WO2024053211A1 - Matériau ignifuge et isolant thermique - Google Patents

Matériau ignifuge et isolant thermique Download PDF

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Publication number
WO2024053211A1
WO2024053211A1 PCT/JP2023/023475 JP2023023475W WO2024053211A1 WO 2024053211 A1 WO2024053211 A1 WO 2024053211A1 JP 2023023475 W JP2023023475 W JP 2023023475W WO 2024053211 A1 WO2024053211 A1 WO 2024053211A1
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Prior art keywords
flame
heat insulating
sheet
inorganic
retardant
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PCT/JP2023/023475
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English (en)
Japanese (ja)
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崇 吉岡
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星和電機株式会社
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Publication of WO2024053211A1 publication Critical patent/WO2024053211A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding

Definitions

  • the present invention relates to a flame-retardant heat insulating material that can be applied to various uses requiring flame retardancy and heat insulation properties, and is suitable, for example, as a heat-insulating material for preventing ignition of secondary battery cells.
  • Insulation materials are used in a wide range of fields in society, including homes, vehicles, aircraft, and packaging materials. Furthermore, insulating materials that have flame-retardant properties in addition to heat-insulating properties are used in a wide range of fields, such as placing them around devices that may generate heat and cause a fire to prevent the spread to other devices. ing. For example, it can be used as mats for vehicles, ceiling materials, dashboards, protective clothing for high-temperature work, gloves, etc., or placed between cells in automobile secondary battery packs to prevent other cells from heating up or catching fire. It is used. Such insulation materials have been developed with various materials and structures.
  • the thickness is 10 to 100 mm, and the whole is made into a sheet by uniformly blending a small amount of low-melting point organic fiber with glass fiber and carbon fiber, and passing hot air vertically through the bulky cotton-like material.
  • a heat insulating mat for a vehicle has been disclosed (for example, see Patent Document 1).
  • a heat insulating material that includes a composite layer containing fibers and silica airgel, and resin struts arranged in the thickness direction in the composite layer.
  • the purpose of this invention is to obtain a heat insulating material that maintains the structure of the heat insulating material against compressive stress and suppresses deterioration of thermal conductivity. has been disclosed (for example, see Patent Document 2).
  • a polymeric foam comprising a brominated flame retardant dispersed therein and an epoxy stabilizer dispersed in the matrix at least 0.1% by weight.
  • a base sheet formed by laminating a film on one side or both sides of a cloth-like body made of filaments is provided, and a flame retardant layer and an adhesive layer are sequentially provided on at least one side of the base sheet.
  • the storage modulus of the combustion layer at 23° C. is 2.0 ⁇ 10 5 Pa or more
  • the storage modulus of the adhesive layer at 23° C. is 5.0 ⁇ 10 4 Pa or more
  • the oxygen index is 26 or more.
  • Flame-retardant adhesive tapes have been disclosed (see, for example, Patent Document 4).
  • the present invention consists of a synthetic laminated mica layer impregnated with silicone resin, an adhesive layer, and a backing material layer, and at least one of the above layers contains aluminum hydroxide or magnesium hydroxide with a particle size of 50 ⁇ m or less.
  • a mica sheet for high temperature electrical insulation is disclosed.
  • the present invention is intended to be used as fireproof heat insulation for fireproof bus ducts, fireproof electric wires, etc. (see, for example, Patent Document 5).
  • the heat insulating mat of the invention disclosed in Patent Document 1 has both nonflammability and heat insulating properties, but it is intended for use in railway vehicles, and cannot be used as a heat insulating material between cells of a secondary battery pack such as a lithium ion battery due to its thickness.
  • the problem is that it is difficult in terms of
  • the present invention also discloses a method of laminating a top sheet made of woven inorganic fibers or felt onto a mat body having a thickness of 10 to 100 mm using a nonflammable resin.
  • a nonflammable resin since sufficient adhesion strength cannot be maintained by bonding with nonflammable resin, there is also the problem that the top sheet easily peels off.
  • the fibers of the composite layer can be made of polyethylene terephthalate, and the resin struts can be made of polystyrene, polypropylene, etc., so flame retardancy is not particularly considered, and there is no possibility of ignition. The problem is that it sometimes burns out.
  • Patent Document 3 uses a brominated flame retardant as a flame retardant dispersed in a foamable polymer, and this is based on a mechanism in which the surface carbonizes during combustion and prevents the progress of combustion.
  • the upper limit temperature for use of this material is around 100°C, there is a problem that it cannot be used in a high temperature range of 100°C or higher.
  • Patent Document 4 is an invention related to a flame-retardant adhesive tape that has a laminated structure of a base sheet and a flame-retardant layer, and has an oxygen index of 26 or more as a whole, thereby imparting flame retardancy. In this invention, there is no disclosure or suggestion of imparting heat insulation properties.
  • the invention described in Patent Document 5 is a mica sheet for high-temperature electrical insulation that has a three-layer structure of a synthetic mica layer impregnated with a silicone resin, an adhesive layer, and a backing layer, and at least one of the three layers has a It is characterized by containing aluminum hydroxide and magnesium hydroxide with a particle size of 50 ⁇ m or less.
  • a synthetic mica layer impregnated with a silicone resin, an adhesive layer, and a backing layer
  • at least one of the three layers has a It is characterized by containing aluminum hydroxide and magnesium hydroxide with a particle size of 50 ⁇ m or less.
  • Hybrid cars and electric cars are equipped with battery packs that have a modular structure of multiple lithium-ion battery cells, which are secondary batteries.
