaining a heat-expandable fire-resistant sheet, the viscosity of the composition can be reduced by heating, the load during kneading can be reduced, and the deterioration of the heat-expandable graphite can be suppressed. Therefore, the generation of gas due to the deterioration of the heat-expandable graphite is suppressed, and a long heat-expandable fire-resistant sheet with good appearance can be obtained.
• hot melt adhesives examples include vinyl acetate resins, vinyl acetate copolymer resins, ethylene-vinyl acetate copolymer resins, rubbers, acrylic resins, polyurethanes, polystyrenes, polyolefins, polyesters, and polyamides.
• the rubber-based material include chloroprene, butadiene, styrene-butadiene, butadiene-acrylonitrile, isobutylene-isoprene, ethylene-propylene, etc.
• the polystyrene-based material is a polymer containing a styrene-based monomer, and may be a copolymer of a styrene-based monomer and an aliphatic monomer. Among these, ethylene-vinyl acetate copolymer resins and polystyrene resins are preferred.
• a tackifier resin may be used in combination. Examples of tackifier resins include rosin-based, terpene-based, petroleum resin-based, and coumarone resin-based resins.
• thermosetting reaction type adhesive is an adhesive that cures at any temperature.
• a thermally expandable composition containing a thermosetting reaction type adhesive can be cured by heat at a temperature lower than the expansion start temperature of thermally expandable graphite, and can be kneaded at a low temperature, so that the load during kneading is particularly easy to reduce, and deterioration of the thermally expandable graphite can be effectively suppressed. Therefore, gas generation caused by deterioration of the thermally expandable graphite is suppressed, and a long thermally expandable fireproof sheet with an extremely good appearance can be obtained.
• thermosetting reactive adhesives include those based on epoxy resins, polyurethane resins, silicone resins, acrylic resins, and polyester resins. Among these, epoxy resin-based adhesives are preferred.
• a curing agent or a catalyst may be used in combination with the epoxy resin.
• the curing agent include amine-based, acid anhydride-based, phenolic resin-based, and amide-based.
• the catalyst include amine salt-based, imidazole-based, and phosphine phosphonium salt-based. More preferably, by using a curing agent and a catalyst in combination, it is possible to reduce the temperature required for the thermosetting reaction, and a long heat-expandable fire-resistant sheet with a good appearance can be obtained.
• the content of the matrix component is preferably 20 to 80 mass %, more preferably 30 to 70 mass %, based on the total amount of the thermally expandable fire-resistant sheet.
• Thermally expandable Graphite is a conventionally known substance that expands when heated, and expands to form large-capacity voids, which inhibits the spread of fire or extinguishes the fire when the fireproof sheet catches fire.
• Thermally expandable graphite is a type of crystalline compound that is produced by treating powders of natural flaky graphite, pyrolytic graphite, kish graphite, or the like with an inorganic acid and a strong oxidizing agent to generate a graphite intercalation compound, and that maintains the layered structure of carbon.
• inorganic acids include concentrated sulfuric acid, nitric acid, and selenic acid.
• strong oxidizing agents include concentrated nitric acid, persulfates, perchloric acid, perchlorates, permanganates, dichromates, dichromates, and hydrogen peroxide.
• the thermally expandable graphite obtained by the acid treatment as described above may be further neutralized with ammonia, aliphatic lower amines, alkali metal compounds, alkaline earth metal compounds, and the like.
• the particle size of the thermally expandable graphite is preferably 20 to 200 mesh. When the particle size of the thermally expandable graphite is within the above range, it expands and easily creates large-capacity voids, improving fire resistance. Also, dispersibility in resin is improved.
• the average aspect ratio of the thermally expandable graphite is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. There is no particular upper limit to the average aspect ratio of the thermally expandable graphite, but from the viewpoint of preventing cracking of the thermally expandable graphite, it is preferably 1,000 or less.
• the average aspect ratio of the thermally expandable graphite is determined by measuring the maximum dimension (major axis) and the minimum dimension (minor axis) of each of 10 pieces of thermally expandable graphite, and averaging the values obtained by dividing the maximum dimension (major axis) by the minimum dimension (minor axis).
