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
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
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  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/18—Fireproof paints including high temperature resistant paints
  • C09D5/185—Intumescent paints
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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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  • C09K21/00—Fireproofing materials
  • C09K21/02—Inorganic materials
  • C09K21/04—Inorganic materials containing phosphorus
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
  • C08K2003/321—Phosphates
  • C08K2003/322—Ammonium phosphate
  • C08K2003/323—Ammonium polyphosphate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D123/04—Homopolymers or copolymers of ethene
  • C09D123/08—Copolymers of ethene
  • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C09D123/0853—Vinylacetate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
  • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C09J123/0853—Vinylacetate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/346—Applications of adhesives in processes or use of adhesives in the form of films or foils for building applications e.g. wrap foil
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C

Definitions

• the present invention relates to a heat-expandable refractory composition, a heat-expandable refractory material formed from the heat-expandable refractory composition, and a method for producing the heat-expandable refractory material.
• a heat-expandable refractory material that expands by heating has been widely used in buildings and the like.
• the expansion residue obtained by expansion by heating forms a fire-resistant heat insulating layer and exhibits fire-resistant heat insulating performance, so that it is possible to prevent the occurrence of a fire or the spread of fire in the event of a fire. Can be done.
• the heat-expandable refractory material for example, as described in Patent Document 1, a material containing a resin and a heat-expandable compound such as expandable graphite is widely used.
• the heat-expandable refractory material is generally fixed to a building or the like via an adhesive layer laminated on the heat-expandable refractory material.
• the heat-expandable refractory material when the heat-expandable refractory material is fixed by an adhesive layer, it is generally applied by hand, and the workability is poor. Further, the heat-expandable refractory material may be physically fixed by a fixing tool such as a metal fitting or a screw without using an adhesive layer, but even in that case, the construction becomes complicated and the workability is not good. Further, if the adhesive layer is not used, there is a high risk that the combustion residue will fall off, and the desired fire resistance may not be satisfied.
• the gist of the present invention is as follows.
• a heat-expandable refractory composition containing an adhesive base and a heat-expandable compound.
• a heat-expandable fire-resistant material composition wherein the heat-expandable fire-resistant material composition has fluidity and can be solidified or cured at room temperature or a temperature lower than the expansion start temperature of the heat-expandable compound.
• the adhesive base is selected from the group consisting of a hot melt type adhesive base, a one-component curable adhesive base, a two-component curable adhesive base, an emulsion type adhesive base, and a solvent-based adhesive base.
• the heat-expandable fire-resistant material composition according to the above [1], which comprises one or more.
• the heat-expandable fire-resistant material composition according to the above [2], which comprises the hot-melt type adhesive base, and the hot-melt type adhesive base contains a main agent resin and a tackifier resin.
• the one-component curable adhesive base consists of a group consisting of a crosslinkable silyl group-containing acrylic polymer, a crosslinkable silyl group-containing polyoxyalkylene polymer, and a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer.
• a heat-expandable fire-resistant material that can be easily applied to an object to be constructed such as a building with good adhesiveness without using an adhesive layer and a fixture.
• the heat-expandable fire-resistant material composition of the present invention contains an adhesive base and a heat-expandable compound, and has fluidity at room temperature (23 ° C.) or a temperature lower than the expansion start temperature of the heat-expandable compound.
• the heat-expandable refractory composition of the present invention is solidifiable or curable, and the fluidity of the heat-expandable refractory composition having fluidity is lost due to solidification or hardening, resulting in heat. It becomes an expandable refractory material.
• the heat-expandable fire-resistant material composition of the present invention has fluidity at room temperature or at a temperature lower than the expansion start temperature of the heat-expandable compound, so that it can be easily applied or filled to a work piece such as a building. Can be constructed in. Further, the heat-expandable refractory composition can be adhered to the work piece with good adhesiveness by being solidified or hardened after being applied by coating or the like. Adhesiveness can be well maintained even after combustion.
• the expansion start temperature of the heat-expandable compound referred to here is as described later, but when two or more types of the heat-expandable compound are present, the expansion start temperature of the heat-expandable compound having the lowest expansion start temperature is used. means.
• solidification means solidifying a fluidized heat-expandable fire-resistant material composition without the reaction of the components constituting the heat-expandable fire-resistant material composition, and is made of water or a solvent. It is solidified by volatilization, phase change from liquid to solid, etc. Further, curing means that the fluidity of the heat-expandable refractory composition is lost and solidified with the reaction of the components constituting the heat-expandable refractory composition.
• the heat-expandable refractory composition of the present invention may be a heat-expandable refractory material due to both solidification and hardening.
• the heat-expandable compound is a compound that expands the heat-expandable refractory material by expanding the heat-expandable compound itself by heating or generating gas or the like. Since the heat-expandable fire-resistant material composition contains the heat-expandable compound, the heat-expandable fire-resistant material expands by being heated to a temperature equal to or higher than the expansion start temperature of the heat-expandable compound, and the expansion residue causes fire resistance. Form a heat insulating layer.
• heat-expandable compound examples include a heat-expandable layered inorganic substance, a foamable flame retardant, a heat-expandable microcapsule, and a pyrolysis type foaming agent.
• the heat-expandable compound may be used alone or in combination of two or more.
• the heat-expandable layered inorganic substance is a conventionally known substance that expands by heating, and examples thereof include vermiculite and heat-expandable graphite. Among them, heat-expandable graphite is preferable.
• the heat-expandable layered inorganic substance may be used alone or in combination of two or more.
• As the heat-expandable layered inorganic substance particulate or flaky substances may be used.
• the heat-expandable layered inorganic substance, particularly the heat-expandable graphite can have a high degree of expansion and can form a large-capacity void during heat expansion. Further, the expansion start temperature can be adjusted to a temperature range suitable for the refractory material. Further, the residual hardness of the expanded residue can be easily increased, and the refractory material can have excellent fire resistance and fire extinguishing performance.
• Thermally expandable graphite is obtained by treating powders such as natural scale graphite, pyrolysis graphite, and kiss graphite with an inorganic acid and a strong oxidizing agent to form a graphite interlayer compound, and maintains a layered structure of carbon. It is a kind of crystalline compound as it is.
• the inorganic acid include concentrated sulfuric acid, nitric acid and selenic acid.
• the strong oxidizing agent include concentrated nitrate, persulfate, perchloric acid, perchlorate, permanganate, dichromate, dichromate, hydrogen peroxide and the like.
• the heat-expandable graphite obtained by acid treatment as described above may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like.
• the particle size of the heat-expandable graphite is preferably 20 to 200 mesh. When the particle size of the heat-expandable graphite is within the above range, it easily expands to form a large-capacity void, and thus the fire resistance is improved. In addition, the dispersibility in the resin is also improved.
• the average aspect ratio of the heat-expandable graphite is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more.
• the upper limit of the average aspect ratio of the heat-expandable graphite is not particularly limited, but is preferably 1,000 or less from the viewpoint of preventing cracking of the heat-expandable graphite.
