WO2023127308A1 - シール材用シリコーンゴム組成物、シール材および電池 - Google Patents

シール材用シリコーンゴム組成物、シール材および電池 Download PDF

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Publication number
WO2023127308A1
WO2023127308A1 PCT/JP2022/041314 JP2022041314W WO2023127308A1 WO 2023127308 A1 WO2023127308 A1 WO 2023127308A1 JP 2022041314 W JP2022041314 W JP 2022041314W WO 2023127308 A1 WO2023127308 A1 WO 2023127308A1
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Prior art keywords
silicone rubber
flame
sealing material
rubber composition
retardant
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PCT/JP2022/041314
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English (en)
French (fr)
Japanese (ja)
Inventor
乙音 江角
勇志 安福
貴美 川端
竜雄 片山
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Uchiyama Manufacturing Corp
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Uchiyama Manufacturing Corp
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Priority to US18/723,937 priority Critical patent/US20250059353A1/en
Priority to JP2023570708A priority patent/JP7701085B2/ja
Publication of WO2023127308A1 publication Critical patent/WO2023127308A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025098427A priority patent/JP2025120421A/ja
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/143—Fireproof; Explosion-proof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
    • H01M50/293—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a silicone rubber composition for sealing materials, sealing materials and batteries.
  • compositions in which various additives are added to silicone rubber have been proposed in order to impart industrially desirable physical properties (see Patent Documents 1 to 3, for example).
  • An object of one aspect of the present invention is to provide a silicone rubber composition for sealing materials with improved flame retardancy compared to conventional ones.
  • the silicone rubber composition according to one aspect of the present invention is comprising a flame-retardant silicone rubber compound and a fibrous flame retardant, Assuming that the content of the flame-retardant silicone rubber compound is 100 parts by weight, the content of the fibrous flame retardant is 5 to 60 parts by weight, The above flame-retardant silicone rubber compound is V-0 or higher in the UL94 standard.
  • a silicone rubber composition for sealing materials with improved flame retardancy over conventional ones.
  • FIG. 1 is a schematic diagram showing an example of a battery using a sealing material according to one embodiment of the present invention
  • a to B representing a numerical range means “A or more and B or less”.
  • a silicone rubber composition for sealing material contains a flame-retardant silicone rubber compound and a fibrous flame retardant. Each component will be described below.
  • a flame-retardant silicone rubber compound is a composition obtained by adding various additives to silicone rubber to impart flame retardancy.
  • the flame-retardant silicone rubber compound has a flame retardancy of V-0 or higher according to the UL94 standard.
  • the UL94 standard is a standard for evaluating the flame retardancy of plastic products and is widely adopted worldwide.
  • the UL94 standard grades include 5VA, 5VB, V-0, V-1, V-2 and HB in descending order of flame resistance. Therefore, flame retardant silicone rubber compounds are 5VA, 5VB or V-0 under the UL94 standard. In one embodiment, the flame retardant silicone rubber compound is V-0 under the UL94 standard. Since the test method of the UL94 standard is well known among those skilled in the art, the explanation is omitted.
  • the flame-retardant silicone rubber compound contains silicone rubber.
  • the silicone gum is an organopolysiloxane resin.
  • the unit having an organopolysiloxane structure out of all the units contained in the main chain is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more.
  • Specific examples of silicone rubber include methylsilicone rubber, vinylmethylsilicone rubber, phenylmethylsilicone rubber, and fluorosilicone rubber. Only one type of these silicone rubbers may be contained, or two or more types may be contained.
  • the flame retardant silicone rubber compound includes vinyl methyl silicone rubber.
  • flame-retardant silicone rubber compounds examples include platinum, platinum compounds, iron oxide, triazole compounds, and aluminum hydroxide. Only one type of these additives may be contained, or two or more types may be contained. Many flame-retardant silicone rubber compounds are on the market, and there are many related patent documents. Therefore, the detailed composition of the flame-retardant silicone rubber compound will be omitted.