• the major axis and minor axis of the thermally expandable graphite can be measured, for example, using a field emission scanning electron microscope (FE-SEM).
• the expansion start temperature of the thermally expandable graphite is 160° C. or lower.
• the expansion start temperature of the thermally expandable graphite is 160° C. or lower, the expansion start temperature of the thermally expandable fire-resistant sheet can be easily adjusted to a low temperature, and the thermally expandable graphite expands in the early stage of a fire to form a fire-resistant heat insulating layer, making it easier to maintain good fire resistance for a long period of time.
• the expansion starting temperature of the thermally expandable graphite is preferably 100 to 160°C, and more preferably 120 to 150°C. The expansion starting temperature of the thermally expandable graphite is measured by the method described in the Examples.
• the expansion start temperature of the thermally expandable graphite is preferably lower than the decomposition start temperature of the matrix component, which improves the expansibility of the thermally expandable fireproof sheet and increases the mechanical strength of the formed fireproof insulation layer, thereby improving the fire resistance.
• the expansion start temperature of the thermally expandable graphite is preferably at least 5° C. lower than the decomposition start temperature of the matrix component, and more preferably at least 10° C. lower.
• the decomposition onset temperature means the temperature at which the matrix component decomposes and starts to lose weight, and is measured using a thermogravimetric analyzer under conditions of a dry air atmosphere and a heating rate of 10° C./min.
• the content of thermally expandable graphite is preferably 3 to 300 parts by mass, more preferably 10 to 200 parts by mass, even more preferably 30 to 100 parts by mass, and even more preferably 30 to 90 parts by mass, per 100 parts by mass of the matrix component.
• the thermally expandable fire-resistant sheet can be given appropriate fire resistance.
• the content of thermally expandable graphite is equal to or less than these upper limits, the amount of gas generated during the manufacturing process of the thermally expandable fire-resistant sheet is reduced, making it easier to obtain long products with good appearance.
• the thermally expandable fire-resistant sheet of the present invention may contain a thermally expandable inorganic material other than thermally expandable graphite.
• Thermally expandable inorganic materials expand when heated.
• the thermally expandable inorganic materials include vermiculite, kaolin, mica, metal phosphites, and shirasuballoons.
• the content thereof is preferably 2 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 30 to 100 parts by mass, relative to 100 parts by mass of the matrix component, from the viewpoint of improving fire resistance.
• the thermally expandable fire-resistant sheet of the present invention may contain an inorganic filler.
• the inorganic filler is an inorganic filler other than thermally expandable graphite and thermally expandable inorganic materials.
• the inorganic filler expands when heated, and when the fireproof and heat insulating layer is formed, it increases the heat capacity and suppresses heat transfer, while acting as an aggregate to improve the strength of the expansion residue.
• Inorganic fillers that can be used in the present invention are not particularly limited, and examples thereof include metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite, metal carbonates such as calcium carbonate, zinc carbonate, strontium carbonate, and barium carbonate, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite, calcium sulfate, gypsum fiber, calcium salts such as calcium silicate, silica, diatomaceous earth, dawsonite, barium sulfate, talc, clay, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloons, various metal powders, potassium titanate, magnesium sulfate, lead
• the inorganic fillers may be used alone or in combination of two or more.
• calcium carbonate, iron oxide, and aluminum hydroxide are preferred from the viewpoint of improving the fire resistance of the thermally expandable fire-resistant sheet, and a combination of calcium carbonate and iron oxide or a combination of calcium carbonate and aluminum hydroxide is preferred.
• the inorganic filler may be used alone or in combination of two or more kinds. From the viewpoint of improving fire resistance, the content of the inorganic filler is preferably 2 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 30 to 100 parts by mass, relative to 100 parts by mass of the matrix component.
• the thermally expandable fireproof sheet of the present invention may contain a plasticizer from the viewpoint of improving moldability.