• the average aspect ratio of the heat-expandable graphite is 2 or more, it is easy to expand and form a large-capacity void, so that the flame retardancy is improved.
• the average aspect ratio of the heat-expandable graphite was measured for each of the 10 heat-expandable graphites in the maximum dimension (major axis) and the minimum dimension (minor axis), and the maximum dimension (major axis) was divided by the minimum dimension (minor axis). Let the average value of the values be the average aspect ratio.
• the major axis and the minor axis of the heat-expandable graphite can be measured using, for example, a field emission scanning electron microscope (FE-SEM).
• the effervescent flame retardant examples include phosphorus-containing compounds such as ammonium phosphate, ammonium polyphosphate, aluminum phosphite, and melamine polyphosphate.
• the effervescent flame retardant is a flame retardant that can impart flame retardancy to a heat-expandable refractory material, but has the property of expanding by heating itself.
• the effervescent flame retardant may be used alone or in combination of two or more.
• the effervescent flame retardant is preferably at least one selected from ammonium polyphosphate and aluminum phosphite from the viewpoint of fire resistance and residual hardness.
• the heat-expandable microcapsules contain a volatile substance such as a low boiling point solvent inside the outer shell resin, and the outer shell resin is softened by heating, and the contained volatile substance volatilizes or expands. The pressure causes the outer shell to expand and the particle size to increase.
• the outer shell of the heat-expandable microcapsules is preferably formed of a thermoplastic resin.
• Thermoplastic resins are made from vinyl polymers such as ethylene, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, butadiene, and chloroprene, copolymers thereof, polyamides such as nylon 6, nylon 66, and polyesters such as polyethylene terephthalate.
• vinyl polymers such as ethylene, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, butadiene, and chloroprene, copolymers thereof, polyamides such as nylon 6, nylon 66, and polyesters such as polyethylene terephthalate.
• acrylonitrile copolymer is preferable because the contained volatile substances are difficult to permeate.
• Volatile substances contained inside the heat-expandable microcapsules include hydrocarbons having 3 to 7 carbon atoms such as propane, propylene, butene, normal butane, isopentane, isopentane, neopentane, normal pentane, hexane, and heptane, and chloride.
• hydrocarbons having 3 to 7 carbon atoms such as propane, propylene, butene, normal butane, isopentane, isopentane, neopentane, normal pentane, hexane, and heptane, and chloride.
• methane halides such as methyl and methylene chloride
• chlorofluorocarbons such as CCl 3 F and CCl 2 F 2
• tetraalkyl silanes such as tetramethyl silane and trimethyl ethyl silane
• petroleum ethers Low boiling liquids above the seed are used.
• heat-expandable microcapsules include microcapsules in which a copolymer of acrylonitrile and vinylidene chloride is used as an outer shell resin and a hydrocarbon having 3 to 7 carbon atoms such as isobutane is contained.
• the heat-expandable microcapsules may be used alone or in combination of two or more.
• pyrolytic foaming agent examples include compounds that foam by heating to generate gas.
• the pyrolysis foaming agent expands the heat-expandable refractory composition by the generated gas.
• an organic or inorganic chemical foaming agent can be used as the pyrolysis foaming agent.
• the organic foaming agent include azodicarbonamides, azodicarboxylic acid metal salts (azodicarboxylic acid barium and the like), azo compounds such as azobisisobutyronitrile, and nitroso compounds such as N, N'-dinitrosopentamethylenetetramine.
• Examples thereof include hydrazodicarbonamides, 4,4'-oxybis (benzenesulfonyl hydrazide), hydrazine derivatives such as toluenesulfonylhydrazide, semicarbazide compounds such as toluenesulfonyl semicarbazide, melamine, dicyandiamide, pentalit (pentaerythritol) and the like.
• Examples of the inorganic foaming agent include ammonium carbonate, sodium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium boron hydride, anhydrous monosoda citrate and the like.
• azo compounds and nitroso compounds are preferable from the viewpoint of obtaining fine bubbles, and from the viewpoint of economy and safety, azodicarbonamide, azobisisobutyronitrile, N, N'-dinitrosopentamethylene. Tetramine is more preferred, and azodicarbonamide is particularly preferred.
• the pyrolysis foaming agent may be used alone or in combination of two or more.
• the heat-expandable fire-resistant composition is a foamable flame-retardant and a flame-retardant agent in order to impart appropriate fire resistance. It is preferable to further contain at least one selected from.
• the expansion start temperature of the heat-expandable compound is preferably 100 to 250 ° C.
• the expansion start temperature is more preferably 125 to 200 ° C, still more preferably 150 to 195 ° C, and even more preferably 155 to 190 ° C.
• the heat-expandable compound having the expansion start temperature is preferably heat-expandable graphite, and therefore, the expansion start temperature of the heat-expandable graphite is preferably 100 to 250 ° C., more preferably 125 to 200 ° C. It is more preferably 150 to 195 ° C, and even more preferably 155 to 190 ° C.
• the expansion start temperature of at least one of the heat-expandable compounds is preferably within the above range, but the expansion start temperature. It is preferable that the thermally expandable compound having the lowest value is within the above range.
• the expansion start temperature of the heat-expandable graphite is lower than the expansion start temperature of the foamable flame retardant. Therefore, as described above, the expansion start temperature of the heat-expandable graphite is preferably within the above range.
• the expansion start temperature As will be described later, a rheometer is used to heat the thermally expandable compound, the temperature at which the force in the normal direction rises is measured, and the measured temperature is defined as the expansion start temperature.
• the expansion start temperature is generally not detected by the above measurement method, but it is preferable that the temperature at which the gas is generated by decomposition (decomposition temperature) is within the above temperature range.
• the content of the heat-expandable compound is preferably 10 to 80% by mass based on the total solid content in the heat-expandable refractory composition.
• the heat-expandable compound at least the above lower limit value, the expansion coefficient at the time of combustion becomes sufficiently high, and the fire resistance performance of the heat-expandable refractory material becomes good.
• the adhesive base can be contained in the heat-expandable refractory composition at a certain level or more, and good adhesiveness can be easily developed. Further, after solidification or curing, the heat-expandable compound is easily held by the adhesive base, so that the mechanical strength of the heat-expandable refractory material is also improved.
• the content of the heat-expandable compound in the heat-expandable refractory composition is more preferably 15 to 70% by mass, still more preferably 20 to 60% by mass, and even more preferably 25 to 55% by mass.
• the heat-expandable graphite and the effervescent flame retardant are preferable to use as the heat-expandable compound.
• the heat-expandable compound imparts flame retardancy to the heat-expandable refractory material, and it becomes easy to improve the fire resistance performance.
• the heat-expandable compound it is more preferable to use at least heat-expandable graphite. By using the heat-expandable graphite, it becomes easy to adjust the expansion start temperature within the above range, and it becomes easy to increase the expansion coefficient and the residual hardness.
• the content of the heat-expandable graphite is preferably 5 to 60% by mass based on the total solid content of the heat-expandable refractory material composition.
• the content of the heat-expandable compound in the heat-expandable refractory composition is more preferably 7 to 50% by mass, still more preferably 10 to 40% by mass, still more preferably 15 to 30% by mass based on the total solid content. %.
