Method for manufacturing thermal insulation material, battery device, heat transfer suppression member, and method for manufacturing thermal insulation material

Abstract

The present invention provides an insulating material capable of exhibiting high thermal insulation effects. Furthermore, it provides a heat transfer suppressing member capable of exhibiting high thermal insulation effects, a method for manufacturing the heat transfer suppressing member that allows for the simpler production of the insulating material, and a method for manufacturing the insulating material. [Solution] An inorganic fiber molded body, an inorganic fiber layer containing heat radiation suppression particles and a surfactant, An insulating material comprising the inorganic fiber layer and a laminated resin layer.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing thermal insulation materials, battery devices, heat transfer suppression members, and a method for manufacturing thermal insulation materials. [Background technology]

[0002] In recent years, there has been a growing demand for longer driving ranges in electric vehicles, and for this reason, attempts are being made to densely pack various types of batteries, such as lithium-ion batteries. In this process, since batteries repeatedly expand and contract and generate heat during use, insulating buffer materials are provided between the battery cells.

[0003] For example, Patent Document 1 discloses a battery device comprising a first plate material and a second plate material arranged so that their surfaces face each other, with a low thermal conductivity layer formed between the first plate material and the second plate material, which is a layer of material with a lower thermal conductivity than the first plate material. It is stated that this enables efficient heat insulation between the energy storage element and other materials. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 6459207 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, in a configuration like that described in Patent Document 1, when the battery cell undergoes thermal expansion, the plate material breaks and fails to maintain the insulation layer, resulting in insufficient insulation. Furthermore, simply creating a space between the plate materials makes it difficult to impart functions other than insulation, such as compression characteristics.

[0006] In view of the above problems, the present invention aims to provide a thermal insulation material that can exhibit a high thermal insulation effect. Furthermore, it aims to provide a heat transfer suppressing member that can exhibit a high thermal insulation effect, a method for manufacturing a heat transfer suppressing member that can produce a thermal insulation material in a simpler way, and a method for manufacturing a thermal insulation material. [Means for solving the problem]

[0007] Disclosure 1 comprises an inorganic fiber molded body, an inorganic fiber layer containing heat radiation suppression particles and a surfactant, This is an insulating material comprising the inorganic fiber layer and a laminated resin layer. Disclosure 2 is the thermal insulation material of Disclosure 1, wherein the heat radiation suppression particles are inorganic oxides, silicon carbide, or inorganic hydrates. Disclosure 3 is the thermal insulation material of Disclosure 2, wherein the inorganic oxide is silica or a metal oxide, and the metal oxide is at least one selected from the group consisting of titanium oxide, alumina, and zirconia oxide. Disclosure 4 is a thermal insulation material according to Disclosure 2 or 3, wherein the inorganic hydrate is a metal hydroxide, and the metal hydroxide is at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, iron hydroxide, manganese hydroxide, zirconium hydroxide, and gallium hydroxide. Disclosure 5 is an insulating material according to Disclosure 1, 2, 3, or 4, wherein the average fiber length of the inorganic fibers is 0.1 to 150 mm. Disclosure 6 is a thermal insulation material according to Disclosure 1, 2, 3, 4, or 5, wherein the average fiber diameter of the inorganic fibers is 1 to 15 μm. Disclosure 7 relates to an inorganic fiber molded article having a density of 100 to 600 kg / m³ 3 The thermal insulation material is as described in disclosure 1, 2, 3, 4, 5, or 6. Disclosure 8 is an insulating material according to Disclosure 1, 2, 3, 4, 5, 6, or 7, wherein the surfactant comprises at least two types, and the two types of surfactants are anionic surfactants, cationic surfactants, or nonionic surfactants. Disclosure 9 is a thermal insulation material according to Disclosure 1, 2, 3, 4, 5, 6, 7, or 8, wherein the mass ratio of the heat radiation suppressing particles to the total of the heat radiation suppressing particles and the inorganic fibers is 3% by mass or more and 70% by mass or less. Disclosure 10 is an insulating material according to Disclosures 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the resin layer is provided on both surfaces of the inorganic fiber layer, and the resin layer contains chlorinated polyvinyl chloride resin. Disclosure 11 is a battery device comprising the thermal insulation material of Disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 and a plurality of battery cells, wherein the thermal insulation material is arranged between the battery cells. This disclosure 12 is a method for manufacturing a heat transfer suppression member, comprising an impregnation step of impregnating an inorganic fiber molded body with heat radiation suppression particles, wherein the impregnation step uses a solution containing the heat radiation suppression particles and a surfactant. Disclosure 13 provides a method for manufacturing an insulating material, comprising the steps of impregnating an inorganic fiber molded body with a solution containing heat radiation suppression particles and a surfactant to obtain an inorganic fiber layer, and laminating and pressing resin layers onto both sides of the inorganic fiber layer. The present invention will be described in detail below.