  • Lithium ion batteries are chemically unstable, so if they deteriorate or a short circuit occurs for some reason, the secondary battery cells may generate heat and go into thermal runaway. If this happens, heat may be transferred to adjacent secondary battery cells, leading to thermal runaway one after another, which may result in a major accident.
  • a heat insulating material that has not only heat insulation properties but also flame retardancy is required.
  • the present invention solves the above-mentioned problems, and is a flame-retardant insulation that has both high heat insulation properties that can effectively block heat and flame retardancy that prevents ignition, and has high strength and excellent economic efficiency.
  • the purpose is to provide materials and their manufacturing methods.
  • the flame-retardant heat insulating material of the present invention includes a sheet-like base material having an oxygen index of 26 or more, and a heat-insulating layer laminated on at least one surface of the sheet-like base material,
  • the heat insulating layer is characterized by comprising an inorganic heat insulating filler and an inorganic binder.
  • the inorganic heat insulating filler may be at least one selected from scaly mica, glass balloons, fly ash balloons, shirasu balloons, perlite, silica xerogel, and silica aerogel.
  • flaky mica, glass balloons, fly ash balloons, shirasu balloons, perlite, silica xerogel, and silica aerogel can each provide good heat insulation even when used alone, but multiple materials may also be used. .
  • the inorganic binder may be at least one selected from a silicone binder, a silica binder, an alumina binder, and a zirconia-silica binder.
  • the inorganic binder is not limited to one type, and by mixing a plurality of types, the tensile strength when formed into a sheet may be further improved.
  • the materials to be mixed may be selected in consideration of materials, costs, or the required tensile strength and thickness of the sheet. By using such a material, the flame retardance of the heat insulating layer can be increased, and the flame retardance of the flame retardant heat insulating material can be increased.
  • the sheet-like base material is a woven fabric or non-woven fabric formed from inorganic fibers or inorganic filaments, or a woven fabric or non-woven fabric made of organic fibers, which is imparted with flame retardancy.
  • the flame retardance of the sheet-like base material itself can be increased, and the sheet can be made thinner.
  • it can be made thin as a flame-retardant heat insulating material, making it easy to apply to various devices.
  • tensile strength, high-temperature interlaminar strength between the heat-insulating layer and the sheet-like base material, flame retardance, and thermal conductivity are important.
  • the tensile strength is preferably 0.5 MPa or more. If the tensile strength is 0.5 MPa or more, stable work can be performed without tearing, for example, when it is placed around a secondary battery cell such as a lithium ion battery.
  • the tensile strength is preferably 5 MPa or more, more preferably 10 MPa or more. If the tensile strength is less than 0.5 MPa, it will be easy to tear and it will not be possible to perform stable work.
  • the tensile strength varies depending on the combination with the inorganic heat-insulating filler, inorganic binder, and sheet-like base material used, and the thickness of the fabric, but the upper limit of the tensile strength required for various uses is approximately 25 MPa. be.
  • the high temperature interlaminar strength needs to be 0.5 N/50 mm or more, preferably 3 N/50 mm or more, and more preferably 5 N/50 mm or more.
  • flame retardancy it is required to pass the flame retardancy test method described below.
  • thermal conductivity is important in terms of heat insulation properties and is desirably low, and is required to be 0.20 W/m ⁇ K or less. Preferably it is 0.15 W/m ⁇ K or less, more preferably 0.10 W/m ⁇ K or less, still more preferably 0.08 W/m ⁇ K or less, particularly preferably 0.05 W/m ⁇ K. K or less, most preferably 0.03 W/m ⁇ K.
  • the secondary battery pack of the present invention includes a storage section, a plurality of battery cells fixed in the storage section, and a flame-retardant heat insulating sheet provided between the plurality of battery cells.
  • the heat insulating sheet is characterized by using the flame retardant heat insulating material described above.
  • the heat insulating layer made of the inorganic heat insulating filler and the inorganic binder is laminated on at least one surface of the sheet-like base material having an oxygen index of 26 or more, it is lightweight, heat resistant, It has excellent flame retardancy, can secure the required tensile strength, and can also increase interlaminar strength, and is highly effective when used in fields where flame retardancy and heat insulation are required.
  • FIG. 1 is a cross-sectional view showing an outline of a flame-retardant heat insulating material according to a first embodiment of the present invention. It is a sectional view showing an outline of a flame-retardant heat insulating material according to a modification of the first embodiment of the present invention.
  • FIG. 2 is a sectional view showing a state in which the flame-retardant heat insulating material of the present invention is used as a flame-retardant heat insulating sheet for a secondary battery pack.
  • FIG. 1 is a cross-sectional view showing an example of a flame-retardant heat insulating material according to this embodiment.
  • the flame retardant heat insulating material 10 according to the present embodiment has a structure in which a heat insulating layer 12 made of an inorganic heat insulating filler and an inorganic binder is laminated on one surface of a sheet-like base material 11.
  • the flame-retardant heat insulating material 10 is produced by, for example, adding and stirring 180 parts by weight of toluene and 60 parts by weight of isopropyl alcohol to an inorganic heat insulating filler and an inorganic binder, and then casting the mixture onto a sheet-like base material 11. It can be manufactured by drying (100°C x 5 minutes) and heat curing (150°C x 8 hours).
  • the flame-retardant heat insulating material may be manufactured by separately forming the heat insulating layer 12 and then laminating it on at least one surface of the sheet-like base material 11 having an oxygen index of 26 or more.