• the heat-expandable compound it is also preferable to use a heat-expandable graphite and a foamable flame retardant in combination.
• the content of the heat-expandable graphite when these are used in combination is as described above.
• the content of the effervescent flame retardant is preferably 5 to 70% by mass based on the total solid content of the heat-expandable refractory composition.
• the content of the effervescent flame retardant is more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, and even more preferably 20 to 35% by mass.
• the mass ratio of the content of the effervescent flame-retardant to the heat-expandable graphite in the heat-expandable refractory material composition is , 0.1-10 is preferable.
• the content ratio is more preferably 0.2 to 5, further preferably 0.5 to 3, and even more preferably 0.8 to 2.
• the heat-expandable refractory composition contains an adhesive base.
• the adhesive base is an adhesive component for exhibiting adhesiveness to the work piece.
• Examples of the adhesive base include a hot melt type adhesive base, a one-component curable adhesive base, a two-component curable adhesive base, an emulsion type adhesive base, and a solvent-based adhesive base.
• the hot melt type adhesive base has no fluidity at room temperature, but becomes fluid when heated. Further, the heated hot melt type adhesive base is solidified by cooling again.
• the heat-expandable refractory composition of the present invention becomes a hot-melt type composition by having a hot-melt type adhesive base.
• the hot-melt adhesive base is used as the adhesive base in the heat-expandable fire-resistant material composition of the present invention, it becomes easy to maintain good adhesiveness to the work piece not only before combustion but also after combustion. Therefore, the expansion residue after combustion can be continuously adhered to the work piece, and the fire resistance becomes better.
• the heat-expandable refractory composition can be cooled and immediately solidified when left at around room temperature after application, so that workability is improved. ..
• a resin conventionally used as the main agent of the hot-melt adhesive (hereinafter, also referred to as “main agent resin”) can be used, and specifically, an ethylene-vinyl acetate copolymer.
• Resins such as resin (EVA), ethylene- (meth) acrylic acid ester copolymer resin, polyolefin resin, and rubber can be used.
• the main resin may be used alone or in combination of two or more. Among these, at least one selected from ethylene-vinyl acetate copolymer resin (EVA) and ethylene- (meth) acrylic acid ester copolymer resin is preferable.
• ethylene-vinyl acetate copolymer resin (EVA) is more preferable as the main resin of the hot melt type adhesive base.
• the ethylene-vinyl acetate copolymer resin (EVA) used in the hot-melt adhesive base is not particularly limited as long as it is a resin obtained by copolymerizing ethylene and vinyl acetate.
• the vinyl acetate content of the ethylene-vinyl acetate copolymer resin is not particularly limited, but is preferably 15 to 45% by mass, more preferably 20 to 40% by mass, from the viewpoint of suitable use as a hot melt type adhesive base. , 25-35% by mass is more preferable.
• the vinyl acetate content is measured according to JIS K 6924-1: 1997.
• Examples of the (meth) acrylic acid ester constituting the ethylene- (meth) acrylic acid ester copolymer resin include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and isobutyl acrylate. It has (meth) acrylic acid alkyl esters such as 2-ethylhexyl acrylate, isooctyl acrylate, methyl methacrylate and ethyl methacrylate, epoxy groups such as 2-hydroxyethyl acrylic acid and glycidyl acrylate, and functional groups such as hydroxyl groups ( Meta) Acrylic acid ester and the like can be mentioned. These may be used alone or in combination of two or more.
• the ethylene- (meth) acrylic acid ester copolymer resin may be a copolymer of a third component such as carbon monoxide or maleic anhydride.
• the ethylene- (meth) acrylic acid ester copolymer resin is preferably an ethylene-methyl methacrylate copolymer (EMMA).
• EMMA ethylene-methyl methacrylate copolymer
• the content of the constituent unit derived from the (meth) acrylic acid ester in the ethylene- (meth) acrylic acid ester copolymer resin is not particularly limited, but is, for example, 5 to 50% by mass, preferably 10 to 40% by mass. More preferably, it is 15 to 35% by mass.
• polyolefin-based resin examples include at least one olefin-based copolymer in which ethylene and an ⁇ -olefin having 3 to 20 carbon atoms are copolymerized.
• ⁇ -olefin having 3 to 20 carbon atoms examples include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.
• olefin-based copolymers a copolymer of ethylene and an ⁇ -olefin having 6 to 8 carbon atoms is preferable, and a copolymer of ethylene and 1-octene is more preferable.
• These olefin-based copolymers may be used alone or in combination of two or more.
• the olefin-based copolymer preferably has an ⁇ -olefin copolymerization ratio of 20 to 40 mol%. Further, the olefin-based copolymer preferably has a melt flow rate (g / 10 minutes) of 5 to 2500, more preferably 150 to 2500. The melt flow rate of the olefin-based copolymer is measured under the conditions of 190 ° C. and a load of 21.2 N in accordance with JIS K7210.
• These commercially available copolymers of ethylene and 1-octene have a copolymerization ratio of 1-octene of 35 to 37 mol%.
• copolymer of ethylene and ⁇ -olefin having 3 to 20 carbon atoms can be used, and polyethylene, polypropylene, polyhexene, polyoctene, propylene-butene copolymer, propylene-hexene copolymer, and propylene-. It may be an octene copolymer or the like.
• polyolefin resins may also be appropriately selected so that, for example, the melt flow rate is within the above range.
• the rubber used for the hot melt type adhesive base is a diene type such as butadiene, styrene-butadiene, chloroprene, butadiene-acrylonitrile, a non-diene type such as isobutylene-isoprene, ethylene-propylene, a styrene type, an olefin type, and an ester type.
• Thermoplastic type such as urethane type (also called thermoplastic elastomer) and the like.
• the melt flow rate (MFR) of the main resin used in the hot melt type adhesive base is not particularly limited, but is, for example, 1 to 3000 g / 10 minutes, preferably 5 to 2500 g / from the viewpoint of coatability and adhesiveness. It is 10 minutes, more preferably 10 to 1500 g / 10 minutes, still more preferably 100 to 1000 g / 10 minutes, and even more preferably 150 to 1000 g / minute.
• the melt flow rate was measured under the conditions of 190 ° C. and a load of 21.2 N, and the ethylene-vinyl acetate copolymer resin may be measured in accordance with JIS K 6924-1: 1997.
• the main resin other than the ethylene-vinyl acetate copolymer resin such as the ethylene- (meth) acrylic acid ester copolymer resin, may be measured in accordance with JIS K7210: 1999.
• the hot melt type adhesive base preferably contains an adhesiveness-imparting resin in addition to the above-mentioned main agent resin.
• the tackifier resin include rosin-based, terpene-based, petroleum resin-based, and kumaron resin-based resins.
• the rosin-based tackifier resin include gum rosin, wood rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, dimerized rosin, and esters of the various rosins with pentaerythritol, glycerin, diethylene glycol, and the like (rosin ester). , Rosinphenol resin and the like.