[0008] The thermal insulation material of the present invention has an inorganic fiber layer comprising an inorganic fiber molded body, heat radiation suppression particles, and a surfactant. Examples of the inorganic fibers mentioned above include ceramic fibers, glass fibers, carbon fibers, mineral fibers, and metal fibers. Examples of the above-mentioned ceramic fibers include silica fibers, alumina fibers, silica-alumina fibers, alumina silicate fibers, zirconia fibers, soluble fibers, refractory ceramic fibers, aerogel composites, magnesium silicate fibers, alkali-earth silicate fibers, potassium titanate fibers, silicon carbide fibers, potassium titanate whisker fibers, and the like. Examples of the carbon fibers mentioned above include PAN-based carbon fibers, pitch-based carbon fibers, cellulose-based carbon fibers, and vapor-grown carbon fibers. Examples of the above-mentioned glass fibers include fibers made from E-glass, C-glass, S-glass, T-glass, etc., as well as glass wool, slag wool, etc. Examples of the above mineral fibers include rock wool, basalt fiber, wollastonite, mullite fiber, etc. Examples of the above metal fibers include fibers made of metals such as iron, gold, silver, copper, aluminum, brass, and stainless steel. Among them, silica fiber, alumina fiber, silica-alumina fiber, rock wool, alkaline earth silicate fiber, glass fiber, and carbon fiber are preferred, and glass fiber is more preferred from the viewpoints of cost and availability. The above inorganic fibers may be used alone or in combination of two or more.

[0009] The above inorganic fibers may be discontinuous fibers in which the fibers are intermittently segmented, or may be continuous fibers that are not segmented. In addition, the above inorganic fibers are not limited to long fibers and may be short fibers. Long fibers have a uniform structure, so the quality of the product is likely to be stable and quality control during the manufacturing process is easy, which is preferable. When the above inorganic fibers are discontinuous fibers, the average fiber length of the above inorganic fibers is preferably 0.1 mm or more, more preferably 0.5 mm or more, preferably 150 mm or less, and more preferably 100 mm or less. When the average fiber length of the above inorganic fibers is 0.1 mm or more, the inorganic fibers can be sufficiently intertwined with each other to sufficiently increase the mechanical strength of the heat insulating material. Also, when the average fiber length of the above inorganic fibers is 150 mm or less, the entanglement of the inorganic fibers with each other is not hindered, and the rounding of only a single inorganic fiber is prevented, making it difficult for continuous voids to occur and enhancing the heat insulation property. The above average fiber length can be measured, for example, by a fiber length measurement system.

[0010] The average fiber diameter of the above inorganic fibers is preferably 1 μm or more, more preferably 2 μm or more, preferably 15 μm or less, and more preferably 10 μm or less. When the average fiber diameter of the inorganic fiber is 1 μm or more, the mechanical strength of the inorganic fiber itself can be sufficiently maintained. Further, when the average fiber diameter of the inorganic fiber is 15 μm or less, an increase in solid heat conduction using the inorganic fiber as a medium can be suppressed, resulting in a more suitable heat insulation property. The average fiber diameter can be measured, for example, using a scanning electron microscope.

[0011] The form of the inorganic fiber molded body is not particularly limited, and examples include inorganic fiber sheets such as woven fabrics, knitted fabrics, and non-woven fabrics. The basis weight of the fibers in the inorganic fiber molded body is preferably 100 g / m 2 or more, more preferably 250 g / m 2 or more, preferably 2500 g / m 2 or less, more preferably 2000 g / m 2 or less.

[0012] The density of the inorganic fiber molded body is preferably 100 kg / m 3 or more, more preferably 150 kg / m 3 or more, still more preferably 200 kg / m 3 or more, preferably 600 kg / m 3 or less, more preferably 500 kg / m 3 or less, still more preferably 420 kg / m 3 or less. When the density of the inorganic fiber molded body is 100 kg / m 3 or more, there is an advantage that heat radiation suppressing particles are easily retained in the inorganic fiber molded body. Further, when the density of the inorganic fiber molded body is 600 kg / m 3 or less, there is an advantage that there is room to introduce heat radiation suppressing particles due to the air layer in the inorganic fiber molded body. The density can be measured, for example, using an electronic specific gravity meter or the like.

[0013] The inorganic fiber molded body may contain an organic binder, a sizing agent, etc. in addition to the inorganic fiber.

[0014] The thickness of the above inorganic fiber molded article is preferably 0.5 mm or more, more preferably 1 mm or more, preferably 10 mm or less, and more preferably 8 mm or less.

[0015] The inorganic fiber content in the above inorganic fiber molded article is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 100% by mass or less, and more preferably 95% by mass or less.

[0016] The inorganic fiber content in the inorganic fiber layer is preferably 30% by mass or more, more preferably 40% by mass or more, preferably 98% by mass or less, and more preferably 95% by mass or less.

[0017] The materials for the above-mentioned organic binder include halogen-containing resins such as rayon, vinylon, nylon, chlorinated polyvinyl chloride (CPVC), and polyvinyl chloride (PVC), polyolefins such as polyethylene and polypropylene, polystyrene (PS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylic resins such as polymethyl methacrylate, polyamide, polycarbonate, polysulfone (PSU resin), polyphenylsulfone (PPSU), polyethersulfone (PES resin), and polyetherimide (PE). Examples of organic binders include polyphenylene sulfide (PPS resin), polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyacetal, polyimide, polyphenylene ether, polyether ether ketone, liquid crystal polymer, polyurethane, phenolic resin, epoxy resin, urea resin, melamine resin, silicone resin, unsaturated polyester resin, alkyd resin, thermosetting polyimide, olefin elastomer, styrene elastomer, ester elastomer, amide elastomer, vinyl chloride elastomer, and other thermoplastic elastomers. Natural fibers such as hemp, cotton, coconut, bamboo, wool, and silk are also used. These organic binders are preferred from the viewpoint of strength and availability. From the viewpoint of cost, polypropylene, polyethylene, and polyethylene terephthalate are preferred. These organic binders may be used in combination of two or more types, but from a recycling perspective, it is preferable to use one type alone.