  • Examples of commercially available flame-retardant silicone rubber compounds include SILASTIC (TM) SH502U, SH502U A/B, SH1447 U A (all from Dow Toray Industries, Inc.); KE-5620W-U, KE-5620BL -U, KE-5612E-U, KE-3494, KE3490, KE3467, KE-4890, KE-40RTV, KE-1831, KE-1867, KE-1891, KE-1204-LTV, KE-1292, KE-1800 , KE-1802 (both from Shin-Etsu Chemical Co., Ltd.); ELASTOSIL (R) LR 3011/50 FR, LR 3001/55 FR, LR 3001/60 FR, LR 3170/40 (both from Asahi Kasei Wacker Silicone Ltd.); TSE2186U, TSE2183U, TSE2187U, TSE2184U, TCM5406U, XE20-A7016 (both of
  • Examples of patent documents disclosing flame-retardant silicone rubber compounds include JP-A-2004-149693, JP-A-2006-182911, and JP-A-2009-144024.
  • a fibrous flame retardant refers to a flame retardant that takes a fibrous form.
  • fibrous morphology intends a shape having an aspect ratio (length/diameter) of 3 or greater.
  • a silicone rubber composition obtained by combining a flame-retardant silicone rubber compound and a fibrous flame retardant has improved flame retardancy compared to the flame-retardant silicone rubber compound itself.
  • flame retardants other than fiber flame retardants phosphorus flame retardants, particulate inorganic flame retardants, etc.
  • the effects of the present invention are realized by selecting the fiber-based flame retardant among various types of flame retardants.
  • the lower limit of the average fiber length of the fibrous flame retardant is preferably 50 ⁇ m or longer, more preferably 70 ⁇ m or longer, and even more preferably 100 ⁇ m or longer.
  • the upper limit of the average fiber length of the fibrous flame retardant is preferably 1500 ⁇ m or less, more preferably 1000 ⁇ m or less, and even more preferably 800 ⁇ m or less.
  • the lower limit of the average diameter of the fibrous flame retardant is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, still more preferably 0.15 ⁇ m or more, and particularly preferably 0.2 ⁇ m or more.
  • the upper limit of the average diameter of the fibrous flame retardant is preferably 10.0 ⁇ m or less, more preferably 5.0 ⁇ m or less, still more preferably 3.0 ⁇ m or less, and particularly preferably 1.0 ⁇ m or less.
  • the lower limit of the aspect ratio is preferably 5 or more, more preferably 50 or more, still more preferably 100 or more, and particularly preferably 150 or more.
  • the upper limit of the aspect ratio is preferably 5000 or less, more preferably 4000 or less, even more preferably 1000 or less, particularly preferably 500 or less, and even more preferably 250 or less.
  • the lower limit of the shot content of the fibrous flame retardant may be 0.1% by weight or more, 0.01% by weight or more, or substantially 0% by weight or more based on the weight of the fibrous flame retardant.
  • the upper limit of the shot content of the fiber-based flame retardant is preferably 5% by weight or less, more preferably 1% by weight or less, and even more preferably 0.5% by weight or less, based on the weight of the fiber-based flame retardant.
  • the shot means non-fibrous particles that have not been fibrillated in the production process of the fibrous flame retardant.
  • fibrous flame retardants include artificial mineral fibers, natural mineral fibers and synthetic organic fibers.
  • man-made mineral fibers include rock wool, stone wool, slag wool, mineral wool, glass wool and mineral glass wool.
  • natural mineral fibers include wollastonite and potassium titanate fibers.
  • synthetic organic fibers include aramid fibers.
  • artificial mineral fibers are preferred.
  • rock wool is preferred.
  • the fibrous flame retardant is an inorganic material. In one embodiment, the fibrous flame retardant is not asbestos.