• terpene-based tackifier resin examples include terpene resin, terpene and styrene copolymer, terpene and ⁇ -methylstyrene copolymer, terpene and phenol copolymer, and hydrogenation thereof. Things etc. can be mentioned.
• the petroleum resin-based tackifier resin examples include aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, and hydrogenated compounds thereof. Be done.
• unhydrogenated C9-based petroleum resin is preferable.
• the unhydrogenated C9-based petroleum resin is a resin obtained by (co) polymerizing the C9 to C10 fractions contained in the decomposed oil fraction produced by steam cracking of petroleum, that is, the aromatic fraction. It is a resin that has not been hydrogenated.
• These unhydrogenated C9-based petroleum resins may be used alone or in combination of two or more.
• (co) polymerization means homopolymerization or copolymerization.
• the C9 to C10 fraction is not particularly limited, and examples thereof include vinyl aromatic hydrocarbons such as vinyltoluene, indene, styrene, and ⁇ -methylstyrene.
• examples of the kumaron resin-based tackifier resin include kumaron resin and kumaron inden resin.
• xylene resin can also be used as the tackifier resin.
• petroleum resin-based and rosin-based resins are preferable as the tackifier resin.
• the tackifier resin may be used alone or in combination of two or more.
• the softening point of the tackifier resin is not particularly limited, but is, for example, 90 to 150 ° C, preferably 100 to 140 ° C, and more preferably 110 to 130 ° C. When the softening point is within the above range, the adhesiveness, coatability, solidification or strength of the heat-expandable refractory composition can be improved in a well-balanced manner.
• the softening temperature is the softening temperature measured by the JIS K2207 ring ball method.
• the content of the tackifier resin is 10 to 300 parts by mass with respect to 100 parts by mass of the above-mentioned base resin. Is preferable.
• the tackifier resin is 10 parts by mass or more, the adhesiveness of the heat-expandable refractory composition can be enhanced by the tackifier resin.
• the amount is 300 parts by mass or less, it is possible to prevent the strength of the heat-expandable refractory material after solidification or curing from being impaired by the tackifier resin.
• the content of the tackifier resin is more preferably 25 to 200 parts by mass, further preferably 40 to 120 parts by mass.
• the content of the heat-expandable compound is preferably 10 to 300 parts by mass with respect to 100 parts by mass of the main agent resin described above.
• the content of the heat-expandable compound is at least the above lower limit value, good fire resistance can be imparted to the heat-expandable refractory material.
• the content is 300 parts by mass or less, the strength of the heat-expandable refractory material tends to be good. From these viewpoints, the content of the heat-expandable compound is more preferably 25 to 250 parts by mass, and even more preferably 50 to 200 parts by mass.
• the melt viscosity of the heat-expandable refractory material composition may be 300,000 mPa ⁇ s or less at a temperature equal to or less than the expansion start temperature of the heat-expandable compound. preferable.
• the melt viscosity is 300,000 mPa ⁇ s or less at a temperature equal to or lower than the expansion start temperature, the workability becomes good. It can be applied to the object to be constructed by its nature. From the viewpoint of coatability and workability, the melt viscosity is more preferably 200,000 mPa ⁇ s or less, still more preferably 150,000 mPa ⁇ s or less.
• the expansion start temperature referred to here means the expansion start temperature of the heat-expandable compound having the lowest expansion start temperature when the heat-expandable fire-resistant material composition contains two or more kinds of heat-expandable compounds. do.
• the melt viscosity of the heat-expandable refractory composition at 150 ° C. is preferably 300,000 mPa ⁇ s or less, more preferably 200,000 mPa ⁇ s. Below, it is more preferably 150,000 mPa ⁇ s or less.
• the melt viscosity at 150 ° C. is not more than these upper limit values, the workability is good even when a thermally expandable compound having a suitable expansion start temperature is used.
• the hot melt adhesive is an adhesive base material that easily causes dripping, but by adding an inorganic filler such as calcium carbonate, the thixo property can be improved and the dripping can be significantly improved.
• the heat-expandable refractory material composition can be made into a one-component curable type by using a one-component curable adhesive base as the adhesive base.
• the one-component curable adhesive base is preferably a moisture-curable adhesive base that cures with moisture in the air.
• a crosslinkable silyl group-containing polymer, an isocyanate group-containing polymer, a cyanoisocyanate-based adhesive base, or the like may be used. These may be used alone or in combination of two or more.
• a crosslinkable silyl group-containing polymer is preferable as the one-component curable adhesive base.
• the crosslinkable silyl group in the crosslinkable silyl group-containing polymer is specifically a functional group represented by the following formula (1).
• the number of crosslinkable silyl groups is not particularly limited as long as it is 1 or more, but for example, it is preferably about 1 to 5 and more preferably about 2 to 4.
• R 1 is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and having 1 to 4 carbon atoms. Alkyl groups are more preferred.
• X indicates a reactive group, and the reactive group represented by X is a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, a ketooxime group, an alkenyloxy group and the like.
• X is a group selected from aminooxy groups, and when there are a plurality of Xs, X may be the same group or different groups.
• X is preferably an alkoxy group or a ketooxime group, and more preferably an alkoxy group. Further, the alkoxy group is more preferably a methoxy group.
• a is an integer of 0, 1 or 2, with 0 or 1 being more preferred.
• the crosslinkable silyl group-containing polymer is selected from a crosslinkable silyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing acrylic polymer, and a crosslinkable silyl group-containing acrylic-modified polyoxyalkylene polymer. At least one of these (these may be collectively referred to as "modified silicone") is preferable.
• modified silicones By using these modified silicones as a one-component curable adhesive base, the residual hardness and expansion ratio can be increased in a well-balanced manner. In addition, it has good weather resistance and can be suitably used for outdoor use. Furthermore, the adhesive strength tends to be good for objects to be constructed of various materials.
• crosslinkable silyl group-containing polyoxyalkylene polymer a polymer containing a crosslinkable silyl group in the molecule and having a polyoxyalkylene in the main chain skeleton is preferable, and the polymer having a polyoxyalkylene in the main chain skeleton and having a polyoxyalkylene is preferable.
• a polymer containing a crosslinkable silyl group at the end of the main chain is more preferable.
• 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 preferable.
• a polymer having a (meth) acrylic-modified polyoxyalkylene and a crosslinkable silyl group at the end of the main chain is more preferable.
• the (meth) acrylic-modified polyoxyalkylene is preferably (meth) acrylic-modified polyoxypropylene.
• the crosslinkable silyl group-containing acrylic polymer examples include a polymer having an acrylic polymer in the main chain skeleton and having one or more crosslinkable silyl groups in the molecule.
• the acrylic polymer conventionally known ones can be used, and are selected from acrylic monomers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, and (meth) acrylamide 1. It is not particularly limited as long as it is an acrylic polymer obtained by polymerizing or copolymerizing seeds or more.