[0018] The content of the organic binder in the inorganic fiber molded article is preferably 0% by mass or more, more preferably 2% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less.

[0019] The content of the organic binder in the inorganic fiber layer is preferably 0% by mass or more, more preferably 2% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less.

[0020] The inorganic fiber layer described above contains heat radiation suppression particles. The inclusion of heat radiation suppression particles can significantly enhance thermal insulation. Here, "thermal radiation suppression" refers to the property of suppressing heat transfer to a low-temperature object by absorbing radiant energy obtained from a high-temperature object and radiating it in all directions, or by reflecting radiant energy obtained from a high-temperature object. Specifically, it refers to materials that satisfy high emissivity of 0.5 to 1.0 or high reflectivity of 0.5 to 1.0.

[0021] Examples of the heat radiation suppression particles mentioned above include inorganic oxides, silicon carbide, and inorganic hydrates. Examples of the inorganic oxides mentioned above include metal oxides such as titanium oxide, alumina, and zirconia oxide, as well as silica. Examples of the inorganic hydrates mentioned above include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, iron hydroxide, manganese hydroxide, zirconium hydroxide, and gallium hydroxide, as well as hydrates of metal salts such as zinc borate hydrate, calcium sulfate hydrate, and magnesium sulfate hydrate.

[0022] The content of the heat radiation suppression particles in the inorganic fiber layer is preferably 3% by mass or more, more preferably 10% by mass or more, preferably 40% by mass or less, and more preferably 30% by mass or less.

[0023] The inorganic fiber layer described above further contains a surfactant. By including a surfactant, the above-mentioned heat radiation suppression particles can be efficiently supported on the inorganic fiber layer. It is preferable to use a surfactant having dispersive properties and a surfactant having surface tension-reducing properties as the above-mentioned surfactants. Alternatively, one surfactant having both dispersive properties and surface tension-reducing properties may be used, but it is preferable to use a combination of a surfactant having dispersive properties and a surfactant having surface tension-reducing properties. Furthermore, surfactants are mainly classified into anionic, cationic, nonionic, and amphoteric types. When using two or more surfactants in combination, it is preferable that the two surfactants are not counterions, such as an anionic and a cationic type. It is preferable to use two anionic surfactants, two cationic surfactants, or two nonionic surfactants.

[0024] Examples of anionic surfactants include fatty acid salts, polysulfonates, polycarboxylates, alkyl sulfates, alkylaryl sulfons, alkylnaphthalene sulfons, dialkyl sulfons, dialkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphate sulfons, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters. Furthermore, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonylphenyl ether sulfate, and sodium salts of β-naphthalene sulfonic acid formalin condensates are also included. Cationic surfactants include alkylamine salts and quaternary ammonium salts. Specifically, these include stearylamine acetate, trimethyl coconut ammonium chloride, trimethyl beef tallow ammonium chloride, dimethyl dioleyl ammonium chloride, methyl oleyl diethanol chloride, tetramethyl ammonium chloride, laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium disulfate, cetylpyridinium bromide, 4-alkyl mercaptopyridine, poly(vinylpyridine)-dodecyl bromide, and dodecylbenzyltriethylammonium chloride. Examples of amphoteric surfactants include aminocarboxylate salts. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and alkyl allyl ethers. Specifically, examples include polyoxyethylene lauryl ether, sorbitan fatty acid ester, and polyoxyethylene octylphenyl ether.

[0025] The surfactant content in the inorganic fiber layer is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 10% by mass or less, and more preferably 5% by mass or less. 3% by mass or less is more preferable.

[0026] In the inorganic fiber layer described above, the amount of the surfactant per 100 parts by mass of the heat radiation suppression particles is preferably 0.002 parts by mass or more, more preferably 0.02 parts by mass or more, 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, preferably 30 parts by mass or less, and more preferably 25 parts by mass or less.

[0027] In the inorganic fiber layer described above, the mass ratio of the heat radiation suppressing particles to the total of the heat radiation suppressing particles and the inorganic fibers (heat radiation suppressing particles / (heat radiation suppressing particles + inorganic fibers)) is preferably 3% by mass or more, more preferably 8% by mass or more, preferably 70% by mass or less, and more preferably 60% by mass or less, 50% by mass or less, or 40% by mass or less. When the above mass ratio is 3% by mass or more, sufficient thermal insulation can be achieved, and when it is 70% by mass or less, the effect on the mechanical strength of the inorganic fiber molded article is suppressed, resulting in a thermal insulation material with sufficient strength.

[0028] The content of the surfactant having the above-mentioned dispersive ability in the inorganic fiber layer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 3% by mass or less.

[0029] The content of the surfactant having the ability to reduce surface tension in the inorganic fiber layer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 3% by mass or less.

[0030] In the inorganic fiber layer described above, the ratio of the content of the surfactant having dispersive ability to the content of the surfactant having surface tension-reducing ability (surfactant having dispersive ability / surfactant having surface tension-reducing ability) is preferably 0.0001 or more, more preferably 0.05 or more, preferably 150 or less, and more preferably 40 or less.