• the plasticizer include phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP), fatty acid ester plasticizers such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA), epoxidized ester plasticizers such as epoxidized soybean oil, adipic acid ester plasticizers such as adipic acid ester and adipic acid polyester, trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM), and process
• TOTM di-2
• the plasticizer may be used alone or in combination of two or more.
• the content of the plasticizer is preferably 1 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the matrix component.
• the thermally expandable fireproof sheet of the present invention may contain additive components other than those described above as necessary, as long as the object of the present invention is not impaired.
• the type of additive component is not particularly limited, and various additives can be used. Examples of such additives include lubricants, shrinkage inhibitors, crystal nucleating agents, colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, antiaging agents, flame retardants, flame retardant assistants, antistatic agents, surfactants, vulcanizing agents, dispersants, and surface treatment agents.
• the amount of additives added can be appropriately selected within a range that does not impair moldability, etc., and the additives may be used alone or in combination of two or more.
• the heat-expandable fireproof sheet of the present invention is a rolled product having a length of 1 m or more.
• the length is the length in the longitudinal direction (MD direction) of the heat-expandable fireproof sheet.
• the heat-expandable fireproof sheet of the present invention contains heat-expandable graphite with a low expansion start temperature, but can be made into a long product having a length of 1 m or more and good appearance. In addition, by making the length 1 m or more, productivity is improved and the range of applications is expanded, which is preferable.
• the length of the heat-expandable fireproof sheet is preferably 5 m or more, more preferably 20 m or more, even more preferably 50 m or more, and even more preferably 100 m or more. In addition, the length of the heat-expandable fireproof sheet is usually 500 m or less.
• the MD direction is an abbreviation for Machine Direction, and is the direction of flow of the composition during coating, etc., which will be described later, and is the longitudinal direction of the sheet.
• the TD direction is an abbreviation for Transverse Direction, and is the direction perpendicular to the MD direction.
• the thermally expandable fire-resistant sheet of the present invention can reduce thickness variation even when the sheet is made to be 1 m or longer in length, and can provide a long product with high dimensional accuracy.
• the present invention it is presumed that by reducing the kneading load when kneading the composition, deterioration of the thermally expandable graphite can be suppressed, and thus gas generation can be suppressed, thereby reducing unevenness in thickness.
• the wound body in the present invention is a heat-expandable fire-resistant sheet having a length of 1 m or more wound into a roll, for example, a heat-expandable fire-resistant sheet having a length of 1 m or more wound around a cylindrical winding core.
• the winding core may not be required.
• the thermally expandable fireproof sheet of the present invention has an average thickness of 0.5 mm or more and a thickness variation of 10% or less of the average thickness.
• the average thickness means the average value when the thickness is measured at 10 points at equal intervals in the longitudinal direction of the thermally expandable fireproof sheet.
• the average thickness is preferably 0.8 mm or more, more preferably 1 mm or more, and preferably 5 mm or less. The thickness is measured at the center of the sheet in the width direction.
• the thickness variation is, as described above, the thickness is measured at 10 points at equal intervals in the longitudinal direction of the thermally expandable fireproof sheet, the absolute value A of the difference between the thickness measured at each point and the average thickness is calculated, and the average value of the absolute values A for the 10 points is taken as the thickness variation.
• the thickness variation is preferably 0.1 mm or less, more preferably 0.08 mm or less, and even more preferably 0.05 mm or less. From the viewpoint of improving the appearance of the sheet, the variation in thickness of the thermally expandable fire-resistant sheet is 10% or less of the average thickness, and preferably 5% or less.
• the width of the thermally expandable fireproof sheet is not particularly limited, but is, for example, 0.005 to 2.0 m.
• the heat-expandable fireproof sheet of the present invention preferably has a heat shrinkage rate of 1% or less in both the MD and TD directions, and more preferably 0.5% or less, even when the sheet has a length of 1 m or more. If the heat shrinkage rate is low, peeling due to shrinkage or dimensional insufficiency can be suppressed, even when heat is applied during the manufacturing process of the roll.