  • the silicone rubber composition for sealing materials according to one embodiment of the present invention may contain components other than those described above. Examples of such ingredients include curing agents.
  • a curing agent is a component that imparts rubber elasticity to a silicone rubber composition.
  • a person skilled in the art can appropriately select a curing agent according to the reaction mechanism for imparting rubber elasticity.
  • reaction mechanisms by curing agents include cross-linking reaction, condensation reaction, and addition reaction.
  • organic peroxide can be used when rubber elasticity is imparted by a cross-linking reaction.
  • organic peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, cumyl-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, di- -t-butyl peroxide.
  • a silicon-containing cross-linking agent and a curing catalyst can be used when rubber elasticity is imparted by a condensation reaction.
  • silicon-containing crosslinkers include alkoxysilanes, acetoxysilanes, cyclic siloxanes.
  • curing catalysts include carboxylic acid metal salts and organic tin compounds.
  • Organohydrogenpolysiloxane is polyorganosiloxane in which an average of two or more hydrogen atoms per molecule are bonded to silicon atoms.
  • the silicone rubber composition may contain oil.
  • oils are preferred, and modified silicone oils are more preferred.
  • Silicone oil represents an oil containing polyorganosiloxane as a main component.
  • Modified silicone oil refers to silicone oil in which some of the methyl groups contained in dimethylsilicone oil have been substituted with other functional groups.
  • modified silicone oils include amino-modified silicone oils, epoxy-modified silicone oils, carboxyl-modified silicone oils, carbinol-modified silicone oils, (meth)acrylic-modified silicone oils, mercapto-modified silicone oils, phenol-modified silicone oils, and polyether-modified silicone oils.
  • Modified silicone oils include non-reactive modified silicone oils and reactive modified silicone oils. Among these, non-reactive modified silicone oils are preferred.
  • the silicone rubber composition may contain various additives known in the technical field.
  • additives include reinforcing fillers (silica, diatomaceous earth, quartz powder, mica, titanium oxide, etc.); extending fillers (diatomaceous earth, quartz powder, mica, clay, glass beads, aluminum oxide, etc.); heat resistance improvers (carbon black, red iron oxide, alkali metal oxides, alkaline earth metal oxides, etc.); and pigments.
  • the lower limit of the content of the flame-retardant silicone rubber compound is preferably 50% by weight or more, more preferably 55% by weight or more.
  • the upper limit of the content of the flame-retardant silicone rubber compound can be, for example, 98% by weight or less.
  • the lower limit of the silicone rubber polymer content is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably 18% by weight or more.
  • the upper limit of the silicone rubber polymer content can be, for example, 98% by weight or less.
  • the silicone rubber composition contains a rubber component other than silicone rubber
  • the ratio of the silicone rubber to the total rubber component is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more. preferable.
  • the silicone rubber composition does not contain rubber components other than silicone rubber.
  • rubber components other than silicone rubber include fluororubber (FKM), natural rubber (NR), styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), and acrylonitrile.
  • NBR butadiene rubber
  • IIR butyl rubber
  • EPM ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • U urethane rubber
  • AEM acrylic rubber
  • ACM acrylic rubber
  • the lower limit of the content of the fibrous flame retardant in the silicone rubber composition is 5 parts by weight or more, preferably 15 parts by weight or more, and 20 parts by weight or more when the content of the flame-retardant silicone rubber compound is 100 parts by weight. is more preferred.
  • the upper limit of the content of the fibrous flame retardant in the silicone rubber composition is 60 parts by weight or less, preferably 50 parts by weight or less, and 45 parts by weight or less when the content of the flame-retardant silicone rubber compound is 100 parts by weight. is more preferable, and 40 parts by weight or less is even more preferable.
  • the silicone rubber composition tends to have a softness suitable for use as a sealing material.
  • the lower limit of the oil content in the silicone rubber composition is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and 0.5% by weight or more, based on the total weight of the silicone rubber composition. More preferred. If the oil content is less than 0.1% by mass, workability may deteriorate.