[0031] As a method for producing the above-mentioned inorganic fiber layer, a method having an impregnation step of impregnating an inorganic fiber molded body with heat radiation suppression particles can be used. In the impregnation process described above, it is preferable to use a solution containing heat radiation suppression particles and a surfactant. As solvents, for example, water, a mixed solvent of water and a water-compatible organic solvent, or an organic solvent can be used. As the above-mentioned organic solvent that is compatible with water, for example, an alcohol-based organic solvent can be used. Examples of the above-mentioned organic solvents include alcohol-based organic solvents, aromatic organic solvents, aliphatic ester-based solvents, ketone-based solvents, lower paraffin-based solvents, ether-based solvents, amide-based solvents, and amine-based solvents. Examples of the above-mentioned alcohol-based organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. Examples of the above-mentioned aromatic organic solvents include xylene, toluene, ethylbenzene, and methyl benzoate. Examples of the above-mentioned aliphatic ester solvents include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, and ethyl acetoacetate. Examples of the ketone-based solvents mentioned above include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, and acetophenone. Examples of the lower paraffinic solvents mentioned above include hexane, pentane, octane, cyclohexane, and decane. Examples of the above-mentioned ether-based solvents include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol diethyl ether. Examples of the above-mentioned amide solvents include N,N-dimethylformamide, N,N-dimethyltesetamide, N-methylpyrrolidone, and acetanilide. Examples of the above-mentioned amine-based solvents include ammonia, trimethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N,N-dimethylaniline, and pyridine.

[0032] When preparing the above solution, it is preferable to add the above heat radiation suppression particles and the above surfactant to the solvent and stir-mix them. Furthermore, since foaming is likely to occur during stirring, it is preferable to adjust the mixture to prevent foaming.

[0033] In the impregnation process described above, examples of methods for applying the solution to the inorganic fiber molded body include casting, roll coating, lip coating, spin coating, screen coating, fountain coating, dipping, and spraying.

[0034] In the impregnation process described above, the amount of solution applied to the inorganic fiber molded body is not particularly limited, as it is set appropriately according to the solution composition and performance requirements. For example, if the density is approximately 150 kg / m³ 3 One possible method is to add 300g of dispersion to 20g of A4-sized, 2mm-thick glass mat.

[0035] In the method for producing the inorganic fiber layer described above, it is preferable to perform a drying step after the impregnation step.

[0036] Methods of drying include natural drying and heat drying. The temperature used for heat drying is preferably above the boiling point of the solvent and below the thermal decomposition temperature of the heat radiation suppression particles and the melting point of the binder resin used in combination as needed. Specifically, a temperature of 100°C to 200°C is preferred, and a temperature of 100°C to 150°C is more preferred. Furthermore, the heating and drying time is preferably 30 minutes or more, and preferably 60 minutes or less. Drying may be carried out under normal pressure or under reduced pressure.

[0037] The solution containing the above-mentioned heat radiation suppressing particles and the above-mentioned surfactant has good mechanical strength, and even when applied to an inorganic fiber molded body in which heat radiation suppressing particles are difficult to impregnate with ordinary solutions, the heat radiation suppressing particles can be impregnated without any special operation, and the heat radiation suppressing particles can be easily distributed throughout the entire inorganic fiber molded body. Therefore, in the method for producing the inorganic fiber layer described above, by performing the impregnation step using a solution containing the heat radiation suppression particles and the surfactant, it becomes possible to produce an insulating material that can exhibit the desired heat transfer suppression effect in a simpler manner.

[0038] The density of the inorganic fiber layer mentioned above is 100 kg / m³. 3 Preferably, it should be 150 kg / m 3 It is more preferable that it be greater than or equal to 550 kg / m 3 Preferably, it is 450 kg / m 3 The following is more preferable: The above density can be measured, for example, using an electronic hydrometer or the like.

[0039] The thickness of the inorganic fiber layer is preferably 1.0 mm or more, more preferably 1.5 mm or more, preferably 10 mm or less, and more preferably 8 mm or less. The inorganic fiber layer described above may be a laminate of multiple inorganic fiber layers obtained by the manufacturing method described above. In the case of multiple laminates, the thickness described above refers to the total thickness of the laminate.

[0040] The thermal insulation material of the present invention comprises the above-mentioned inorganic fiber layer and a laminated resin layer. By incorporating the above-mentioned resin layer, the fibers are not exposed on the surface of the insulation material, making it easier to handle. The thermal insulation material of the present invention preferably has a resin layer on at least one side of the inorganic fiber layer, and more preferably has a laminated structure of resin layer / inorganic fiber layer / resin layer. Alternatively, a laminate may be made by laminating multiple inorganic fiber layers, and the laminate may have a resin layer on at least one side.

[0041] Examples of resins constituting the above-mentioned resin layer include synthetic resins such as thermoplastic resins and thermosetting resins, and elastomers.

[0042] Examples of the thermoplastic resins mentioned above include halogen-containing resins such as chlorinated polyvinyl chloride resin (CPVC) and polyvinyl chloride resin (PVC), polyolefins such as polyethylene and polypropylene, polystyrene (PS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylic resins such as polymethyl methacrylate, polyamide, polycarbonate, polysulfone (PSU resin), polyphenylsulfone (PPSU), polyethersulfone (PES resin), polyetherimide (PEI resin), polyphenylene sulfide (PPS resin), polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyacetal, polyimide, polyphenylene ether, polyetherether ketone, and liquid crystal polymers. Among these, halogen-containing resins, polycarbonate, and polyamide are preferred, chlorinated polyvinyl chloride resin and vinyl chloride resin are more preferred, and chlorinated polyvinyl chloride resin is even more preferred.