• the heat shrinkage rate is calculated based on the following formula from the length before and after the heat treatment by cutting out an evaluation sample of 100 mm square and heat treating it at 60° C. for 6 hours.
• Heat shrinkage rate (%) 100 ⁇ (length before heat treatment - length after heat treatment) / length before heat treatment
• the heat shrinkage rate in the MD direction and the heat shrinkage rate in the TD direction can be calculated based on the above formula from the lengths before heat treatment and after heat treatment in the MD direction and the TD direction, respectively.
• 10 or more evaluation samples of 100 mm square are prepared at equal intervals in the longitudinal direction of the sheet, and the heat shrinkage percentages calculated from the individual evaluation samples are averaged to determine the heat shrinkage percentage in the MD direction and the heat shrinkage percentage in the TD direction.
• the thermal shrinkage rate can be adjusted by adjusting the contents of the various components constituting the thermally expandable fire-resistant sheet.
• the thermally expandable fireproof sheet of the present invention has an expansion start temperature of 160° C. or less. By having an expansion start temperature of 160° C. or less, the sheet expands in the early stage of a fire when the temperature is relatively low to form a fire-resistant heat insulating layer, which makes it easier to maintain good fire resistance for a long period of time.
• the expansion initiation temperature of the thermally expandable fire-resistant sheet is preferably 155° C. or lower, more preferably 150° C. or lower, and preferably 120° C. or higher.
• the expansion initiation temperature of the thermally expandable fire-resistant sheet is measured by the method described in the Examples.
• the thermally expandable fireproof sheet of the present invention preferably has an expansion ratio of 5 or more when heated at 200° C. for 30 minutes. By having an expansion ratio of 5 or more, gaps in fire prevention equipment can be easily blocked in the event of a fire, improving fire resistance.
• the expansion ratio when heated at 200° C. for 30 minutes is preferably 6 times or more, more preferably 8 times or more.
• the upper limit of the expansion ratio is not particularly limited, but is, for example, 50 times.
• the expansion ratio of the thermally expandable fire-resistant sheet is measured by the method described in the Examples.
• the heat-expandable fireproof sheet of the present invention preferably has an elution rate of 3% or less after immersion in pure water at 60° C. for one week. If the elution rate is 3% or less, even if the heat-expandable fireproof sheet is placed in a high humidity environment or in an environment where it comes into contact with water, the elution of the components constituting the heat-expandable fireproof sheet can be suppressed, and a decrease in fire resistance can be prevented. In addition, when the heat-expandable fireproof sheet is installed in a fireproof facility, contamination of the fireproof facility and the occurrence of poor appearance can be prevented.
• the elution rate of the thermally expandable fireproof sheet is preferably 2% or less, more preferably 1% or less.
• the lower the elution rate, the better, and the lower limit is 0%.
• the elution rate can be adjusted by appropriately selecting each component to be blended in the heat-expandable fireproof sheet. Specifically, it is sufficient to use compounds with low solubility in water for the matrix component, heat-expandable graphite, inorganic filler blended as required, and other additives.
• the dissolution rate is measured by the method described in the Examples.
• the matrix component contained in the heat-expandable fire-resistant sheet of the present invention preferably does not contain a phosphorus component.
• a matrix component that does not contain a phosphorus component the phosphorus component of the heat-expandable fire-resistant sheet can be reduced.
• the components other than the matrix component contained in the heat-expandable fire-resistant sheet do not contain a phosphorus component.
• the heat-expandable fire-resistant sheet does not contain a phosphorus component.
• the matrix component and the thermally expandable fireproof sheet may contain an amount of phosphorus component that is an unavoidable impurity.
• not containing phosphorus component means that the content of phosphorus component is 0.1 mass % or less, preferably 0.01 mass % or less.
• the phosphorus component is a compound containing a phosphorus atom, and it is preferable not to use a compound containing a phosphorus atom as the above-mentioned matrix component, thermally expandable graphite, and inorganic filler that is mixed as necessary, or other additives.
• the thermally expandable fireproof sheet of the present invention is made of a thermally expandable composition containing a matrix component and thermally expandable graphite, and is obtained by molding the thermally expandable composition by a method such as extrusion or coating described below.