  • the upper limit of the oil content in the silicone rubber composition is preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, based on the total weight of the silicone rubber composition. If the oil content exceeds 15% by mass, excessive softening or bleeding may occur.
  • the content of the curing agent can be 0.2 to 5.0 parts by weight when the content of the flame-retardant silicone rubber compound is 100 parts by weight.
  • the Shore A hardness of the silicone rubber composition is preferably 85 or less, more preferably 80 or less. If the Shore A hardness is within the above range, it can be said that the sealing material has suitable softness. As used herein, Shore A hardness is measured with a type A durometer based on JIS K6253. For more specific examples of measuring methods, see Examples of the present application. Note that the Shore A hardness of the silicone rubber composition is measured for the cured silicone rubber composition in a normal state (a state in which no heat test or combustion test is applied).
  • the compression set of the silicone rubber composition after the heat resistance test is preferably 50 or less, more preferably 30 or less. If the compression set after the heat resistance test is within the above range, it can be said that the material has sufficient elasticity even after being exposed to high temperatures.
  • the compression set after the heat resistance test is measured based on JIS K6262. For more specific examples of measuring methods, see Examples of the present application.
  • the compression set of the silicone rubber composition after the heat resistance test the cured silicone rubber composition is to be measured.
  • the silicone rubber composition has improved flame retardancy compared to the flame retardant silicone rubber compound contained alone.
  • improved flame retardancy means that one or more (preferably two or more, more preferably all) of the following three conditions are satisfied. See the examples of the present application for the method of conducting the flame retardant test. ⁇ Smoke generation time is delayed. ⁇ Flame generation time is delayed. - Shorter flame duration.
  • a sealing material according to an aspect of the present invention contains the silicone rubber composition for a sealing material described above.
  • the term "sealing material” refers to a molded product that is interposed between two or more members.
  • the two or more members may be members whose relative positions change, or may be members that are relatively stationary.
  • the sealing material for example, has the function of sealing the movement of a fluid (gas, liquid, or mixture thereof).
  • the application of the sealing material is not particularly limited. Since the sealing material according to one embodiment of the present invention has improved flame retardancy, it is preferably used for products that require flame retardancy. Examples of such products include batteries, vehicles, housing materials, home appliances, and mobile terminals.
  • Battery 10 includes sealing material 1 , cell 2 , heat insulating material 3 and container 4 .
  • Battery 10 is configured to draw power from two or more cells 2 (12 cells 2 in FIG. 1). In addition, in FIG. 1, members for taking out electric power from the cell 2 are omitted.
  • a specific example of the battery 10 is a nonaqueous electrolyte secondary battery (such as a lithium ion secondary battery).
  • the sealing material 1 is a sealing material according to one aspect of the present invention.
  • the cell 2 is a power generation element in which a positive electrode, a negative electrode, a separator, an electrolytic solution, and the like are packaged.
  • the heat insulating material 3 is a member that prevents heat generation from the cells 2 from being transmitted.
  • the container 4 is a member that stores the sealing material 1 , the cells 2 and the heat insulating material 3 .
  • the interior of the container 4 is divided into two or more compartments by the heat insulating material 3.
  • it is divided into four compartments, compartment A, compartment B, compartment C and compartment D.
  • Two or more cells 2 are arranged in two or more partitions.
  • the cells 2 are arranged in all four sections A to D, but there may be sections in which the cells 2 are not arranged.
  • the sealing material 1 is arranged so as to close the gap between the heat insulating material 3 and the container 4 .
  • the sealing material 1 is a sealing material according to one aspect of the present invention, it has improved flame retardancy compared to conventional sealing materials. Therefore, battery 10 has improved safety over conventional batteries.