[0043] Examples of the thermosetting resins mentioned above include polyurethane, phenolic resin, epoxy resin, urea resin, melamine resin, silicone resin, unsaturated polyester resin, alkyd resin, and thermosetting polyimide.

[0044] Examples of the above-mentioned elastomers include thermoplastic elastomers such as olefin-based elastomers, styrene-based elastomers, ester-based elastomers, amide-based elastomers, and vinyl chloride-based elastomers.

[0045] Among these, chlorinated polyvinyl chloride resin is preferred because the decomposition gases generated by the resin at high temperatures block the supply of oxygen from the outside, and furthermore, under low-oxygen conditions, carbonization occurs, causing foaming and thickening, which makes it easier to maintain the space between cells.

[0046] Furthermore, if the above resin contains chlorinated polyvinyl chloride resin, the chlorine content of the chlorinated polyvinyl chloride resin is preferably 57% by mass or more, more preferably 60% by mass or more, preferably 72% by mass or less, and more preferably 71% by mass or less. By setting it within the above range, good heat resistance and moldability can be achieved. The chlorine content mentioned above can be measured, for example, by a method compliant with JIS K 7229.

[0047] The average degree of polymerization of the above-mentioned chlorinated polyvinyl chloride resin is preferably 400 or higher, more preferably 500 or higher, preferably 3000 or lower, and more preferably 2000 or lower. When the average degree of polymerization is within the above range, pyrolysis products are less likely to scatter during combustion, a decrease in strength can be suppressed, and high flame-retardant performance can be maintained. The above average degree of polymerization can be measured, for example, by a method conforming to JIS K 6720-2:1999.

[0048] The above-mentioned chlorinated polyvinyl chloride resin preferably has the constituent units (b) and (c) shown in the following formulas (b) and (c).

[0049] [ka]

[0050] In the above-mentioned chlorinated polyvinyl chloride resin, the ratio of constituent unit (b) to the total constituent units is preferably 5.1 mol% or more, more preferably 15.2 mol% or more, preferably 39.8 mol% or less, and more preferably 30.0 mol% or less. Furthermore, in the above-mentioned chlorinated polyvinyl chloride resin, the ratio of constituent unit (c) to the total constituent units is preferably 5.2 mol% or more, more preferably 25.1 mol% or more, preferably 54.9 mol% or less, and more preferably 40.0 mol% or less.

[0051] The molar ratios of constituent units (b) and (c) of the chlorinated polyvinyl chloride resin described above reflect the sites where chlorine is introduced when polyvinyl chloride resin (PVC) is chlorinated. Before chlorination, PVC has 0 mol% of constituent units (b) and (c), but these increase with chlorination. The molar ratio of constituent units (b) and (c) of the above-mentioned chlorinated polyvinyl chloride resin can be measured by molecular structure analysis using NMR. NMR analysis can be performed in accordance with the method described in RAKomoroski, RG Parker, JP Shocker, Macromolecules, 1985, 18, 1257-1265.

[0052] The chlorinated polyvinyl chloride resin mentioned above is a resin obtained by chlorinating polyvinyl chloride resin (PVC). As the vinyl chloride resin mentioned above, vinyl chloride homopolymers, copolymers of vinyl chloride monomer and a monomer having an unsaturated bond copolymerizable with vinyl chloride monomer, and graft copolymers obtained by graft copolymerizing vinyl chloride monomer into a polymer can be used. These polymers may be used individually or in combination of two or more.

[0053] Examples of monomers having unsaturated bonds that can copolymerize with the vinyl chloride monomer include α-olefins, vinyl esters, vinyl ethers, (meth)acrylic acid esters, aromatic vinyls, vinyl halides, N-substituted maleimides, and one or more of these can be used. Examples of the above-mentioned α-olefins include ethylene, propylene, and butylene. Examples of the vinyl esters mentioned above include vinyl acetate and vinyl propionate. Examples of the vinyl ethers mentioned above include butyl vinyl ether and cetyl vinyl ether. Examples of the above-mentioned (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl acrylate, and phenyl methacrylate. Examples of the aromatic vinyls mentioned above include styrene and α-methylstyrene. Examples of the above-mentioned vinyl halogens include vinylidene chloride and vinylidene fluoride. Examples of the above-mentioned N-substituted maleimides include N-phenylmaleimide and N-cyclohexylmaleimide.

[0054] The polymer used for graft copolymerization of the vinyl chloride monomer is not particularly limited, as long as it is a polymer that graft polymerizes vinyl chloride monomer. Examples include ethylene copolymers, acrylonitrile-butadiene copolymers, polyurethanes, chlorinated polyethylene, and chlorinated polypropylene. These may be used individually or in combination of two or more. Examples of the above-mentioned ethylene copolymers include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, and ethylene-propylene copolymer.

[0055] The average degree of polymerization of the above-mentioned PVC is not particularly limited, but is preferably 400 to 3000, and more preferably 500 to 2000, which are commonly used. The average degree of polymerization can be measured by the method described in JIS K 6720-2:1999. The polymerization method for the above-mentioned PVC is not particularly limited, and conventionally known methods such as aqueous suspension polymerization, bulk polymerization, solution polymerization, and emulsion polymerization can be used.

