WO2023084885A1 - Composition de caoutchouc de silicone résistante au feu, procédé pour la production de celle-ci, corps moulé et batterie - Google Patents

Composition de caoutchouc de silicone résistante au feu, procédé pour la production de celle-ci, corps moulé et batterie Download PDF

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Publication number
WO2023084885A1
WO2023084885A1 PCT/JP2022/033004 JP2022033004W WO2023084885A1 WO 2023084885 A1 WO2023084885 A1 WO 2023084885A1 JP 2022033004 W JP2022033004 W JP 2022033004W WO 2023084885 A1 WO2023084885 A1 WO 2023084885A1
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Prior art keywords
fire
silicone rubber
iron
resistant silicone
rubber composition
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PCT/JP2022/033004
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English (en)
Japanese (ja)
Inventor
木村裕子
長谷航希
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富士高分子工業株式会社
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Priority to JP2022574321A priority Critical patent/JP7281022B1/ja
Publication of WO2023084885A1 publication Critical patent/WO2023084885A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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 fire-resistant silicone rubber composition, a method for producing the same, a molded article and a battery.
  • EV electric vehicles
  • PHEV plug-in hybrid vehicles
  • HEV hybrid vehicles
  • a battery is generally used by arranging a plurality of battery cells and housing them in a cell case. Batteries are manufactured on the assumption of various abnormal situations, one of which is abnormal heat generation such as thermal runaway reaction. When a vehicle battery undergoes thermal runaway, the expansion of the cells deforms or breaks the cell materials, and the heat transfer between the cells spreads the thermal runaway one after another, leading to combustion of the cells.
  • the thermal conductivity is 1 W/m K or more at 80 ° C.
  • Patent Literature 3 proposes a radiator that includes a cylindrical, U-shaped or spiral heat-conducting sheet, a cushion material, and an adhesive layer in order to dissipate the heat of the battery.
  • JP 2019-172762 A Japanese Patent Publication No. 2020-507194 JP 2021-015696 A
  • the present invention provides a silicone rubber composition with high fire resistance and high dimensional stability at high temperatures, a method for producing the same, a molded article, and a battery.
  • the present invention provides a fire-resistant silicone rubber composition containing silicone and an inorganic fire-resistant agent, wherein the silicone is (A1) an organopolysiloxane having two or more alkenyl groups per molecule; (A2) Cross-linking component: 0.01 to 3 organopolysiloxane containing on average one or more silicon atoms bonded with hydrogen atoms per molecule per 1 mol of silicon-bonded alkenyl groups in component A1 including moles,
  • the inorganic refractory agent is (B) Silica (C) Aluminum hydroxide (D) At least one iron component selected from iron, iron oxide and metal oxides containing iron (E) Titanium oxide (F) Fire-resistant silicone rubber containing platinum or a platinum compound composition.
  • the method for producing a fire-resistant silicone rubber composition of the present invention comprises mixing uncrosslinked silicone with at least one iron component selected from iron, iron oxide, and metal oxides containing iron to form a masterbatch mixture; A method for producing a fire-resistant silicone rubber composition in which a predetermined amount of a batch mixture is weighed and mixed with components (A1) to (F) to form a composition.
  • the fire-resistant silicone rubber molded article of the present invention is obtained by molding and curing the fire-resistant silicone rubber composition. ⁇ 20%, a length variation of 1-10%, and a thickness variation of 1-40%.
  • the fire-resistant silicone rubber molded article is arranged as a cushioning material interposed between the cells of the battery.
  • the present invention provides a silicone rubber composition having high fire resistance and high dimensional stability at high temperatures by containing the above (A1) and (A2) as the silicone and containing the above (B) to (F) as the inorganic fire resistant agent.
  • a silicone rubber composition having high fire resistance and high dimensional stability at high temperatures by containing the above (A1) and (A2) as the silicone and containing the above (B) to (F) as the inorganic fire resistant agent.
  • the production method of the present invention can efficiently and rationally obtain the fire-resistant silicone rubber composition of the present invention with good dispersibility of the iron component.
  • FIG. 1A is a schematic cross-sectional view showing fire-resistant silicone rubber moldings arranged between battery cells according to an embodiment of the present invention
  • FIG. 1B is a schematic cross-sectional view when abnormal heat generation occurs.
  • FIG. 2 is a schematic cross-sectional view of a comparative example in which silicone rubber moldings are placed between battery cells and abnormal heat generation occurs.
  • FIG. 3 is a schematic cross-sectional view of a battery in which fire-resistant silicone rubber moldings are arranged between a plurality of battery cells according to one embodiment of the present invention.
  • the present invention is a fire resistant silicone rubber composition containing silicone and an inorganic component.
  • the silicone is (A1) an organopolysiloxane having two or more alkenyl groups per molecule; (A2) Cross-linking component: 0.01 to 3 organopolysiloxane containing on average one or more silicon atoms bonded with hydrogen atoms per molecule per 1 mol of silicon-bonded alkenyl groups in component A1 Including moles.
  • the inorganic fireproof agent is preferably 5 to 200 parts by mass, more preferably 10 to 180 parts by mass, and still more preferably 15 to 150 parts by mass, relative to 100 parts by mass of silicone.
  • the silica is preferably amorphous silica or wet silica.
  • Component (C) aluminum hydroxide, is preferably 50 to 300 parts by mass, more preferably 60 to 280 parts by mass, and still more preferably 70 to 250 parts by mass, relative to 100 parts by mass of silicone.
  • At least one iron component selected from component (D), iron, iron oxide, and metal oxides containing iron is preferably 1 to 15 parts by mass, more preferably 2 to 12 parts by mass, relative to 100 parts by mass of silicone. and more preferably 3 to 10 parts by mass.
  • the iron oxide is preferably iron black, triiron tetroxide (Fe 3 O 4 ), or diiron trioxide (Fe 2 O 3 ). They are also useful as colorants, stabilizers and flame retardants.
  • the (E) component titanium oxide is preferably 1 to 10 parts by mass, more preferably 2 to 9 parts by mass, and still more preferably 3 to 8 parts by mass, relative to 100 parts by mass of silicone.
  • Component (F) platinum or platinum compound is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, still more preferably 0.5 to 3 parts by mass, per 100 parts by mass of silicone. part by mass.
  • the platinum or platinum compound include simple platinum, platinum chloride salts, chloroplatinic acid, platinum-olefin complexes such as platinum-dihydrotetramethyldisiloxane complexes, platinum-alcohol complexes, and platinum coordination compounds.