• the thermally expandable composition may contain a thermally expandable inorganic material other than the thermally expandable graphite described above, an inorganic filler, etc.
• the heat-expandable fire-resistant sheet of the present invention can be obtained by extrusion molding a mixture of a heat-expandable composition, or by applying the mixture to any object and solidifying or drying the applied heat-expandable composition.
• the Mooney viscosity ML(1+4) of the thermally expandable composition at 100°C is preferably 10 to 70, and more preferably 30 to 60.
• the thermally expandable composition is melted and extrusion molded by an extruder.
• the extruder may be a single-screw extruder or a twin-screw extruder.
• the extruder is preferably an extruder having a vent mechanism. This allows gas generated during kneading of the thermally expandable composition to be discharged outside the system, making it easier to obtain a thermally expandable fireproof sheet with high thickness accuracy and good appearance.
• the kneading temperature during extrusion molding should be equal to or lower than the expansion start temperature of the thermally expandable graphite, preferably 80 to 160°C, and more preferably 90 to 120°C.
• the viscosity of the thermally expandable composition measured with a rheometer at room temperature (40° C.) and a shear rate of 25 s -1 is preferably 0.1 to 20 Pa ⁇ s, more preferably 2 to 8 Pa ⁇ s.
• the viscosity of the thermally expandable composition measured by a rheometer at 120°C and a shear rate of 25 s -1 is preferably 0.1 to 200 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s.
• the thermally expandable fireproof sheet can be formed by drying the thermally expandable composition after application to remove the solvent. Drying may be performed by leaving it at around room temperature (about 25°C), but it is preferable to perform drying by heating. Heating is preferably performed at a temperature below the expansion start temperature of the thermally expandable graphite, for example, at about 50 to 160°C, preferably 60 to 120°C.
• the thermally expandable composition When using a hot melt adhesive as the matrix component, it is preferable to knead the thermally expandable composition and apply the molten mixture to any object to obtain a thermally expandable fireproof sheet.
• the kneading temperature should be equal to or lower than the expansion start temperature of the thermally expandable graphite, preferably 80 to 160°C, and more preferably 90 to 120°C.
• the object to which the thermally expandable composition is applied is not particularly limited, but may be, for example, a release-treated resin film, or when producing a thermally expandable fire-resistant sheet that includes a substrate, the substrate may be the object to which the thermally expandable composition is applied.
• the heat-expandable fireproof sheet of the present invention may be used alone, or may be used as a multi-layer sheet by appropriately attaching other members.
• the heat-expandable fireproof sheet may have a substrate or an adhesive layer on at least one side.
• the heat-expandable fireproof sheet may have a substrate on one side (substrate/heat-expandable fireproof sheet multi-layer sheet), an adhesive layer on one side (adhesive layer/heat-expandable fireproof sheet multi-layer sheet), or a substrate on one side and an adhesive layer on the other side (adhesive layer/heat-expandable fireproof sheet/substrate multi-layer sheet).
• the heat-expandable fireproof sheet may have a separator, for example, a separator may be provided on the surface of the adhesive layer.
• the substrate may be in the form of, for example, a woven fabric, a nonwoven fabric, a film, or the like, and may be made of a thermoplastic resin, a thermosetting resin, an elastomeric resin, or the like, and is preferably made of a thermoplastic resin among these.
• the substrate may also be made of glass fiber, ceramic fiber, cellulose fiber, polyester fiber, carbon fiber, graphite fiber, thermosetting resin fiber, or the like.
• the preferred form of the substrate is a film. A film having a cavity therein can also be suitably used as the film.
• thermoplastic resins include polyesters such as polyvinyl chloride, polyethylene terephthalate, and polybutylene terephthalate; polyolefins such as polyethylene, polypropylene, poly(1-butene), and polypentene; polyvinyl acetate, polystyrene, acrylic resins, acrylonitrile-butadiene-styrene (ABS) resins, polycarbonates, polyamides, polyphenylene ethers, and polyethersulfones.