• the acrylic polymer preferably contains a (meth) acrylic acid ester monomer as a main component (for example, 50% by mass or more, preferably 70% by mass or more in the polymer), and has a carbon number of the ester portion. Examples thereof include 1 to 20 acrylic acid esters. Further, the acrylic polymer can be copolymerized with a monomer copolymerizable with the acrylic monomer in addition to the acrylic monomer. Examples of the copolymerizable monomer include vinyl-based monomers such as fluoroolefins, ⁇ -olefins, vinyl esters and vinyl ethers.
• the number average molecular weight of the modified silicone is not particularly limited, but is, for example, 5000 to 100,000, preferably 10,000 to 50,000.
• the number average molecular weight is a value measured by the GPC method in terms of polystyrene.
• Commercially available products can also be used as the modified silicone.
• the crosslinkable silyl group-containing polyoxyalkylene polymer "MS Polymer S203" and “MS Polymer S303" manufactured by Kaneka Corporation can be used.
• crosslinkable silyl group-containing polymer a crosslinkable silyl group-containing silicone resin may be used in addition to the above.
• the crosslinkable silyl group-containing silicone resin is a polymer having a polyorganosiloxane in the main chain and a crosslinkable silyl group at the end.
• crosslinkable silyl group-containing silicone resin "Sekisui Silicone Sealant" manufactured by Sekisui Fuller Co., Ltd. can also be used.
• the two-component curable adhesive base is an adhesive base that cures by mixing two liquids.
• the heat-expandable refractory composition can be made into a two-component curable type by using a two-component curable adhesive base as the adhesive base.
• the adhesive strength can be relatively high.
• it is easy to control the curing time by appropriately changing the adhesive base used.
• the two-component curable adhesive base is composed of a main agent and a curing agent, and may be stored separately until immediately before use. Therefore, when a two-component curable adhesive base is used, the components other than the two-component curable adhesive base may be blended in either the main agent or the curing agent. Then, it is advisable to mix the 1st liquid containing the main agent and the 2nd liquid containing the curing agent immediately before use to obtain a heat-expandable refractory material composition.
• a resin generally used for the two-component curable adhesive may be used, and examples thereof include polyurethane-based resin, epoxy-based resin, and acrylic-based resin. Among these, epoxy is used. Based resin is preferable.
• an epoxy compound having an epoxy group may be used as the main agent, and a curing agent for curing the epoxy group may be used as the curing agent.
• Known curing agents can be used, and polyamine-based, imidazole-based, polypeptide-based, acid anhydride-based, and the like can be used.
• the epoxy resin a commercially available product can be used, and for example, "Esdyne 3120" manufactured by Sekisui Fuller Co., Ltd. can be used.
• the emulsion-type adhesive base is dispersed in a dispersion medium, preferably water, in the heat-expandable refractory composition.
• a dispersion medium preferably water
• the heat-expandable fire-resistant material composition is made into an emulsion dispersion liquid to form an emulsion type.
• the emulsion-type heat-expandable refractory composition can be solidified by volatilizing the dispersion medium.
• the residual hardness and the expansion ratio can be increased in a well-balanced manner.
• the emulsion type adhesive base vinyl acetate resin type, ethylene-vinyl acetate resin type, acrylic resin type, aqueous polymer-isocyanate type and the like can be used.
• an ethylene-vinyl acetate resin system is preferable.
• an ethylene vinyl acetate copolymer resin may be used as an adhesive base.
• a commercially available product can also be used.
• the ethylene-vinyl acetate resin system "Esdyne K-474" manufactured by Sekisui Fuller Co., Ltd. can be used.
• solvent-based adhesive base The solvent-based adhesive base is dissolved in an organic solvent in the heat-expandable refractory composition.
• the heat-expandable fire-resistant material composition becomes a solvent-based material in which the organic solvent is contained and the solvent-based adhesive base is dissolved in the organic solvent.
• the solvent-based heat-expandable refractory composition can be solidified by volatilizing an organic solvent.
• the solvent-based adhesive base examples include vinyl acetate resin-based, chloroprene rubber-based, and acrylic resin-based, and among these, chloroprene rubber-based and acrylic resin-based are preferable.
• chloroprene rubber-based adhesive base chloroprene rubber conventionally used for solvent-based adhesives may be used.
• acrylic resin-based adhesive base the acrylic resin conventionally used for the solvent-based adhesive may be used.
• the solvent-based adhesive base when a chloroprene rubber-based adhesive is used as the solvent-based adhesive base, the residual hardness and the expansion ratio can be increased in a well-balanced manner. Further, when the acrylic resin system is used, it becomes easy to maintain good adhesiveness to the work piece not only before combustion but also after combustion.
• the adhesive base uses a base other than the hot melt adhesive base (that is, for example, the base other than the hot melt adhesive base is the main component, and the heat-expandable refractory material composition is a one-component curing type or two-component adhesive.
• the viscosity of the heat-expandable refractory material composition at room temperature (23 ° C.) is preferably 500,000 mPa ⁇ s or less. It is more preferably 300,000 mPa ⁇ s or less, still more preferably 200,000 mPa ⁇ s or less, still more preferably 150,000 mPa ⁇ s or less.
• the viscosity of the heat-expandable refractory composition at room temperature is not particularly limited, but is preferably 400 mPa ⁇ s or more, more preferably 4000 mPa ⁇ s or more, from the viewpoint of preventing dripping when the composition is applied. It is preferable, and more preferably 10,000 mPa ⁇ s or more.
• the content of the adhesive base in the heat-expandable refractory composition of the present invention is preferably 10 to 80% by mass based on the solid content.
• the content of the adhesive base is preferably 10 to 80% by mass based on the solid content.
• the adhesiveness of the heat-expandable refractory material obtained by solidifying or curing the heat-expandable refractory material composition to the work piece can be improved.
• the content is 80% by mass or less, components other than the adhesive base such as a heat-expandable compound can be contained in a certain amount or more, and various performances such as fire resistance are improved.
• the content of the adhesive base in the heat-expandable refractory composition is more preferably 15% by mass or more, further preferably 20% by mass or more, still more preferably 70% by mass or less, and more preferably 60% by mass or less. Is even more preferable.
• the hot-melt adhesive base, one-component curable adhesive base, two-component curable adhesive base, emulsion-type adhesive base, and solvent-based adhesive base described above are each heat-expandable fire-resistant materials. It is preferable to use it alone in the composition.
• the adhesive base contains a hot melt type adhesive base
• the hot melt type adhesive base may be used alone as the adhesive base. The same applies to other adhesive bases.
• the heat-expandable fireproof material composition may contain an adhesive base other than the hot melt type adhesive base in addition to the hot melt type adhesive base, for example, in addition to the hot melt type adhesive base. It may contain a one-component curable adhesive base.
• the hot-melt type adhesive base may be the main component. Therefore, even if the hot-melt type heat-expandable fireproof material composition contains other adhesive bases, it is preferable that the content of the hot-melt type adhesive base is higher than that of the other adhesive bases.
• the content thereof is, for example, 50 to 100% by mass, preferably 75 to 100% by mass, and more preferably 85 to 100% by mass based on the total amount of the adhesive base.
• the one-component curable adhesive base is mainly used. It may be an ingredient.