  • the sheet-like base material 11 and the heat insulating layer 12 may be laminated using an adhesive.
  • the adhesive is not particularly limited as long as it can firmly bond the sheet-like base material 11 and the heat insulating layer 12 and is flame retardant.
  • inorganic adhesives such as silica adhesives, ceramics, cement, solder, and water glass are adhesives with good properties.
  • synthetic adhesives are preferable, and among them, ⁇ -olefin adhesives, epoxy resin adhesives, and cyanoacrylate adhesives that have flame retardancy or have flame retardancy added. It is more preferable.
  • the thickness of the flame-retardant heat insulating material 10 according to this embodiment is not particularly limited, and can be determined as appropriate depending on its purpose and use.
  • the thickness of the flame-retardant heat insulating material 10 is preferably 100 mm or less from the viewpoint of economy and ease of processing, more preferably 0.1 to 50 mm, and even more preferably 0.3 to 30 mm. be.
  • the total ratio (weight ratio) of the sheet-like base material 11 and the heat insulating layer 12 is such that the ratio of sheet-like base material/insulating layer is 10/90 to 99/1, preferably 20/80 to 97/3, and more preferably It may be from 25/75 to 95/5, particularly preferably from 30/70 to 90/10. With such a ratio, a flame-retardant heat insulating material 10 having excellent heat resistance and flame retardancy can be obtained.
  • the flame-retardant heat insulating material 10 preferably has a bulk density in the range of 0.01 to 10 g/cm 3 from the viewpoint of flame retardancy, heat insulation, tensile strength, interlaminar strength, workability, etc. , more preferably within the range of 0.05 to 8 g/cm 3 , even more preferably within the range of 0.08 to 5 g/cm 3 , particularly preferably within the range of 0.1 to 3 g/cm 3 desirable.
  • the bulk density is not limited to the above.
  • the proportion of air (oxygen) in the flame retardant heat insulating material 10 can be controlled within a certain range, resulting in excellent flame retardancy and heat insulation. Easy to obtain.
  • the flame-retardant heat insulating material 10 according to the present embodiment may be colored with a dye or a pigment as necessary.
  • a coloring method a method of adding a coloring agent to the heat insulating layer 12 may be used.
  • the sheet-like base material 11 may be colored. In this case, a spun yarn obtained by mixing a dye or pigment with a polymer before spinning may be used, or the sheet-like base material 11 may be colored after being formed.
  • the flame retardant heat insulating material 10 may contain an acrylic resin emulsion, a phosphate ester flame retardant, or a halogen, if necessary, in order to further improve its flame retardancy, tensile strength, and interlaminar strength. It may be coated or impregnated with an acrylic resin emulsion or an acrylic resin solution containing a known flame retardant such as a flame retardant or a hydrated metal compound.
  • additives can be added to the flame-retardant heat insulating material 10 according to the present embodiment depending on the purpose.
  • additives include antioxidants such as organic phosphorus and thioether; light stabilizers such as hindered amine; ultraviolet absorbers such as benzophenone, benzotriazole, and benzoate; antistatic agents; bisamide and wax.
  • dispersants such as amide-based and organic metal salt-based; lubricants such as amide-based and organic metal salt-based; flame retardants such as brominated organic-based, phosphoric acid-based, melamine cyanurate-based, and antimony trioxide; low-density polyethylene, wire Stretching aids such as low-density polyethylene; organic pigments; inorganic pigments; inorganic fillers; organic fillers; inorganic antibacterial agents such as metal ion-based antibacterial agents, organic antibacterial agents, and the like.
  • any suitable shape and composition can be used as long as the material has low thermal conductivity and can provide a heat insulating effect.
  • silicate minerals such as sepiolite, talc, kaolin, mica powder, sericite, magnesium carbonate, calcium carbonate, hard clay, calcined clay, barium sulfate, calcium silicate, wollastonite, sodium bicarbonate, white carbon/fused silica.
  • Synthetic silica such as, natural silica such as diatomaceous earth, silica nanoparticles, inorganic balloons such as aluminum hydroxide, magnesium hydroxide, and glass beads may be used alone or in combination.
  • the balloon structure refers to a structure containing a gas layer inside the beads.
  • the gas layer include air, nitrogen, and rare gases.
  • examples of such inorganic balloons include glass balloons, fly ash balloons, silica balloons, and perlite. Among these, glass balloons are particularly preferred. Addition of these inorganic fillers exhibits effects such as maintaining shape under high temperature atmosphere and improving heat insulation.
  • the particle size of the inorganic balloon is not particularly limited as long as it can be mixed uniformly with the inorganic binder, but the average particle size is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 3 ⁇ m or more and 70 ⁇ m or less.
  • silica nanoparticles wet silica, dry silica, airgel, fumed silica, etc. can be used.
  • Silica nanoparticles are nanometer-order silica particles that are spherical or nearly spherical and have an average particle diameter of less than 1 ⁇ m.
  • the average particle diameter of the silica nanoparticles is more preferably 2 nm or more, and even more preferably 3 nm or more. Further, the average particle diameter of the silica nanoparticles is more preferably 50 nm or less, and even more preferably 10 nm or less.
  • the airgel is obtained by drying a wet gel body obtained by hydrolysis and polycondensation using a sol-gel method using a supercritical fluid or a subcritical fluid.