• polyesters such as polyvinyl chloride, polyethylene terephthalate, and polybutylene terephthalate
• polyolefins such as polyethylene, polypropylene, poly(1-butene), and polypentene
• polyvinyl acetate polystyrene, acrylic resins, acrylonitrile-butadiene-styrene (ABS) resins
• ABS acrylonitrile-butadiene-styren
• thermoplastic resins are polyvinyl chloride, polyethylene terephthalate, polyolefin, and polyvinyl acetate. Furthermore, from the viewpoint of flame retardancy, polyvinyl chloride is more preferred. Also preferred is a polyethylene terephthalate film having a cavity inside.
• thermosetting resins are epoxy resins, urethane resins, phenolic resins, unsaturated polyesters, alkyd resins, urea resins, and polyimides.
• elastomer resins include isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluororubber, urethane rubber, polyisobutylene rubber, and chlorinated butyl rubber.
• thermoplastic resins, thermosetting resins and elastomer resins are used.
• the thickness of the substrate is preferably 1 to 20% of the thickness of the multilayer sheet. If the thickness is 1% or more of the thickness of the multilayer sheet, the substrate will be able to easily support the heat-expandable fire-resistant sheet. Furthermore, if the thickness of the substrate is 20% or less of the thickness of the multilayer sheet, peeling between the substrate and the heat-expandable fire-resistant sheet and the occurrence of wrinkles in the substrate are suppressed when the multilayer sheet is curved, and the appearance of the multilayer sheet can be maintained in a good condition.
• the thickness of the substrate is, for example, 10 to 500 ⁇ m, preferably 20 to 450 ⁇ m, and more preferably 30 to 400 ⁇ m.
• the substrate can be given the strength to support the thermally expandable fire-resistant sheet.
• the thickness of the substrate can be prevented from becoming thicker than necessary, making it easier to use the multilayer sheet in fire-resistant equipment such as doors.
• the adhesive layer may be a single layer (hereinafter also referred to as adhesive layer) consisting of only a layer formed by an adhesive, or may be a double-sided adhesive tape in which adhesive layers are provided on both surfaces of a substrate for a double-sided adhesive tape, but is preferably made of an adhesive layer.
• the adhesive layer of the double-sided adhesive tape is formed by bonding one of the adhesive layers to a heat-expandable fire-resistant sheet or a separator.
• the adhesive constituting the adhesive layer is not particularly limited, and examples thereof include acrylic adhesives, urethane adhesives, rubber adhesives, etc.
• the thickness of the adhesive layer is not particularly limited, and is, for example, 10 to 500 ⁇ m, and preferably 50 to 200 ⁇ m.
• the substrate for the double-sided pressure-sensitive adhesive tape is not particularly limited as long as it is a substrate used in general double-sided pressure-sensitive adhesive tapes, and examples thereof include nonwoven fabrics, paper such as Japanese paper, woven fabrics made of natural fibers, synthetic fibers, etc., resin films made of polyester, polyolefin, soft polyvinyl chloride, hard polyvinyl chloride, acetate, etc., and flat yarn cloth.
• the separator may be, for example, one that includes a separator substrate and a release layer provided on at least one surface of the separator substrate.
• the release layer can be formed by subjecting the separator substrate to a release treatment.
• the separator may be disposed so that the surface on which the release layer is provided is in contact with the adhesive layer.
• the separator may be such that both surfaces of the separator substrate are subjected to a release treatment, and release layers are provided on both surfaces.
• the release layer is not particularly limited, but may be made of, for example, an organic resin.
• any known release agent may be used, such as a fluorine-based resin, a long-chain alkyl-containing resin, an alkyd-based resin, a polyolefin-based resin, or a rubber-based elastomer.
• the separator substrate may be a resin film, paper, or the like.
• the resin film may be formed from a thermoplastic resin, a thermosetting resin, an elastomer resin, or the like. Specific examples of the thermoplastic resin, the thermosetting resin, or the elastomer resin may include those listed in the resin film, but a thermoplastic resin is preferred.