  • Silicone rubber composition for sealing material and method for producing sealing material The method for producing the silicone rubber composition for sealing material according to one aspect of the present invention is not particularly limited. For example, by kneading the components described in section [1], a silicone rubber composition for sealing materials can be produced.
  • a kneader can be used for kneading the components. Examples of kneaders include open rolls, kneaders, planetarium mixers, Banbury mixers, and extruders.
  • the kneading temperature may be 25-200°C.
  • the kneading time may be from 1 minute to 1 hour.
  • a sealing material can be produced by molding and curing the silicone rubber composition for a sealing material described above.
  • molding methods include injection molding, transfer molding, injection molding, compression molding, pressing, and extrusion. Curing temperatures may range from 25 to 200°C. Curing times may be from 10 seconds to 120 minutes.
  • the order of curing and molding is not particularly limited.
  • the cured silicone rubber composition may be molded, the silicone rubber composition during the curing reaction may be molded, or the molded body may be cured after molding.
  • the cured molding may be further cured secondary.
  • the secondary curing temperature may be 25-250°C. Secondary cure times may range from 30 minutes to 4 hours.
  • the present invention includes the following configurations. ⁇ 1> comprising a flame-retardant silicone rubber compound and a fibrous flame retardant, Assuming that the content of the flame-retardant silicone rubber compound is 100 parts by weight, the content of the fibrous flame retardant is 5 to 60 parts by weight, A silicone rubber composition for a sealing material, wherein the flame-retardant silicone rubber compound is V-0 or higher in the UL94 standard. ⁇ 2> The silicone rubber composition for a sealing material according to ⁇ 1>, wherein the fibrous flame retardant contains one or more selected from the group consisting of artificial mineral fibers, natural mineral fibers and synthetic organic fibers.
  • the fibrous flame retardant contains the artificial mineral fiber, The artificial mineral fiber contains rock wool, The silicone rubber composition for sealing materials according to ⁇ 2>.
  • ⁇ 6> The silicone rubber composition for a sealing material according to any one of ⁇ 1> to ⁇ 5>, which has a Shore A hardness of 85 or less.
  • a sealing material comprising the silicone rubber composition for sealing material according to any one of ⁇ 1> to ⁇ 6>.
  • a battery comprising two or more cells, a heat insulating material, a container, and the sealing material according to ⁇ 7>, The two or more cells, the insulating material and the sealing material are stored in the container, The heat insulating material is arranged to divide the inside of the container into two or more compartments, The two or more cells are divided into two or more of the two or more sections, and The sealing material is arranged to close the gap between the heat insulating material and the container, battery.
  • a battery comprising two or more cells, a thermal insulator, a container, and a seal
  • a battery, wherein the sealant comprises the silicone rubber composition for a sealant according to any one of ⁇ 1> to ⁇ 6>.
  • the present invention also includes the following configurations.
  • a method for producing a silicone rubber composition for a sealing material comprising: mixing a flame retardant silicone rubber compound and a fibrous flame retardant; When the amount of the flame-retardant silicone rubber compound is 100 parts by weight, the amount of the fibrous flame retardant is 5 to 60 parts by weight, The production method, wherein the flame-retardant silicone rubber compound is V-0 or higher in the UL94 standard.
  • a method for improving flame retardancy of a flame retardant silicone rubber compound comprising: mixing a flame retardant silicone rubber compound and a fibrous flame retardant; When the amount of the flame-retardant silicone rubber compound is 100 parts by weight, the amount of the fibrous flame retardant is 5 to 60 parts by weight, The method, wherein the flame-retardant silicone rubber compound is V-0 or higher in the UL94 standard.