  • the obtained airgel has a porous structure with a pore diameter of 5 to 30 nm, in which particles with an average particle diameter of 20 nm are connected in a bead shape, and an apparent specific gravity of 0.03 to 0.3 g/cm 3 ,
  • the specific surface area is 500 to 900 m 2 /g, the solid content is 5% or less, and the remaining 95% or more is surrounded by an air layer.
  • aerogel is sometimes distinguished from those obtained by drying with a supercritical fluid, and xerogels are those obtained by drying at a subcritical fluid, and in the present invention, aerogel includes xerogel.
  • the specific surface area is the surface area per unit weight.
  • fumed silica is obtained by a method of hydrolyzing a halogenated silane such as silicon tetrachloride in an oxyhydrogen flame (so-called dry method).
  • the obtained fumed silica has a porous structure with a pore size of 10 nm to 100 nm, in which spherical particles with a particle size of 10 to 30 nm are aggregated and fused in the form of beads, and has an apparent specific gravity of 0.03 to 100 nm. It is an aggregate with a particle size of 0.1 g/cm 3 , a specific surface area of 40 to 400 m 2 /g, and a particle size of 100 to 400 nm.
  • Silica gel has a structure with an apparent specific gravity of 0.7 to 1.3 g/cm 3 , a specific surface area of 300 to 800 m 2 /g, and an average pore diameter of 1 nm to 10 nm, and silica airgel and fumed silica are common Unlike silica gel, it has a small apparent specific gravity. (Inorganic binder)
  • the inorganic binder may be any inorganic substance that can form a film.
  • silicone binders silica binders, alumina binders, zirconia-silica binders, saponite, hectorite, smectite groups such as montmorillonite, vermiculite groups, kaolinite groups such as kaolinite and halloysite, serpentine groups, sepiolite, etc.
  • examples include colloidal silica, colloidal alumina, and modified products thereof, synthetic inorganic polymer compounds, calcium sulfate, calcium silicate, water glass, Portland cement, alumina cement, alumina silicate, calcium oxide, and clay. These film-forming inorganic substances can be used alone or in combination.
  • the thickness of the heat insulating layer 12 formed using the above-mentioned inorganic heat insulating filler and inorganic binder is not particularly limited, and can be determined as appropriate depending on the purpose and use.
  • the thickness of the heat insulating layer 12 is preferably 100 mm or less from the viewpoint of economy and ease of processing, more preferably 0.1 to 50 mm, and even more preferably 0.3 to 30 mm.
  • the total ratio (weight ratio) of the inorganic heat insulating filler to the inorganic binder is such that the ratio of inorganic heat insulating filler/inorganic binder is 10/90 to 97/3, preferably 20/80 to 95/5, and more preferably 25/75 to It may be 92/8, particularly preferably 30/70 to 90/10. With such a ratio, a flame-retardant heat insulating material with excellent heat resistance and flame retardancy can be obtained.
  • this heat insulating layer can be formed not only by cast (spread coating) molding methods, but also by general film molding methods such as T-die extrusion molding, inflation molding, and calendar molding. Can be done.
  • the heat insulating layer 12 may be colored with a dye or pigment if necessary.
  • known materials such as acrylic resin emulsion, phosphate ester flame retardant, halogen flame retardant, or hydrated metal compound may be added to the heat insulating layer 12, as necessary. It may be coated or impregnated with an acrylic resin emulsion or acrylic resin solution containing a flame retardant.
  • additives may be added to the heat insulating layer 12 depending on the purpose.
  • additives include silica fiber, alumina fiber, basalt fiber, aramid fiber, polyarylate fiber, polybenzoxazole (PBO) fiber, polybenzthiazole fiber, polybenzimidazole (PBI) fiber, polyimide fiber, and polyetherimide.
  • short fibers such as fibers, polyetheretherketone fibers, polyetherketone fibers, polyamideimide fibers, flame-resistant fibers; antioxidants such as organophosphorus and thioether; light stabilizers such as hindered amines; UV absorbers such as benzophenone, benzotriazole, and benzoate; antistatic agents; dispersants such as bisamide, wax, and organic metal salts; lubricants such as amide and organic metal salts; bromine-containing organics Flame retardants such as , phosphoric acid type, melamine cyanurate type, antimony trioxide; stretching aids such as low density polyethylene and linear low density polyethylene; organic pigments; inorganic pigments; inorganic fillers; organic fillers; metal ion type Examples include inorganic antibacterial agents and organic antibacterial agents.
  • the heat insulating layer 12 is prepared by, for example, adding a volatile solvent such as methyl ethyl ketone (MEK), toluene, N,N-dimethylformamide, etc. to an inorganic heat insulating filler and an inorganic binder and thoroughly kneading them. This is done by dispersing the
  • a volatile solvent such as methyl ethyl ketone (MEK), toluene, N,N-dimethylformamide, etc.
  • the sheet-like base material 11 may have various shapes, such as a paper-like material, a non-woven fabric-like material, a film-like material, a plate-like material, or a cloth-like material (woven fabric material).
  • the thickness is preferably in the range of 0.005 to 5 mm. A more preferable thickness is 0.015 to 1 mm, and an especially preferable thickness is 0.05 to 0.5 mm. If the thickness is thinner than 0.005 mm, handling efficiency becomes poor, which is not preferable. Further, it is more preferable to set the thickness to 0.015 mm or more, since this can greatly improve workability. Furthermore, if the thickness is 0.05 mm or more, workability can be greatly improved, which is particularly preferable.