• the content of the one-component curable adhesive base is higher than the content of other adhesive bases, and the content is, for example, 50 to 100% by mass, preferably 60 to 100% based on the total amount of the adhesive base. It is by mass, more preferably 70 to 100% by mass.
• other adhesive bases may be used in combination, and for example, a one-component curable adhesive base and a solvent-based adhesive base may be used in combination.
• the heat-expandable refractory composition of the present invention may contain an inorganic filler other than the above-mentioned heat-expandable compound.
• an inorganic filler When the inorganic filler is heated to form an expanded heat insulating layer, it acts as an aggregate to improve the strength of the expanded residue while increasing the heat capacity and suppressing heat transfer.
• the inorganic filler that can be used in the present invention is not particularly limited, and for example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite, calcium carbonate, and the like.
• Metallic carbonates such as zinc carbonate, strontium carbonate and barium carbonate, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide and hydrotalcite, calcium sulfates, gypsum fibers, calcium salts such as calcium silicate, Silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, active white clay, sepiolite, imogolite, phosphoric acid, glass fiber, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, carbon black.
• metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide and hydrotalcite
• calcium sulfates such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide and hydrotalcite
• calcium sulfates such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide and hydrotalcite
• calcium salts
• the inorganic filler may be used alone or in combination of two or more.
• calcium carbonate, barium sulfate, aluminum hydroxide and the like are preferable from the viewpoint of improving the fire resistance performance of the heat-expandable fire-resistant material, and calcium carbonate is more preferable among these.
• the inorganic filler may be used alone or in combination of two or more. Further, calcium carbonate is particularly preferably used in combination with ammonium polyphosphate. When these are used together, it becomes easy to increase the residual hardness.
• the content thereof is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, based on the total solid content of the heat-expandable refractory composition. %, More preferably 10 to 40% by mass.
• the heat-expandable refractory composition of the present invention may contain a plasticizer.
• a plasticizer By containing the plasticizer, the viscosity of the heat-expandable refractory composition can be lowered, and the coatability and workability can be improved.
• the plasticizer is not particularly limited, but can be suitably used, for example, when modified silicone is used as an adhesive base.
• the plasticizer include polyether-based plasticizers such as polyalkylene oxide.
• the content of the plasticizer is, for example, 1 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 75 parts by mass with respect to 100 parts by mass of the adhesive base.
• the heat-expandable refractory composition of the present invention may contain a flame retardant other than the above-mentioned effervescent flame retardant.
• flame retardants include phosphoric acid ester compounds.
• the phosphoric acid ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, and tris (2,3-).
• Dichloropropyl) phosphate tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate , Tris (2 ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate (TCP), tricylenyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate and the like.
• the heat-expandable refractory composition of the present invention may further contain a catalyst, a polymerization initiator and the like.
• the catalyst can be suitably used as a curing catalyst when the heat-expandable refractory composition has curability, such as a one-component curing type and a two-component curing type.
• the heat-expandable refractory composition of the present invention can accelerate the curing reaction by containing a curing catalyst.
• a titanium-based catalyst, a tin-based catalyst, a zirconium-based catalyst, an aluminum-based catalyst, a bismuth-based catalyst, or the like can be used, and among these, a tin-based catalyst is preferable.
• the content of the catalyst in the heat-expandable refractory composition is not particularly limited, but is about 0.1 to 15 parts by mass with respect to 100 parts by mass of the adhesive base.
• polymerization initiator examples include organic peroxides such as dicumyl peroxide and polymerization initiators such as azo compounds.
• the content of the polymerization initiator is, for example, about 0.1 to 15 parts by mass with respect to 100 parts by mass of the adhesive base.
• the polymerization initiator may be added, for example, when a hot melt adhesive base is used, from the viewpoint of maintaining the shape of the heat-expandable refractory material so that it does not easily collapse when expanded.
• the heat-expandable refractory composition of the present invention may contain additives other than the above, if necessary, as long as the object of the present invention is not impaired.
• additives include, for example, lubricants, shrinkage agents, crystal nucleating agents, colorants (pigments, dyes, etc.), UV absorbers, antioxidants, antioxidants, flame retardants, antistatic agents, surfactants, interfaces. Examples thereof include activators, vultures, dispersants, surface treatment agents and the like.
• the additive may be used alone or in combination of two or more.
• the heat-expandable fire-resistant material composition may contain an organic solvent for dissolving the adhesive base in a solvent system, and may contain a dispersion medium such as water for dispersing the adhesive base in an emulsion system.
• the heat-expandable fire-resistant material composition of the present invention can be obtained by mixing an adhesive base, a heat-expandable compound, an inorganic filler to be blended as needed, and other components. Further, in the case of an emulsion type or a solvent type, the heat-expandable fire-resistant material composition is blended with an organic solvent in which an adhesive base is previously dissolved, a dispersion medium in which the adhesive base is dispersed, a heat-expandable compound, and the like, if necessary. It is good to manufacture by adding and mixing the components.
• a main agent and a curing agent are prepared as an adhesive base, and a heat-expandable compound and other components to be blended as necessary are added to at least one of the main agent and the curing agent. It is advisable to prepare a liquid and two liquids. In this case, it is advisable to mix the 1st liquid and the 2nd liquid immediately before use to prepare a heat-expandable refractory material composition.
• the heat-expandable refractory material of the present invention is obtained by solidifying or curing the above-mentioned heat-expandable refractory material composition.
• the heat-expandable refractory material of the present invention it is preferable that the above-mentioned heat-expandable refractory composition is applied to a work piece and solidified or hardened, and it is preferable that the heat-expandable refractory material is formed in a film shape on the work piece. ..
• the thickness of the heat-expandable refractory material formed in the form of a film on the work piece is not particularly limited, but is 0.1 to 20 mm, preferably 0.3 to 10 mm, and more preferably 0.5 to 5 mm.
• the heat-expandable refractory material may be one that is filled in the gaps of the work piece and the like, and the filled heat-expandable refractory material composition is solidified or hardened.
• the object to be constructed include members having a hollow portion inside such as a square pipe and a sash frame, and the hollow portion may be filled with a heat-expandable refractory composition.
• the size of the heat-expandable refractory material filled in the gap of the work piece is not particularly limited and may have a size corresponding to the gap.
• the heat-expandable refractory material of the present invention preferably has a volume expansion coefficient of 10 times or more and a residual hardness of 0.1 kgf / cm 2 or more when heated at 600 ° C. for 10 minutes.
• the heat-expandable refractory material can have good fire resistance when the coefficient of thermal expansion and the residual hardness are at least the above lower limit values.
• the volume expansion coefficient is more preferably 20 times or more, still more preferably 30 times or more.
• the upper limit of the volume expansion coefficient is not particularly limited, but is, for example, 150 times, preferably 100 times, from the viewpoint of setting the expansion residue hardness to a certain value or more.
• the residual hardness is more preferably 0.15 kgf / cm 2 or more, still more preferably 0.25 kgf / cm 2 or more, and the upper limit of the volume expansion coefficient is not particularly limited, but for example, 1. It is 5 kgf / cm 2 .