• the thickness of the separator is preferably 0.3 to 10% of the thickness of the multilayer sheet. If the thickness of the separator is 0.3% or more of the thickness of the multilayer sheet, the separator is more likely to be prevented from being broken. Furthermore, if the thickness of the separator is 10% or less of the thickness of the multilayer sheet, peeling between the heat-expandable fire-resistant sheet and the separator and the occurrence of wrinkles in the separator are prevented when the multilayer sheet is bent, and the appearance of the multilayer sheet can be maintained in a good condition.
• the thickness of the separator is, for example, 1 to 200 ⁇ m, preferably 2 to 150 ⁇ m, and more preferably 5 to 100 ⁇ m. By making the thickness of the separator equal to or greater than these lower limits, the separator can be given sufficient strength to withstand breakage. Furthermore, by making the thickness equal to or less than the upper limits, peeling between the fireproof material and the separator and the occurrence of wrinkles in the separator can be prevented when the multilayer sheet is curved.
• a fire prevention facility in which at least a part of the heat-expandable fireproof sheet cut out from the above-mentioned roll is mounted.
• fire prevention facilities include fittings such as windows, shoji screens, doors, doors, and sliding doors, pillars, walls such as steel-framed concrete, floors, and roofs.
• the heat-expandable fireproof sheet of the present invention is mounted on a part of such fire prevention facilities and expands in the event of a fire, thereby reducing or preventing the intrusion of flames and smoke.
• the heat-expandable fireproof sheet is preferably used in the gap between a window and a window frame, or between a door and a door frame.
• ⁇ Viscosity during kneading (40°C, 120°C)>
• the viscosity of the thermally expandable composition during kneading was measured by a rheometer.
• the rheometer used was Discovery HR20 manufactured by TA Instruments, and the measurement was performed at temperatures of 40° C. and 120° C. under the condition of a shear rate of 25 s ⁇ 1 .
• thermally expandable fireproof sheet ⁇ Expansion start temperature of thermally expandable fireproof sheet>
• the thermally expandable fireproof sheet was used as a sample, and the temperature at which the normal force started to rise was measured using a rheometer ("Discovery HR2" manufactured by TA Instruments) at a temperature rise rate of 10°C/min. This was taken as the expansion starting temperature.
• ⁇ Thickness variation> The thickness was measured at 10 points at equal intervals in the longitudinal direction of the thermally expandable fire-resistant sheet, and the thicknesses at these 10 points were averaged to obtain the average thickness. Next, the thickness was measured at 10 points at equal intervals in the longitudinal direction of the thermally expandable fireproof sheet, and the absolute value A of the difference between the thickness measured at each point and the average thickness was calculated, and the average of the absolute values A for the 10 points was taken as the thickness variation. Then, the ratio (%) of the thickness variation to the average thickness was calculated.
• the appearance of the resulting thermally expandable fire-resistant sheet was evaluated according to the following criteria. After producing a long fireproof sheet, the sheet was cured at 40° C. for one week and then re-unfolded for evaluation. During the unfolding process, the appearance of the sheet was observed to judge whether air bubbles were observed on the surface. If no air bubbles of 5 mm or more in the width direction were observed, the sheet was rated as A, and if air bubbles were observed, the sheet was rated as B.
• the strength of the obtained thermally expandable fire-resistant sheet was evaluated according to the following criteria.
• the long fireproof sheets obtained in each of the Examples and Comparative Examples were wound up into rolls of fireproof sheets, which were then re-deployed at 20° C. for evaluation. During the unfolding process, the appearance of the sheet was observed to check whether the surface was cracked or broken. Evaluation was based on the following criteria. A: The sheet could be unfolded without breaking. B: The sheet broke when deployed.