  • the sheet-like base material 11 can also be made into the laminated sheet which laminated
  • Examples of materials used for the sheet-like base material 11 include cellophane, celluloid, synthetic paper, art paper, retroreflective sheets, glass fiber cloth, polyethylene cloth, and polypropylene cloth, which have flame retardancy. Any material can be used as long as it has flame retardant properties. Further, as the material for the sheet-like base material 11, elastic resins, thermoplastic resins, etc. can be used as long as they have flame retardancy or are imparted with flame retardancy.
  • the above elastic resins include styrene-butadiene rubber, acrylonitrile-butadiene rubber, olefin-based elastomer resin, styrene-based elastomer resin, urethane-based elastomer resin, polyester-based elastomer resin, polyamide-based or aramid-based elastomer resin, and have flame retardancy.
  • a flame retardant material or a flame retardant material can be used.
  • thermoplastic resins include high-pressure low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene polymers such as ethylene/vinyl acetate copolymers, polypropylene, and propylene/ ⁇ -olefins mainly composed of propylene.
  • ethylene polymers such as ethylene/vinyl acetate copolymers, polypropylene, and propylene/ ⁇ -olefins mainly composed of propylene.
  • propylene-based polymers such as copolymers, polyvinyl chloride, polyester, polyamide, polyimide, or thermoplastic resins such as acrylic resins, as long as they have flame retardancy or are flame retardant. Can be done.
  • the sheet-like base material 11 When manufacturing the sheet-like base material 11 from these thermoplastic resins, it can be formed by T-die extrusion molding, cast molding, calendar molding, or inflation molding. Alternatively, the obtained sheet may be biaxially stretched and used. This is preferable because the sheet-like base material 11 can have increased stiffness, tensile strength, and the like.
  • a known filament made of a thermoplastic resin material such as a stretched thermoplastic resin monofilament, tape, yarn, split yarn, multifilament, or staple fiber is used. It can be manufactured using a woven fabric method.
  • the term "striate body” broadly refers to a long object that can form a sheet-like object, and includes ribbon-like objects, string-like objects, monofilaments, multifilaments, etc. Twisting is applied.
  • the striated bodies may have any structure, and can be used in the form of a tape by slitting a thermoplastic resin film to a predetermined width and uniaxially stretching it.
  • the striated body is made into a cloth-like body by weaving it into plain weave, twill weave, oblique weave, ribbed weave, double weave, mock weave, etc. Furthermore, it is also possible to form a cloth-like body by knitting in warp knitting, horizontal knitting, raschel knitting, tricot knitting, or the like.
  • a loom for weaving a known loom such as a circular loom, a sluzer type loom, or a water jet type loom can be used.
  • It may also be a cross-bonded cloth (soft) made by arranging a large number of filamentary bodies made of thermoplastic resin materials orthogonally in parallel to form a planar shape, and joining the intersection points.
  • a knitted fabric or a braided fabric formed using a filament made of the above-mentioned thermoplastic resin material may also be used.
  • the filament used when manufacturing cross-linked cloth is mainly composed of a high melting point resin component whose melting point is higher than the temperature of thermocompression bonding, but it does not contain a low melting point resin component whose melting point is lower than the temperature of thermocompression bonding. It's okay to stay.
  • the obtained cloth-like body can be used as the sheet-like base material 11 as it is, but it can also be used as a laminated resin sheet in which film layers of thermoplastic resin are laminated.
  • the sheet-like base material 11 has an oxygen index of 26 or more. Therefore, when the oxygen index of the material used is less than 26, the oxygen index is increased to 26 or more by adding a flame retardant. Further, even if the oxygen index is 26 or more, a flame retardant may be added to further improve flame retardancy.
  • flame retardant used to make the oxygen index 26 or more those known as flame retardants for paper, nonwoven fabric, film, board, and woven fabric can be used.
  • flame retardants for paper, nonwoven fabric, film, board, and woven fabric.
  • halogen-based flame retardants combinations of halogen-based flame retardants and antimony trioxide, phosphorus-based flame retardants, metal hydroxyl group-based flame retardants, phosphinate metal salt-based flame retardants, nitrogen-containing compounds such as melamine cyanurate and triazine compounds, or , sodium polyphosphate, and the like.
  • halogenated flame retardants examples include brominated flame retardants such as tetrabromobisphenol A, hexabromocyclodecane, dibromodiphenyl oxide, tetrabromobisphenol A polycarbonate oligomer, brominated polystyrene, and ethylene bistetrabromophthalimide; chlorinated paraffin , chlorine-based flame retardants such as perchlorocyclopentadecane; halogen-containing phosphate esters such as tris (tribromoneopentyl) phosphate and tris (chloropropyl) phosphate; product name "CR-504L” manufactured by Daihachi Chemical Industry Co., Ltd.; Examples include halogen-containing condensed phosphoric acid esters such as "CR-570" and "DAIGUARD-540".
  • brominated flame retardants such as tetrabromobisphenol A, hexabromocyclodecane, dibromodipheny
  • Examples of the phosphorus-based flame retardants include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, 2-naphthyldiphenyl phosphate, and cresyl di-2,6-xylenyl phosphate.
  • Non-halogenated phosphate esters such as; Aromatic condensed phosphate esters such as product names "CR-733S", “CR-741", and "PX-200" manufactured by Daihachi Chemical Industries; products manufactured by Daihachi Chemical Industries, Ltd.
  • Examples include non-halogen condensed phosphate esters such as "DAIGUARD-580", “DAIGUARD-610", and “DAIGUARD-880".
  • Examples of the metal hydroxyl flame retardant include magnesium hydroxide, aluminum hydroxide, and the like.