• the coefficient of thermal expansion and the residual hardness can be measured by the measuring method described in Examples described later.
• the heat-expandable refractory material of the present invention can be produced by applying the above-mentioned heat-expandable refractory composition to a work piece and solidifying or curing the heat-expandable refractory material applied to the work piece.
• the method of applying the thermal expansion property to the work piece is not particularly limited, but the method of applying the work piece to the work piece by a brush or a known coating device, or the method of applying the work piece to the work piece by spraying. How to do it.
• the heat-expandable refractory material of the present invention is obtained by filling the gaps and the like of the work piece with the heat-expandable fire-resistant material composition and solidifying or hardening the heat-expandable refractory material filled in the work piece. It can also be manufactured.
• the heat-expandable refractory composition has a hot-melt type adhesive base, and when the heat-expandable refractory composition is a hot-melt type, the heat-expandable refractory composition is heated to form the heat-expandable refractory material. It is preferable to melt the object, and the melted heat-expandable refractory composition may be applied or filled in the object to be constructed.
• the heat-expandable refractory composition is preferably heated to a temperature equal to or lower than the expansion start temperature of the heat-expandable compound when melted, and the heating temperature is, for example, 100 to 160 ° C, preferably 120 to 155 ° C. be.
• the expansion start temperature of the heat-expandable compound referred to here is the expansion of the heat-expandable compound having the lowest expansion start temperature when the heat-expandable fire-resistant material composition contains two or more kinds of heat-expandable compounds. The starting temperature.
• the method for solidifying or curing the heat-expandable refractory composition applied or filled in the work piece is not particularly limited.
• the heat-expandable refractory composition can be left at around room temperature (for example, about 0 to 40 ° C.) in the atmosphere. Can be solidified or hardened.
• the heat-expandable refractory composition applied or filled in the work piece may be heated or the like, if necessary.
• the adhesive base is either an emulsion type adhesive base or a solvent-based adhesive base
• the heat-expandable fire-resistant material composition is promoted to be solidified by heating to volatilize the organic solvent or water. You may let me.
• the adhesive base is a two-component curable adhesive base
• the heat-expandable refractory composition may be heated to accelerate the curing.
• the heat-expandable fire-resistant material composition and the heat-expandable fire-resistant material of the present invention include various buildings such as detached houses, apartment houses, high-rise houses, high-rise buildings, commercial facilities, public facilities, and various vehicles such as automobiles and trains. , Can be used for ships, aircraft, electronic devices, etc. For example, as a building, it is applied to fittings such as windows, shoji, doors, doors, and bran, and building materials other than fittings such as walls, beams, pillars, floors, bricks, roofs, plates, pipes, and wiring. can do.
• a fireproof sash having a heat-expandable refractory material can be obtained by applying a heat-expandable refractory material composition to the sash and solidifying or hardening the sash.
• the heat-expandable refractory material is filled with the heat-expandable refractory composition inside the frame material such as the sash frame that constitutes the fitting, and the inside of the square pipe that constitutes the pillar, beam, etc., and solidified or hardened. It may be a fitting, a pillar, a beam, etc. Further, it can be applied to the outer wall of a building or the like, or can be used as a refractory joint material by filling the gaps in the outer wall.
• the heat-expandable fire-resistant material composition of the present invention is applied to the surface of a battery case such as a lithium ion battery, a cover material of an electronic device, or the like in an electronic device such as a battery case or a smartphone, or a gap in the battery case, an electron, or the like. It can also be used by filling the gaps inside the device.
• the heat-expandable fire-resistant material composition of the present invention can prevent a fire or the like from occurring even if a battery such as a lithium-ion battery causes thermal runaway.
• the heat-expandable refractory composition of the present invention can also be used as an adhesive, and adheres to various parts in various buildings, various vehicles such as automobiles and trains, ships, aircraft, electronic devices, and the like. May be used to. Further, it may be used as a packing for sealing between parts in various buildings, various vehicles such as automobiles and trains, ships, aircrafts, electronic devices and the like.
• an adhesive, packing, etc. around a battery such as a lithium-ion battery in an electric vehicle or an electronic device such as a smartphone
• a ship it may be used as an adhesive, a watertight material, or the like in a fireproof regulated portion of the ship.
• EVA Ethylene-vinyl acetate copolymer resin
• hot melt type adhesive base "Ultrasen 726", manufactured by Tosoh Corporation
• vinyl acetate content 33% by mass
• melt flow rate 700 g / 10 minutes (190 ° C, load 21.
• EMMA Ethylene-methyl methacrylate copolymer, hot melt adhesive base, "Aklift CM5021", manufactured by Sumitomo Chemical Co., Ltd., MMA (methyl methacrylate) content 28% by mass, melt flow rate 450 g / 10 minutes (190 ° C) , Load 21.2N) Modified Silicone: 1-component curable adhesive base, "MS Polymer S303", manufactured by Kaneka Corporation, polyalkylene oxide having a main chain skeleton made of polypropylene oxide and a propyldimethoxysilyl group at the end of the main chain, number average molecular weight 20000
• EVA emulsion Emulsion type adhesive base, "Esdyne K-474", manufactured by Sekisui Fuller, water-based adhesive mainly composed of ethylene-vinyl acetate copolymer resin, solid content 40% by mass CR rubber solvent-based: solvent-based adhesive base, "Esdyne 235L”, manufactured
• Silicone resin 1-component curable adhesive base, "Sekisui Silicone Sealant”, manufactured by Sekisui Fuller, silicone resin with ketooxime silyl group (adhesive-imparting resin) C9 unhydrogenated: unhydrogenated C9 petroleum resin (aromatic petroleum resin), "Petcol 120", manufactured by Tosoh, glass transition temperature (Tg) 120 ° C, softening point 120 ° C Rosin: Rosin ester, "Super Ester A-125", manufactured by Arakawa Chemical, glass transition temperature (Tg) 115 ° C, softening point 125 ° C (Non-adhesive base) Polyethylene: “L405", manufactured by Sumitomo Chemical
• Thermal expandable compound> (Thermal expandable graphite) Thermally expandable graphite 1: “ADT351", ADT's thermally expandable graphite 2: “EXP50S150”, Fuji Kokuen's thermally expandable graphite 3: “EXP50S160”, Fuji Kokuen's thermally expandable graphite 4: “EXP42S160” , Made by Fuji Graphite Co., Ltd. (foamable flame retardant) Aluminum Phosphate: "APA100”, Ammonium Polyphosphate 1: “AP422” manufactured by Taihei Chemical Co., Ltd., Ammonium Polyphosphate 2: “AP462” manufactured by Clariant, manufactured by Clariant.
• Example 1 Each component was uniformly heated, melted and kneaded at 130 ° C. according to the formulation shown in Table 1 to obtain a hot melt type heat-expandable refractory composition.
• Example 11 According to the formulation shown in Table 1, components other than the adhesive base were added to the EVA emulsion dispersion (Esdyne K-474) containing the adhesive base, and the mixture was mixed at room temperature to obtain a heat-expandable fire-resistant composition.