  • Commercially available addition reaction-curing silicone base polymers are usually divided into component A and component B, one of which contains a platinum-based catalyst and the other contains a cross-linking agent. ) component is added as an inorganic refractory agent.
  • the D50 (median diameter) of the cumulative particle size distribution based on the volume of the inorganic refractory agent is (B) silica: 1 nm to 100 ⁇ m, (C) aluminum hydroxide: 1 to 10 ⁇ m, (D) at least one iron component selected from iron, iron oxide and metal oxides containing iron: 0.1 to 10 ⁇ m; (E) titanium oxide: 1 to 1000 nm, is preferred.
  • the fire-resistant silicone rubber composition preferably further contains an organic peroxide as a vulcanizing agent.
  • the peroxide vulcanization type has better workability than addition vulcanization. As used herein, vulcanization is synonymous with curing.
  • Organic peroxides include, for example, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, (bis(2,4-dichlorobenzoyl) peroxide), p-methylbenzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-butylperoxide, t-butylperbenzoate, 1,6-hexanediol- bis-t-butyl peroxycarbonate and the like.
  • the amount of the organic peroxide to be added is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the silicone rubber component. If the amount is too small, the cross-linking reaction does not proceed sufficiently, and physical properties such as a decrease in hardness, insufficient rubber strength, and an increase in compression set may occur. Physical properties such as increased compression set and discoloration of the resulting molded product may be increased.
  • the fire-resistant silicone rubber composition is thermally conductive, and preferably has a thermal conductivity of 0.2 to 1.0 W/mK, more preferably 0.5 to 1.0 W/mK. It is preferably 0.7 to 1.0 W/mK. With the above thermal conductivity, even if the battery cells generate heat during normal use, the heat can be transferred to the radiator and the battery cells can be prevented from becoming hot.
  • the method for producing a fire-resistant silicone rubber composition of the present invention includes mixing uncrosslinked silicone with at least one iron component selected from iron, iron oxide, and metal oxides containing iron to form a masterbatch mixture; A predetermined amount of the batch mixture is weighed and mixed with the components (A1) to (F) to form a composition.
  • a predetermined amount of the batch mixture is weighed and mixed with the components (A1) to (F) to form a composition.
  • the fire-resistant silicone rubber molded article of the present invention has a width change rate of 1 to 20% and a length change rate of 1 to 20% after being cured in an electric furnace and burned for 20 minutes in an atmosphere of 800°C. 10% and a thickness change rate of 1 to 40%. With this fire resistance, there is little risk of combustion even if the battery cells generate abnormal heat.
  • the molded body has a width of about 30 mm, a length of about 50 mm, and a thickness of about 1.0 to 3.0 mm.
  • the fire-resistant silicone rubber molding preferably has an initial hardness after curing of 1 to 90 in Asker A hardness. This results in a material that is flexible and less deformed by cell expansion while maintaining fire resistance and thermal insulation properties.
  • the fire-resistant silicone rubber composition can be used in a variety of applications, and because of its high fire resistance and high dimensional stability at high temperatures, it is useful as a cushioning material interposed between battery cells.
  • FIG. 1A is a schematic cross-sectional view in which a silicone rubber molding 1 is arranged between battery cells 2a and 2b according to one embodiment of the present invention.
  • FIG. 1B is a schematic cross-sectional view when abnormal heat generation occurs. Since the silicone rubber molding 1 has fire resistance, it prevents deformation between the cells 2a and 2b due to expansion of the cells while maintaining the thickness.
  • FIG. 2 is an example of a silicone rubber molding 3 of a comparative example.
  • the silicone rubber molded body 3 of the comparative example is arranged between the battery cells 2a and 2b, abnormal heat generation causes deformation of the battery cell 2b, for example, which becomes an expanded portion 4, which damages the adjacent battery cell 2a.
  • Fig. 3 is a schematic cross-sectional view of a battery in which a silicone rubber molding 1 is arranged between a plurality of battery cells 2a, 2b, ... according to one embodiment of the present invention.
  • a thermally conductive sheet (TIM) 6 is placed on a cooling unit 5, battery cells 2a, 2b, . It is The upper part is covered with a cushioning material sheet 7 and a cell case 8, and wiring 9 is led out from the cell.
  • ⁇ Fire resistance> A silicone rubber molded body having a width of about 30 mm, a length of about 50 mm, and a thickness of about 1.0 to 3.0 mm is placed in an electric furnace, and after burning for 20 minutes in an atmosphere of 800° C., the width, length, and thickness are measured. It was measured and the rate of change was obtained.
  • ⁇ Hardness> Using a rubber hardness tester specified in JIS K 7312, initial hardness after curing and Asker A hardness were measured.
  • Examples 1 to 3 had high dimensional stability, especially thickness after the fire resistance and combustion test. This characteristic can prevent deformation of the material even when the battery overheats. On the other hand, each comparative example had low dimensional stability especially in thickness after the combustion test, and the fire resistance was not favorable.
  • the silicone rubber molded article of the present invention is useful not only as a cushioning material for battery cells, but also as various cushioning materials.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de caoutchouc de silicone résistante au feu, qui contient un silicone et un agent résistant au feu inorganique. Le silicone contient : (A1) un organopolysiloxane ayant au moins 2 groupes alcényle par molécule ; et (A2) un composant de réticulation en une quantité telle que la quantité d'organopolysiloxanes ayant une moyenne d'au moins 1 atome de silicium lié à un atome d'hydrogène par molécule est de 0,01 à 3 moles pour 1 mole de groupes alcényle liés à un atome de silicium dans le composant A1. L'agent résistant au feu inorganique contient : (B) de la silice ; (C) de l'hydroxyde d'aluminium ; (D) un composant de fer ; (E) de l'oxyde de titane ; et (F) du platine ou un composé du platine. L'invention concerne également un corps moulé en caoutchouc de silicone obtenu par moulage et durcissement de cette composition, qui est disposé entre des cellules de batterie 2a et 2b. Selon cette configuration, l'invention concerne : une composition de caoutchouc de silicone ayant une résistance au feu élevée et une stabilité dimensionnelle élevée à des températures élevées ; un corps moulé ; et une batterie.
PCT/JP2022/033004 2021-11-09 2022-09-01 Composition de caoutchouc de silicone résistante au feu, procédé pour la production de celle-ci, corps moulé et batterie WO2023084885A1 (fr)