[0056] The resin content in the above resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 100% by mass or less, and more preferably 99% by mass or less.

[0057] The above resin layer may contain an inorganic filler. Examples of inorganic fillers include calcium carbonate, calcium carbide, and talc.

[0058] The content of the inorganic filler in the resin layer is preferably 0% by mass or more, more preferably 0.1% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.

[0059] The above resin layer may further contain additives such as heat stabilizers, lubricants, and foaming agents.

[0060] The above-mentioned heat stabilizers are not particularly limited and include, for example, organotin-based heat stabilizers, lead-based heat stabilizers, calcium-zinc-based heat stabilizers, barium-zinc-based heat stabilizers, barium-cadmium-based heat stabilizers, and so on. Examples of the above organotin-based heat stabilizers include dibutyltin mercapto, dioctyltin mercapto, dimethyltin mercapto, dibutyltin mercapto, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer, dibutyltin laurate, and dibutyltin laurate polymer. Examples of the lead-based heat stabilizers mentioned above include lead stearate, dibasic lead phosphate, and tribasic lead sulfate. These may be used individually or in combination of two or more.

[0061] Examples of the above-mentioned lubricants include internal lubricants and external lubricants. Internal lubricants are used to reduce the flow viscosity of the molten resin during molding and to prevent frictional heat generation. The internal lubricants are not particularly limited and include, for example, butyl stearate, lauryl alcohol, stearyl alcohol, epoxy soybean oil, glycerin monostearate, stearic acid, and bisamide. These may be used alone or in combination of two or more. The above-mentioned external lubricant is used to improve the sliding effect between the molten resin and the metal surface during molding. The external lubricant is not particularly limited and examples include paraffin wax, polyolefin wax, ester wax, and montanic acid wax. These may be used individually or in combination of two or more. The same items as those described above can be used.

[0062] The blowing agent mentioned above may be a chemical blowing agent or a physical blowing agent. Examples of the above-mentioned chemical blowing agents include thermal decomposition type inorganic blowing agents, thermal decomposition type organic blowing agents, inorganic reactive blowing agents using sodium bicarbonate and acid, and organic reactive blowing agents using isocyanate and water. Examples of the above-mentioned thermal decomposition type inorganic blowing agents include thermally expandable graphite, ammonium acid, sodium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and anhydrous monosodium citrate. Examples of the above-mentioned pyrolysis-type organic blowing agents include azodicarbonamide, azodicarboxylic acid metal salts (such as barium azodicarboxylic acid), azobisisobutyronitrile and other azo compounds, nitroso compounds such as N,N'-dinitrosopentamethylenetetramine, hydrazodicarbonamide, hydrazine derivatives such as 4,4'-oxybis(benzenesulfonyl hydrazide) and toluenesulfonyl hydrazide, and semicarbazide compounds such as toluenesulfonyl semicarbazide. Examples of physical blowing agents include vermiculite and thermally expandable particles containing hydrocarbons.

[0063] The specific gravity of the above resin layer is preferably 0.7 or higher, more preferably 0.8 or higher, preferably 2.5 or lower, and more preferably 2.0 or lower. The above specific gravity can be measured, for example, by an electronic hydrometer.

[0064] The thickness of the above resin layer is preferably 0.1 mm or more, more preferably 0.2 mm or more, preferably 10 mm or less, and more preferably 5 mm or less.

[0065] Methods for forming the above-mentioned resin layer include, for example, hand lay-up molding, spray-up molding, resin transfer molding, bag molding, injection molding, extrusion molding, and stamping molding.

[0066] The inorganic fiber content constituting the inorganic fiber layer in the thermal insulation material of the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, preferably 100% by mass or less, and more preferably 99% by mass or less.

[0067] The content of the organic binder constituting the inorganic fiber layer in the thermal insulation material of the present invention is preferably 0% by mass or more, more preferably 2% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.

[0068] The content of heat radiation suppressing particles constituting the inorganic fiber layer in the thermal insulation material of the present invention is preferably 3% by mass or more, more preferably 8% by mass or more, preferably 70% by mass or less, and more preferably 60% by mass or less.

[0069] The surfactant content constituting the inorganic fiber layer in the thermal insulation material of the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 3% by mass or less.

[0070] The resin content constituting the resin layer in the thermal insulation material of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less.

[0071] The density of the thermal insulation material of the present invention is 150 kg / m³. 3 The above is preferable, and 200 kg / m 3 The above is more preferable, 650 kg / m 3 The following is preferable: 600 kg / m 3 The following are preferable. The above density can be measured, for example, by an electronic hydrometer.

[0072] The thickness of the thermal insulation material of the present invention is preferably 1 mm or more, more preferably 1.5 mm or more, preferably 7 mm or less, and more preferably 6 mm or less.

[0073] One method for producing the thermal insulation material of the present invention is to laminate the inorganic fiber layer and the resin layer by heating, cooling, and pressing them together. Alternatively, a method can be used in which multiple inorganic fiber layers are laminated by needle punch molding, and then laminated with a resin layer by heating, cooling, and pressing them together.

[0074] Another method for manufacturing a heat insulating material is also part of the present invention, comprising the steps of impregnating an inorganic fiber molded body with a solution containing heat radiation suppression particles and a surfactant to obtain an inorganic fiber layer, and laminating and pressing resin layers onto both sides of the inorganic fiber layer.