  • Flame-retardant silicone rubber compound Flame-retardant silicone rubber compound A (KE-5612E-U, Shin-Etsu Chemical Co., Ltd., vinyl methyl silicone rubber compound, UL94 standard: V-0) ⁇ Flame-retardant silicone rubber compound B (SH502U, Dow Toray Industries, Inc., vinyl methyl silicone rubber compound, UL94 standard: V-0) ⁇ Flame retardant/fiber flame retardant A (rock wool, RS490ELS-Roxul1000, Rapinus, fiber length: 150-250 ⁇ m, shot content: 0.2% (average)) ⁇ Fibrous flame retardant B (rock wool, FS021, JFE Rock Fiber Co., Ltd., shot content: 30-40%) ⁇ Fibrous flame retardant C (aramid fiber, Twaron (registered trademark) 3091, Teijin Limited, fiber length: 650 to 1150 ⁇ m) ⁇ Phosphorus-based flame retardant (Fireguard FCX-
  • a vulcanized rubber sheet was produced by the following procedure.
  • the vulcanized rubber sheet serves as a material for producing test pieces in tests described later. 1.
  • Each component shown in Table 1 was kneaded with an open roll. The temperature during kneading was 20 to 100°C. The kneading time was 10-30 minutes. 2.
  • An unvulcanized rubber sheet was produced from the resulting kneaded material. 3.
  • the unvulcanized rubber sheet was press vulcanized at 165° C. for 10 minutes. 4. Further, secondary vulcanization was performed at 200° C. for 4 hours. Thus, a vulcanized rubber sheet having a thickness of 2 mm was obtained.
  • ⁇ Test method ⁇ [1. Hardness in normal state] Based on JIS K6253, the Shore A hardness of the silicone rubber composition was measured before imposing a heat resistance test or a combustion test. Specific procedures are as follows. 1. Three vulcanized rubber sheets with a thickness of 2 mm were stacked to form a test piece. 2. Measurements were made at 23° C. and 50% relative humidity using a type A durometer. The durometer peak value was defined as Shore A hardness.
  • the dispersibility of the fibrous flame retardant was evaluated from the appearance of the silicone rubber composition. Specific procedures are as follows. 1. The kneaded unvulcanized rubber sheet produced in Examples or Comparative Examples was cut out with a cutter. 2. A filler dispersion meter (Dispersion Checker DCF50A, M&K Co., Ltd.) was used to measure the degree of dispersion of the fibrous flame retardant in the cross section of the cut unvulcanized rubber sheet. The measurement results were evaluated according to the following criteria. A higher degree of dispersion is preferred. 1: less than 80% dispersion 2: 80% or more, less than 90% dispersion 3: 90% or more dispersion
  • a flame test was performed on the silicone rubber composition to evaluate flame retardancy and shape retention after burning. Specific procedures are as follows. 1. A test piece was obtained by cutting a sheet of width 10 mm ⁇ length 100 mm from a vulcanized rubber sheet of thickness 2 mm. 2. The test piece was fixed to a jig, and the flame of the burner was adjusted so that the temperature of the combustion site reached 800°C. 3. The specimen was flamed for 2 minutes. At this time, the time (seconds) at which smoke was generated and the time (seconds) at which flames were generated were recorded, assuming that the time when the flame began to be applied was 0 seconds. Also, the duration (seconds) from the start of the flame until it was extinguished was recorded. 4. After burning, the deflection and appearance of the test piece were visually confirmed.
  • Criteria for judging the deflection and appearance of the test piece after the combustion test are as follows. ⁇ Deflection 1: There is a large deflection. 2: Moderate deflection. 3: There is a small deflection. 4: No deflection (or only slight deflection). - Appearance 1: Defective. There are many cracks, peelings, breaks, crushing, etc. 2: Normal. It has a big crack. 3: Good. Has small or medium cracks. 4: Very good. Only whitened and no cracks (or only microcracks).
  • Table 1 shows the test results.
  • a comparison between Examples 1 to 5 and Comparative Example 1 shows that the silicone rubber composition to which the fibrous flame retardant is added has improved flame retardancy. That is, Examples 1 to 5 were later than Comparative Example 1 in terms of smoke generation time and flame generation time. Further, the duration of flame was shorter in Examples 1 to 5 than in Comparative Example 1.