  • Examples of the above metal phosphinate flame retardants include those manufactured by Clariant under the trade names "Exolit OP1230" and “Exolit OP930.”
  • a synergistic effect can be obtained by using flame retardants with different mechanisms of action in combination, rather than using them alone.
  • the phosphorus-based flame retardants exemplified above are preferred, and ammonium polyphosphate coated with melamine or the like is particularly preferred since it suppresses hydrolysis and has excellent moist heat resistance.
  • the sheet-like base material 11 in the present invention is not limited to the above materials and configuration, and may contain inorganic balloons or silica nanoparticles in order to further improve flame retardancy and heat insulation properties.
  • the flame-retardant heat insulating material 10 of the present invention may have different shapes and sizes depending on the purpose of use, but the thickness ratio of the sheet-like base material 11 used therein is determined according to the flame-retardant heat insulating material 10.
  • the ratio is preferably 3 to 50% of the thickness, more preferably 5 to 40%.
  • the flame-retardant heat insulating material 10 can be given appropriate strength and rigidity, and can be easily molded into a desired shape. Further, if the sheet-like base material 11 is mixed at a maximum of 50%, sufficient heat insulation and flame retardancy can be imparted.
  • the ratio of the thickness of the sheet-like base material 11 is larger than 50% of the total thickness, the ratio of the heat insulating layer 12 will be relatively reduced, which is not preferable because the heat insulating performance and flame retardant performance will decrease.
  • FIG. 2 is a sectional view showing an example of a flame-retardant heat insulating material 20 according to a modification of the present embodiment.
  • the flame-retardant heat insulating material 20 of this modification has a structure in which heat insulating layers 22 made of an inorganic heat insulating filler and an inorganic binder are laminated on both surfaces of a sheet-like base material 21.
  • Such a flame-retardant heat insulating material 20 can be produced, for example, by adding and stirring 180 parts by weight of toluene and 60 parts by weight of isopropyl alcohol to an inorganic heat insulating filler and an inorganic binder, and mixing the mixture with stirring. After casting coating on one side and drying (100°C x 5 minutes), cast coating on the other side in the same way, drying (100°C x 5 minutes), and then heat curing (150°C ⁇ 8 hours). Alternatively, it can be manufactured by slightly arranging the various manufacturing methods described in the first embodiment.
  • the heat insulating layers 22 formed on both sides may be made of the same material, or may be made of different materials on each side. Furthermore, it is not required that the thicknesses be the same.
  • the drying temperature and time, and the heat curing temperature and time may be set according to each material.
  • Interlaminar strength at 60°C was measured in accordance with JIS K-6854-3. From the viewpoint of workability and abrasion resistance, it needs to be 0.5 N/50 mm or more, preferably 3 N/50 mm or more, and more preferably 5 N/50 mm or more.
  • Flame retardancy test Based on UL-94 5V flat plate test piece vertical combustion test.
  • Thermal conductivity Measured in accordance with JIS A-1412-2.
  • Table 1 shows the inorganic fillers used in the Examples described below
  • Table 2 shows the inorganic binders
  • Table 3 shows the sheet-like base materials.
  • the inorganic fillers used were three types of glass balloons, one type each of fly ash balloons, shirasu balloons, perlite, silica airgel, and scaly mica powder. Details of each inorganic filler are shown in Table 1.
  • the inorganic binders used were silicone-based binders, silica-based binders, alumina-based binders, and zirconia-silica-based binders. Note that a polyurethane binder was used as a comparative example. Details of each inorganic binder are shown in Table 2.
  • the sheet-like base materials include flame-resistant fiber woven fabric, basalt fiber woven fabric, basalt fiber non-woven fabric, glass fiber woven fabric, silica fiber woven fabric, alumina fiber woven fabric, polyester flame-retardant non-woven fabric, and polyethylene flame-retardant non-woven fabric. was used. Note that a general nonwoven fabric was used as a comparative example. Details of each sheet-like base material are as shown in Table 3.
  • Example 1-1 uses 90 parts by weight of glass balloon A and 10 parts by weight of silicone binder;
  • Example 1-2 uses 40 parts by weight of glass balloon A and 60 parts by weight of silicone binder;
  • Example 1- In Example 3, the glass balloon A was 60 parts by weight and the silicone binder was 40 parts by weight, and in Example 1-4, the glass balloon A was 10 parts by weight and the silicone binder was 90 parts by weight.
  • Comparative Example 1-1 the glass balloon A was 98 parts by weight, and the silicone binder was 2 parts by weight.
  • Comparative Example 1-2 the glass balloon A was used in an amount of 5 parts by weight, and the silicone binder was used in an amount of 95 parts by weight.
  • the curing agent was set as shown in Table 4 according to the weight part of the silicone binder.
  • the tensile strength was 16.0 MPa in Example 1-1, 21.0 MPa in Example 1-2, 19.0 MPa in Example 1-3, and 24.0 MPa in Example 1-4. From this result, it was confirmed that the tensile strength increased as the amount of glass balloon A mixed as an inorganic filler decreased. Furthermore, the target values were cleared in all of Examples 1-1 to 1-4.
  • Comparative Example 1-1 glass balloon A was used in an amount of 98 parts by weight, and the tensile strength, flame retardancy, and thermal conductivity all cleared the target values, but the high-temperature interlaminar strength was 0.3 N/50 mm. Therefore, the target value of 0.5N/50mm was not cleared.