[0075] Because the above-mentioned insulating material can exhibit a high insulating effect, it can be suitably used as an insulating material placed between multiple parts to suppress the transfer of heat from one part to an adjacent part. In particular, the above-mentioned heat insulating material can be suitably used as an inter-cell component in batteries such as lithium-ion batteries. Furthermore, even when a battery experiences thermal runaway due to an external impact such as a collision, it can prevent flames and heat generated from ignition inside the battery from being transmitted to adjacent battery cells. Therefore, it can be suitably used as an inter-cell component in automotive batteries. A battery device comprising the thermal insulation material of the present invention and a plurality of battery cells, wherein the thermal insulation material is arranged between the battery cells, is also one of the present inventions.

[0076] Examples of the batteries mentioned above include primary batteries such as nickel-manganese batteries, lithium batteries, and zinc-air batteries; secondary batteries such as nickel-metal hydride batteries, lithium-ion batteries, and lead-acid batteries; solar cells such as silicon-based solar cells, dye-sensitized solar cells, and perovskite solar cells; and fuel cells such as polymer electrolyte membrane fuel cells, alkaline fuel cells, phosphoric acid fuel cells, and solid oxide fuel cells.

[0077] Furthermore, a heat transfer suppression member can be manufactured by impregnating an inorganic fiber molded body with heat radiation suppression particles using a solution containing heat radiation suppression particles and a surfactant. The present invention also includes a method for manufacturing a heat transfer suppressing member, which involves an impregnation step in which heat radiation suppressing particles are impregnated into an inorganic fiber molded body, and the impregnation step uses a solution containing the heat radiation suppressing particles and a surfactant.

[0078] As a method for manufacturing the heat transfer suppressing member described above, the same method as the method for producing the inorganic fiber layer described above can be used. The heat transfer suppressing member described above can be suitably used for the same purposes as the thermal insulation material described above. In particular, the heat transfer suppression member can be suitably used as an inter-cell member in batteries such as lithium-ion batteries. Furthermore, even when a battery experiences thermal runaway due to an external impact such as a collision, it can prevent flames and heat generated by ignition from inside the battery from being transmitted to adjacent battery cells, making it suitable for use as an inter-cell member in automotive batteries. [Effects of the Invention]

[0079] According to the present invention, it is possible to provide an insulating material that can exhibit a high thermal insulation effect. Furthermore, it is possible to provide a heat transfer suppressing member that can exhibit a high thermal insulation effect, a method for manufacturing a heat transfer suppressing member that can produce the insulating material in a simpler way, and a method for manufacturing an insulating material. [Brief explanation of the drawing]

[0080] [Figure 1] This is a photograph showing the state of solution penetration in Example 1. [Figure 2] This is a photograph showing the state of solution osmosis in Reference Example 1. [Modes for carrying out the invention]

[0081] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples.

[0082] (Example 1) (Preparation of resin layer) A 0.2 mm thick resin layer was prepared by uniformly mixing 100 parts by mass of chlorinated polyvinyl chloride resin (CPVC, manufactured by Tokuyama Sekisui Co., Ltd., degree of polymerization 500, chlorine content 67.3% by mass, oxygen index 60) and 10 parts by mass of a heat stabilizer (manufactured by Nitto Kasei Co., Ltd., organotin-based heat stabilizer "AT-1000") and forming it into a sheet using an 8-inch roll. The specific gravity of the resin layer was measured using an electronic hydrometer and found to be 1.5.

[0083] (Fabrication of inorganic fiber layer) As an inorganic fiber molded product, glass fiber sheet (basis weight 1615g / m²) 2 Average fiber diameter 9 μm, average fiber length 50 mm, average fiber specific gravity 2.4, density 394 kg / m³ 3 A material with a thickness of 4.1 mm was used. The basis weight of the inorganic fibers was calculated by cutting a glass fiber sheet into 10cm squares and measuring its weight using an electronic balance. The average fiber diameter was measured using a scanning electron microscope. The average fiber length was measured using the FiberShape fiber length measurement system. The average fiber specific gravity was measured using an electronic hydrometer. The sheet density was measured using an electronic hydrometer.

[0084] To 485 parts by mass of water, 17.7 parts by mass of heat radiation suppression particles and 1.8 parts by mass of a surfactant having surface tension reducing ability were added. The mixture was then stirred by hand using a stirrer, adjusting to prevent foam formation in the aqueous solution, to prepare a dispersion. Furthermore, silica 1 (KE-P250, manufactured by Nippon Shokubai Co., Ltd.) was used as the heat radiation suppression particle. In addition, Sanmorin OT-70 (surfactant 1: manufactured by Sanyo Chemical Industries, Ltd., anionic surfactant, sodium dioctyl sulfosuccinate, surfactant with surface tension-reducing ability) was used as the surfactant with surface tension-reducing ability. The obtained dispersion was sprinkled uniformly onto the sheet to ensure a uniform coating amount. After standing for 30 minutes, it was confirmed that the dispersion had penetrated the sheet and that there was no accumulation of heat radiation suppression particles, as shown in Figure 1. Afterward, the material was dried in an oven set to 120°C to create an inorganic fiber layer with a thickness of 4.8 mm. When measured using an electronic hydrometer, the density of the inorganic fiber layer was found to be 301 kg / m³. 3 That was the case. Furthermore, when the inorganic fiber molded body was impregnated with a dispersion to form an inorganic fiber layer, the weight change and the content ratio of each component in the dispersion were used to calculate the component content of the inorganic fiber layer. The content of each component is shown in Table 1.