  • the degree of improvement in flame retardancy was greater in Examples 2 to 5 than in Example 1. Therefore, from the viewpoint of flame retardancy, the content of the fibrous flame retardant is preferably higher than in Example 1 (for example, 15 parts by weight or more per 100 parts by weight of the flame-retardant silicone rubber compound).
  • the content of the fibrous flame retardant is preferably less than that in Example 5 (for example, 45 parts by weight per 100 parts by weight of the flame-retardant silicone rubber compound). the following).
  • the fibrous flame retardant A is the best (Examples 1 to 6), and the fibrous flame retardant B is second best (Examples 7 and 8 ), followed by fiber-based flame retardant C (Example 9). Therefore, from the viewpoint of dispersibility, the fibrous flame retardant is preferably rock wool. Similarly, from the viewpoint of dispersibility, the shot content of the fibrous flame retardant is preferably small (for example, 0.5% by weight or less based on the weight of the fibrous flame retardant).
  • the present invention can be used, for example, as a sealing material for batteries.
  • sealing material 2 cell 3: heat insulating material 4: container 10: battery

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Fireproofing Substances (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
PCT/JP2022/041314 2021-12-28 2022-11-07 シール材用シリコーンゴム組成物、シール材および電池 Ceased WO2023127308A1 (ja)

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US18/723,937 US20250059353A1 (en) 2021-12-28 2022-11-07 Silicone rubber composition for sealing material, sealing material, and battery
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JP2025098427A JP2025120421A (ja) 2021-12-28 2025-06-12 電池シール材用シリコーンゴム組成物および電池シール材

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Publication number Priority date Publication date Assignee Title
WO2024101135A1 (ja) * 2022-11-09 2024-05-16 内山工業株式会社 シール材用積層体、シール材および電池

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JP7202736B1 (ja) * 2021-12-28 2023-01-12 内山工業株式会社 電池
JP7837039B2 (ja) * 2022-01-26 2026-03-30 内山工業株式会社 シール材用シリコーンゴム積層体、シール材および電池

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JPS57141476A (en) * 1981-02-25 1982-09-01 Haraden Koji Kk Refractory airtight sealing material
JPS60238380A (ja) * 1984-05-10 1985-11-27 Nitto Boseki Co Ltd 耐火性シ−リング材
JPS61174287A (ja) * 1985-01-28 1986-08-05 Nitto Boseki Co Ltd 耐火性シ−リング材
JPS6426694A (en) * 1987-04-23 1989-01-27 Toyota Motor Corp Silicone sealant with high tear resistance
JPH02107691A (ja) * 1988-10-18 1990-04-19 Nitto Boseki Co Ltd シーリング材
JPH08127716A (ja) * 1994-10-31 1996-05-21 Shin Etsu Chem Co Ltd 耐火性シリコーンゴム組成物

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JP7202736B1 (ja) * 2021-12-28 2023-01-12 内山工業株式会社 電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57141476A (en) * 1981-02-25 1982-09-01 Haraden Koji Kk Refractory airtight sealing material
JPS60238380A (ja) * 1984-05-10 1985-11-27 Nitto Boseki Co Ltd 耐火性シ−リング材
JPS61174287A (ja) * 1985-01-28 1986-08-05 Nitto Boseki Co Ltd 耐火性シ−リング材
JPS6426694A (en) * 1987-04-23 1989-01-27 Toyota Motor Corp Silicone sealant with high tear resistance
JPH02107691A (ja) * 1988-10-18 1990-04-19 Nitto Boseki Co Ltd シーリング材
JPH08127716A (ja) * 1994-10-31 1996-05-21 Shin Etsu Chem Co Ltd 耐火性シリコーンゴム組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024101135A1 (ja) * 2022-11-09 2024-05-16 内山工業株式会社 シール材用積層体、シール材および電池

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