• Moisture curing reaction type modified silicone resin system polymer having a crosslinkable silyl group, Kaneka Corporation "Silyl EST280” Moisture curing reaction type silylated urethane system: Momentive Performance Materials Japan "SPUR3030” Ethylene-vinyl acetate copolymer resin (EVA-based), Mitsui Chemicals'"V5774ETWR", hot melt adhesive, polystyrene-based, Mitsui Chemicals'"FTR6100", hot melt adhesive, epoxy resin-based, Mitsubishi Chemical's "jER807", amine-based hardener, Mitsubishi Chemical's "FL052", catalyst, Shikoku Chemicals'"Curesol1.2DMZ", heat-curing reaction adhesive
• Example 1 Each component was introduced into an extruder so as to obtain the composition shown in Table 1, and the kneaded heat-expandable composition was extruded at 110°C to obtain a heat-expandable fire-resistant sheet.
• the heat-expandable fire-resistant sheet (length 100 mm, thickness 1.5 mm, width 10 mm) was subjected to various evaluations.
• the extruder used had a vent mechanism.
• Examples 4 to 6, Comparative Example 1 A thermally expandable fire-resistant sheet was obtained in the same manner as in Example 1, except that the composition was changed as shown in Table 1. The thermally expandable fire-resistant sheet was subjected to various evaluations.
• Example 2 The components were mixed at 40°C using a stirrer to obtain the composition shown in Table 1, and dissolved in toluene to a solid content of 40%, to obtain a thermally expandable composition. The thermally expandable composition was then applied to a release PET film using a roll coater, and the applied product was dried to evaporate the solvent, forming a thermally expandable fireproof sheet on the release PET film. Various evaluations were performed on the thermally expandable fireproof sheet (length 100 mm, thickness 1.5 mm, width 10 mm).
• Example 3 The components were mixed at 25°C with a stirrer to obtain a thermally expandable composition as shown in Table 1.
• the thermally expandable composition was then applied onto a release PET film with a roll coater, and the applied product was dried at 120°C to evaporate the solvent, forming a thermally expandable fire-resistant sheet on the release PET film.
• Various evaluations were performed on the thermally expandable fire-resistant sheet (length 100 mm, thickness 1.5 mm, width 10 mm).
• Example 7 and 8 A thermally expandable fire-resistant sheet was obtained in the same manner as in Example 3, except that the composition and drying temperature were changed to those shown in Table 1. Various evaluations were performed on the thermally expandable fire-resistant sheet.
• Example 9 The components were mixed with a stirrer to obtain a thermally expandable composition according to the composition shown in Table 1.
• the thermally expandable composition was then heated to 110°C to melt and knead, and then coated on a release PET film with a roll coater.
• the coated product was cooled to room temperature (25°C) and solidified to form a thermally expandable fireproof sheet on the release PET film.
• Various evaluations were performed on the thermally expandable fireproof sheet (length 100 mm, thickness 1.5 mm, width 10 mm).
• Example 10 A thermally expandable fire-resistant sheet was obtained in the same manner as in Example 9, except that the composition was changed to that shown in Table 1. The thermally expandable fire-resistant sheet was subjected to various evaluations.
• thermally expandable composition was obtained by mixing the components at 25° C. using a stirrer to obtain the composition shown in Table 1.
• the thermally expandable composition was then applied onto a release PET film using a roll coater, and the applied product was cured at 50° C. to form a thermally expandable fire-resistant sheet on the release PET film.
• Various evaluations were performed on the thermally expandable fire-resistant sheet (length 20 mm, thickness 1.5 mm, width 10 mm).
• Example 19 The components were mixed at 40°C with a stirrer to obtain a thermally expandable composition as shown in Table 1.
• the thermally expandable composition was then applied to a release PET film with a roll coater, and the applied material was thermally cured to form a thermally expandable fireproof sheet on the release PET film.
• Various evaluations were performed on the thermally expandable fireproof sheet (length 100 mm, thickness 1.5 mm, width 10 mm).
• Table 1 shows the composition of the thermally expandable fire-resistant sheet and the composition of the solid content of the thermally expandable composition.
• thermally expandable graphite with a low thermal expansion onset temperature was used, a long thermally expandable fire-resistant sheet with good appearance was obtained.
• the thermally expandable fire-resistant sheet of Comparative Example 1 had a large variation in thickness and was inferior in appearance and strength.

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