[0085] (Preparation of insulation material) The above resin layer, inorganic fiber layer, and resin layer were stacked and then hot-pressed at 200°C for 5 minutes using a hand press machine, followed by a cooling press for 5 minutes to obtain a 5.0 mm thick thermal insulation material. Measurements using an electronic hydrometer revealed that the density of the insulation material is 466 kg / m³. 3 That was the case.

[0086] (Examples 2-11) An insulating material was prepared in the same manner as in Example 1, except that the composition of the inorganic fiber molded body and dispersion was changed as shown in Table 1. The following surfactants and heat radiation suppression particles were used. <Surfactants> Surfactant 2: SN Dispersant 5040 (manufactured by Sunopco, a polycarboxylic acid-type surfactant with dispersive properties) Surfactant 3: Carribon L-400 (manufactured by Sanyo Chemical Industries, Ltd., polycarboxylic acid type surfactant, surfactant with dispersive properties) <Heat radiation suppression particles> Titanium oxide (ST-750SA, manufactured by Titanium Industries Co., Ltd.) Alumina (manufactured by Nippon Light Metal Co., Ltd., "A33F") Silica 2 (KE-P10 manufactured by Nippon Shokubai Co., Ltd.) Aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., "BF013")

[0087] (Comparative Example 1) The thermal insulation material was prepared in the same manner as in Example 1, except that the composition of the inorganic fiber molded body was changed as shown in Table 1 and a dispersion liquid was not used.

[0088] (Reference example 1) A dispersion was prepared in the same manner as in Example 1, except for the presence or absence of a surfactant. When the obtained dispersion was applied to a sheet in the same manner as in Example 1, the aqueous solution did not penetrate the sheet, as shown in Figure 2. Furthermore, after drying, the deposition of heat radiation suppression particles and other materials was observed on the sheet.

[0089] (evaluation) The thermal insulation layers obtained in the examples and comparative examples were evaluated as follows. The results are shown in Table 1.

[0090] (Thermal insulation performance) The surface of the obtained insulation material was placed on a 650°C iron plate and heated for 3 minutes. After that, the temperature of the surface opposite to the surface heated by the iron plate (back surface temperature) was measured using a K-type thermocouple (sheath type). The lower the temperature on the underside, the better the insulation performance.

[0091] [Table 1] [Industrial applicability]

[0092] According to the present invention, it is possible to provide an insulating material that can exhibit a high thermal insulation effect. Furthermore, it is possible to provide a heat transfer suppressing member that can exhibit a high thermal insulation effect, a method for manufacturing a heat transfer suppressing member that can produce the insulating material in a simpler way, and a method for manufacturing an insulating material.

Claims

1. An inorganic fiber molded body, an inorganic fiber layer containing heat radiation suppression particles and a surfactant, An insulating material comprising the inorganic fiber layer and a laminated resin layer.

2. The thermal insulation material according to claim 1, wherein the heat radiation suppression particles are inorganic oxides, silicon carbide, or inorganic hydrates.

3. The inorganic oxide is silica or a metal oxide. The thermal insulation material according to claim 2, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, alumina, and zirconia oxide.

4. The inorganic hydrate is a metal hydroxide, The thermal insulation material according to claim 2, wherein the metal hydroxide is at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, iron hydroxide, manganese hydroxide, zirconium hydroxide, and gallium hydroxide.

5. The thermal insulation material according to claim 1, 2, 3, or 4, wherein the average fiber length of the inorganic fibers is 0.1 to 150 mm.

6. The thermal insulation material according to claim 1, 2, 3, or 4, wherein the average fiber diameter of the inorganic fibers is 1 to 15 μm.

7. The density of the inorganic fiber molded body is 100 to 600 kg / m³ ３ The thermal insulation material according to claim 1, 2, 3, or 4.

8. The thermal insulation material according to claim 1, 2, 3, or 4, wherein the surfactant comprises at least two types, and the two types of surfactants are anionic surfactants, cationic surfactants, or nonionic surfactants.

9. The thermal insulation material according to claim 1, 2, 3, or 4, wherein the mass ratio of the heat radiation suppressing particles to the total of the heat radiation suppressing particles and the inorganic fibers is 3% by mass or more and 70% by mass or less.

10. The thermal insulation material according to claim 1, 2, 3, or 4, wherein the resin layer is provided on both surfaces of the inorganic fiber layer, and the resin layer contains chlorinated polyvinyl chloride resin.

11. The invention comprises a thermal insulation material according to claim 1, 2, 3, or 4, and a plurality of battery cells, A battery device in which the insulating material is placed between the battery cells.

12. The process involves impregnation of an inorganic fiber molded body with heat radiation suppression particles. The impregnation step uses a solution containing the heat radiation suppression particles and a surfactant. A method for manufacturing a heat transfer suppression member.

13. A step of impregnating an inorganic fiber molded body with a solution containing heat radiation suppression particles and a surfactant to obtain an inorganic fiber layer, A method for manufacturing an insulating material, comprising the step of laminating and pressing resin layers onto both sides of the inorganic fiber layer.

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