  • Comparative Example 1-2 uses 5 parts by weight of glass balloon A, and although the tensile strength, high-temperature interlaminar strength, and flame retardance meet the standards, the thermal conductivity is 0.4 W/m ⁇ K and did not clear the target value of 0.2 W/m ⁇ K.
  • Example 3-1 a silica binder was used in Example 3-1
  • an alumina binder was used in Example 3-2
  • a zirconia-silica binder was used in Example 3-3.
  • a flame-retardant heat insulating material was prepared using the method, and its properties were evaluated.
  • Comparative Example 3-1 a flame retardant heat insulating material was also produced using a urethane binder and its properties were evaluated.
  • a flame-retardant heat insulating material was produced in the same manner as in Example 1, except that no curing agent was used and the thermosetting conditions were changed to 150° C. for 1 hour.
  • the total thickness of the flame-retardant heat insulating material is 0.8 mm
  • the thickness of the flame-resistant fiber woven fabric that is the sheet-like base material is 0.4 mm
  • the heat insulating material formed on one side of The layer thickness is also 0.4 mm.
  • Table 6 shows the details of the inorganic filler, inorganic binder, and sheet-like base material, and the results of evaluating the physical properties of the produced flame-retardant heat insulating material.
  • Examples 3-1 to 3-3 all cleared the target values in tensile strength, high-temperature interlaminar strength, flame retardancy, and thermal conductivity.
  • a good flame-retardant heat insulating material can be obtained by using not only a silicone-based binder but also a silica-based binder, an alumina-based binder, and a zirconia-silica-based binder as the inorganic binder.
  • a urethane-based binder was used, the tensile strength, high-temperature interlaminar strength, and thermal conductivity cleared the target values, but the flame retardancy test did not clear the standard values.
  • the urethane binder is an organic material, it was found that even if the inorganic filler, glass balloon A, was used in an amount of 90 parts by weight and the urethane binder was added in an amount of 10 parts by weight, the flame retardancy test could not be passed.
  • Example 4-1 was a basalt fiber woven fabric
  • Example 4-2 was a basalt fiber non-woven fabric
  • Example 4-2 was a basalt fiber non-woven fabric.
  • Glass fiber woven fabric was used in Example 4-3
  • silica fiber woven fabric was used in Example 4-4
  • alumina fiber woven fabric was used in Example 4-5.
  • the method for manufacturing the flame-retardant heat insulating material was the same as in Example 1, and the total thickness of the flame-retardant heat insulating material was all 0.8 mm.
  • the thickness of the basalt fiber woven fabric which is the sheet-like base material, is 0.4 mm, and the thickness of the heat insulating layer formed on one surface thereof is also 0.4 mm.
  • the thickness of the basalt fiber nonwoven fabric was 0.3 mm, and the thickness of the heat insulating layer was 0.5 mm.
  • the thickness of the glass fiber woven fabric was 0.05 mm, and the thickness of the heat insulating layer was 0.75 mm.
  • Example 4-4 the thickness of the silica fiber woven fabric was 0.2 mm, and the thickness of the heat insulating layer was 0.6 mm. Furthermore, in Example 4-5, the thickness of the alumina fiber woven fabric was 0.3 mm, and the thickness of the heat insulating layer was 0.5 mm. Table 7 shows the details of the inorganic filler, inorganic binder, and sheet-like base material, and the results of evaluating the physical properties of the produced flame-retardant heat insulating material.
  • This example describes the manufacture of a flame-retardant heat insulating material according to a modification of the first embodiment and its characteristics.
  • Example 5-1 a glass fiber woven fabric was used as the sheet-like base material, and a heat insulating layer made of glass balloon A and a silicone binder was formed on both sides.
  • the manufacturing method is to cast the glass fiber woven fabric on one side and dry it (100°C x 5 minutes), then cast it on the other side in the same way and dry it (100°C x 5 minutes). 5 minutes) and then thermally cured (150°C x 8 hours) to obtain a flame retardant heat insulating material with a total thickness of 0.8 mm.
  • Example 5-2 a heat insulating layer was formed on both sides using a polyethylene flame-retardant woven fabric as the sheet-like base material.
  • Example 5-3 a heat insulating layer was formed on both sides using polyester flame-retardant nonwoven fabric as the sheet-like base material.
  • Example 5-4 a glass fiber woven fabric was used as the sheet-like base material, and a heat insulating layer containing 45 parts by weight of glass balloon A and 45 parts by weight of silica airgel was formed on both sides.
  • Comparative Example 5-1 a heat insulating layer was formed on both sides using a general nonwoven fabric.
  • Example 5-2 to Comparative Example 5-1 the method of forming the heat insulating layer on both sides is the same as in Example 5-1. Further, the total thickness of the flame-retardant heat insulating material was all 0.8 mm, and the thickness of the heat insulating layer formed on both sides was set depending on the thickness of the sheet-like base material. Table 8 shows the details of the inorganic filler, inorganic binder, and sheet-like base material, and the results of evaluating the physical properties of the produced flame-retardant heat insulating material.
  • the flame-retardant heat insulating materials of Examples 5-1 to 5-4 cleared the target values in all of tensile strength, high-temperature interlaminar strength, flame retardancy, and thermal conductivity.
  • the polyethylene flame-retardant woven fabric has an oxygen index of 33, and the polyester flame-retardant non-woven fabric has an oxygen index of 29, and these were also found to have good flame retardancy.
  • FIG. 3 is a cross-sectional view showing a state in which the flame-retardant heat insulating material of the present invention is used as a heat insulating sheet for a secondary battery pack.