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JP2022574321A JP7281022B1 (ja) 2021-11-09 2022-09-01 耐火性シリコーンゴム組成物、その製造方法、成形体及びバッテリー

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JP2021182444 2021-11-09
JP2021-182444 2021-11-09

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001342255A (ja) * 2000-05-31 2001-12-11 Shin Etsu Chem Co Ltd シリコーン重合物及びシリコーン組成物並びにそれを用いた化粧料
JP2016124967A (ja) * 2014-12-26 2016-07-11 東レ・ダウコーニング株式会社 硬化性シリコーン組成物、それからなる半導体用封止剤および半導体装置
JP2017206624A (ja) * 2016-05-19 2017-11-24 富士高分子工業株式会社 常温熱伝導性かつ高温断熱性組成物
JP2019172762A (ja) * 2018-03-27 2019-10-10 積水化学工業株式会社 熱伝導性熱膨張性部材
WO2021059567A1 (fr) * 2019-09-25 2021-04-01 富士高分子工業株式会社 Feuille de transfert de chaleur pour matériaux d'étanchéité et composant électrique/électronique générant de la chaleur dans lequel celle-ci est incorporée
WO2022049902A1 (fr) * 2020-09-03 2022-03-10 富士高分子工業株式会社 Matériau thermoconducteur de dissipation thermique en silicone

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001342255A (ja) * 2000-05-31 2001-12-11 Shin Etsu Chem Co Ltd シリコーン重合物及びシリコーン組成物並びにそれを用いた化粧料
JP2016124967A (ja) * 2014-12-26 2016-07-11 東レ・ダウコーニング株式会社 硬化性シリコーン組成物、それからなる半導体用封止剤および半導体装置
JP2017206624A (ja) * 2016-05-19 2017-11-24 富士高分子工業株式会社 常温熱伝導性かつ高温断熱性組成物
JP2019172762A (ja) * 2018-03-27 2019-10-10 積水化学工業株式会社 熱伝導性熱膨張性部材
WO2021059567A1 (fr) * 2019-09-25 2021-04-01 富士高分子工業株式会社 Feuille de transfert de chaleur pour matériaux d'étanchéité et composant électrique/électronique générant de la chaleur dans lequel celle-ci est incorporée
WO2022049902A1 (fr) * 2020-09-03 2022-03-10 富士高分子工業株式会社 Matériau thermoconducteur de dissipation thermique en silicone

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JPWO2023084885A1 (fr) 2023-05-19

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