• Example 12 According to the formulation shown in Table 1, components other than the adhesive base were added to a CR rubber solution (Esdyne 235L) containing an adhesive base and mixed at room temperature to obtain a heat-expandable refractory composition.
• a CR rubber solution Esdyne 235L
• Example 13 According to the formulation shown in Table 1, a component other than the adhesive base was added to an acrylic resin solution (Esdyne 7858) containing an adhesive base and mixed at room temperature to obtain a heat-expandable refractory composition.
• Example 14 Each component other than the adhesive base was mixed with the main agent of "Esdyne 3120" containing an epoxy compound to prepare one liquid, and the curing agent of "Esdyne 3120" was made into two liquids. These 1st and 2nd liquids were mixed immediately before the measurement and evaluation of each physical property to obtain a heat-expandable refractory composition.
• the measurement method and evaluation method for each physical property are as follows. [Evaluation methods] (Expansion start temperature of thermally expandable graphite) 100 mg of heat-expandable graphite was collected as a sample, and the temperature was raised at a temperature rise temperature of 10 ° C./min using a leometer (TA Instrument Co., Ltd., "Discovery HR2") to obtain a force in the normal direction. The rising temperature was measured and used as the expansion start temperature.
• the heat-expandable refractory composition obtained in each example was applied to a 98 mm square iron plate in a 30 mm square, and left at room temperature in the air for the curing or solidification time described later in each example.
• the heat-expandable refractory composition was solidified or hardened to form a heat-expandable refractory material having a thickness of about 1.5 mm on an iron plate.
• the temperature of the heat-expandable refractory composition at the time of coating was 150 ° C. in Examples 1 to 8 and 16, and 23 ° C. in Examples 9 to 15, 17 and 18.
• the sheet-shaped heat-expandable fire-resistant material composition was thermocompression-bonded to an iron plate at a temperature of 130 ° C. to be adhered. rice field. An iron plate on which a heat-expandable refractory material was formed was put into an electric furnace preheated to 600 ° C., heated and burned for 10 minutes, and then taken out.
• the expansion ratio was calculated by the following formula.
• Coefficient of expansion Volume of expansion residue after combustion / Volume of thermally expandable refractory material before combustion
• compression is performed from the top surface of the expansion residue using a compression tester (“Finger Filling Tester” manufactured by Kato Tech Co., Ltd.). Compression was applied at a rate of 0.1 cm / sec with a child (three-point indenter with a diameter of 1 mm), and the largest compression load was read at a compression depth of 0 to 8 mm to obtain the residual hardness.
• the iron plate on which the heat-expandable refractory material is formed before being heated and burned in the electric furnace and the iron plate having the expansion residue after heating (600 ° C.) are vertically tilted so that the heat-expandable refractory material or the expansion residue can be removed.
• the case where it was attached to the iron plate was designated as "A”
• the case where the heat-expandable refractory material or the expansion residue fell off was designated as "B”.
• an iron plate on which a heat-expandable refractory material was formed was put into an electric furnace preheated to 500 ° C., heated and burned for 10 minutes, then taken out and evaluated in the same manner.
• the SUS plate had a length of 12 mm, a width of 50 mm, a thickness of 4.0 mm, and a flat rectangular shape.
• a heat-expandable refractory material composition was applied to the surface of one SUS plate, and the other SUS plate was superposed on the coated surface of the heat-expandable refractory material composition to prepare a laminated body.
• the heat-expandable refractory composition was coated on an aluminum alloy plate so that the coating width (vertical direction) was 12 mm, the coating length (horizontal direction) was 10 mm, and the coating thickness was 0.3 mm.
• the temperature of the heat-expandable refractory composition of each example at the time of coating was the same as that of the above-mentioned fire resistance test.
• the laminate was left in an environment of 23 ° C. and 50% RH for 7 days, and two SUS plates were bonded and integrated with a heat-expandable refractory material to prepare a test body.
• a universal tensile tester manufactured by Instron
• Instron is used to pull in the shear direction at a speed of 5 mm / min to perform a tensile test, and the thermal expansion fireproof material constituting the test piece is performed.
• the tensile shear strength at the time of breaking was measured.
• a heat-expandable refractory composition was applied onto a metal at 23 ° C. and a 50% RH atmosphere with a coating thickness of 2 mm, and immediately after application (1 second later) and every 5 minutes after application.
• the surface of the refractory refractory composition was touched with a metal spatula, and the time until the heat-expandable refractory composition applied to the spatula did not adhere was measured as the curing or solidification time.
• a heat-expandable refractory composition is applied onto a zinc-plated steel plate of 75 mm square and 0.5 mm thick so as to have a size of about 30 mm square, and then cured or solidified to obtain a thickness.
• a heat-expandable refractory material of about 1.5 mm was formed.
• a galvanized steel sheet on which a heat-expandable refractory material was formed was heated at 200 ° C. for 10 minutes in an upright state. The sagging property was evaluated according to the following evaluation criteria according to the state of the heat-expandable refractory material at that time.
• the viscosities in Table 1 are the melt viscosities at 150 ° C. in Examples 1 to 8 and 16, and the viscosities at room temperature (23 ° C.) in Examples 9 to 15, 17 and 18.
• the heat-expandable refractory composition of Comparative Example 1 did not flow at 150 ° C., and the melt viscosity at 150 ° C. could not be measured.
• the blending amount in Table 1 is indicated by the mass part based on the solid content.
• the hot melt type heat-expandable fire-resistant material compositions of Examples 1 to 8 and 16 have fluidity by heating to a temperature lower than the expansion start temperature of the heat-expandable compound, and the heating thereof is performed.
• the heat-expandable fire-resistant material composition was applied to the iron plate, it immediately solidified, and a heat-expandable fire-resistant material adhered to the iron plate with high adhesive strength could be obtained.
• the one-component curable thermal expansion fireproof material composition of Examples 9, 10, 15, 17, and 18 has fluidity at room temperature, and when applied to an iron plate and left at room temperature, it takes a relatively short time. It was possible to obtain a heat-expandable fire-resistant material that was cured and adhered to an iron plate with high adhesive strength.
• the emulsion-type or solvent-based heat-expandable refractory compositions of Examples 11 to 13 have fluidity at room temperature, and when applied to an iron plate and left at room temperature, they solidify in a relatively short time and are high. It was possible to obtain a heat-expandable refractory material bonded to an iron plate with adhesive strength. Further, the two-component curable thermal expansion fireproof material composition of Example 14 has fluidity at room temperature immediately after mixing the first and second liquids, and is compared with the case where it is applied to an iron plate and left at room temperature. It was possible to obtain a heat-expandable fireproof material that was cured in a short period of time and adhered to an iron plate with high adhesive strength.
• the heat-expandable refractory materials of each example had good adhesiveness even after combustion. Further, the heat-expandable refractory materials obtained in each example had a high coefficient of thermal expansion after combustion, a high residual hardness, and excellent fire resistance. On the other hand, the heat-expandable refractory composition of Comparative Example 1 did not flow even when heated to the expansion start temperature of the heat-expandable compound, and could not be adhered to the iron plate with high adhesive strength.

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