  • the secondary battery pack 30 of the present invention includes a storage section 33, a plurality of battery cells 31 fixed in the storage section 33, and a flame-retardant heat insulating sheet 32 provided between the plurality of battery cells 31.
  • the flame retardant heat insulating sheet 32 uses the flame retardant heat insulating material of the present invention.
  • the flame-retardant heat insulating sheet 32 surrounding them prevents heat conduction to other battery cells 31 and prevents the ignition. It can be prevented.
  • the flame-retardant heat insulating material of the present invention is in the form of a sheet, it can be easily processed into an appropriate size, shape, etc. by applying known methods according to its purpose and use. Therefore, it can be used for various purposes.
  • the flame-retardant heat insulating material of the present invention can be used in applications where flame retardancy and heat insulation are required.
  • packaging for vehicles such as automobiles and freight cars, interior materials for transportation equipment such as aircraft and ships, civil engineering and construction materials such as wall materials, floor materials and ceiling materials, and refrigerated containers. It can be suitably used for materials, bedding, sound absorbing members, etc.
  • the flame retardant heat insulating material of the present invention is in the form of a sheet, it is flexible and can be easily punched into the required shape, and has flame retardant and heat insulating properties, so it does not require heat shielding or heat insulating properties. It is useful in a wide range of fields.

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  • General Engineering & Computer Science (AREA)
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  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : un matériau ignifuge et isolant thermique qui présente une propriété d'isolation thermique élevée permettant une isolation efficace de la chaleur, une propriété ignifuge pour empêcher l'inflammation, et une résistance et une efficacité économique élevées ; et son procédé de fabrication. Le matériau ignifuge et isolant thermique comprend un substrat en forme de feuille ayant un indice d'oxygène supérieur ou égal à 26, et une couche d'isolation thermique empilée sur au moins une surface du substrat en forme de feuille, la couche d'isolation thermique étant composée d'une charge d'isolation thermique inorganique et d'un liant inorganique. La charge d'isolation thermique inorganique peut être au moins un élément choisi parmi les flocons de mica, les ballons de verre, les ballons de cendres volantes, les ballons de silas, la perlite, le xérogel de silice et l'aérogel de silice. Le liant inorganique peut être au moins un liant choisi parmi un liant à base de silicone, un liant à base de silice, un liant à base d'alumine et un liant à base de zircone-silice.
PCT/JP2023/023475 2022-09-05 2023-06-26 Matériau ignifuge et isolant thermique WO2024053211A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5140647A (ja) * 1974-10-02 1976-04-05 Hitachi Ltd Dannetsuzai
JPH10193496A (ja) * 1997-01-14 1998-07-28 Nitto Denko Corp 保護材料
JP2014224648A (ja) * 2013-05-16 2014-12-04 ダイワボウホールディングス株式会社 防炎断熱材、及び車両用防炎断熱材
US20180309107A1 (en) * 2017-04-19 2018-10-25 Unifrax I Llc Insulation barrier for electrochemical battery and electrochemical battery including same
WO2020213637A1 (fr) * 2019-04-15 2020-10-22 マツダ株式会社 Matériau d'isolation thermique, moteur comprenant un matériau d'isolation thermique, liquide de dispersion de nanoparticules, et procédé de production de matériau d'isolation thermique
JP2021034278A (ja) * 2019-08-27 2021-03-01 イビデン株式会社 組電池用断熱シート及び組電池
JP2021086820A (ja) * 2019-11-29 2021-06-03 三菱製紙株式会社 熱暴走抑制耐火シート
WO2021144758A1 (fr) * 2020-01-15 2021-07-22 3M Innovative Properties Company Barrière contre l'emballement thermique pour système de stockage d'énergie électrique rechargeable
JP2021144879A (ja) * 2020-03-12 2021-09-24 住友理工株式会社 バッテリーパック用断熱材およびバッテリーパック
JP2021143733A (ja) * 2020-03-12 2021-09-24 住友理工株式会社 断熱材およびその製造方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5140647A (ja) * 1974-10-02 1976-04-05 Hitachi Ltd Dannetsuzai
JPH10193496A (ja) * 1997-01-14 1998-07-28 Nitto Denko Corp 保護材料
JP2014224648A (ja) * 2013-05-16 2014-12-04 ダイワボウホールディングス株式会社 防炎断熱材、及び車両用防炎断熱材
US20180309107A1 (en) * 2017-04-19 2018-10-25 Unifrax I Llc Insulation barrier for electrochemical battery and electrochemical battery including same
WO2020213637A1 (fr) * 2019-04-15 2020-10-22 マツダ株式会社 Matériau d'isolation thermique, moteur comprenant un matériau d'isolation thermique, liquide de dispersion de nanoparticules, et procédé de production de matériau d'isolation thermique
JP2021034278A (ja) * 2019-08-27 2021-03-01 イビデン株式会社 組電池用断熱シート及び組電池
JP2021086820A (ja) * 2019-11-29 2021-06-03 三菱製紙株式会社 熱暴走抑制耐火シート
WO2021144758A1 (fr) * 2020-01-15 2021-07-22 3M Innovative Properties Company Barrière contre l'emballement thermique pour système de stockage d'énergie électrique rechargeable
JP2021144879A (ja) * 2020-03-12 2021-09-24 住友理工株式会社 バッテリーパック用断熱材およびバッテリーパック
JP2021143733A (ja) * 2020-03-12 2021-09-24 住友理工株式会社 断熱材およびその製造方法

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