WO2017188059A1 - Liquid silicone rubber composition and sealing component for solid polymer fuel cell separator - Google Patents

Liquid silicone rubber composition and sealing component for solid polymer fuel cell separator Download PDF

Info

Publication number
WO2017188059A1
WO2017188059A1 PCT/JP2017/015577 JP2017015577W WO2017188059A1 WO 2017188059 A1 WO2017188059 A1 WO 2017188059A1 JP 2017015577 W JP2017015577 W JP 2017015577W WO 2017188059 A1 WO2017188059 A1 WO 2017188059A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicone rubber
liquid silicone
rubber composition
fuel cell
talc
Prior art date
Application number
PCT/JP2017/015577
Other languages
French (fr)
Japanese (ja)
Inventor
昭寛 鈴木
秀人 小紫
Original Assignee
Nok株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nok株式会社 filed Critical Nok株式会社
Priority to JP2018514512A priority Critical patent/JPWO2017188059A1/en
Publication of WO2017188059A1 publication Critical patent/WO2017188059A1/en

Links

Classifications

    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • 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
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a liquid silicone rubber composition and a sealing component for a polymer electrolyte fuel cell separator using the same.
  • polymer electrolyte fuel cells operate at lower temperatures than other types of fuel cells, so there is no risk of material corrosion of the components that make up the cells, and they are relatively large for low-temperature operation. It has the feature of being able to discharge current, and is attracting attention as an alternative power source for in-vehicle internal combustion engines as well as for home cogeneration.
  • the separator is generally formed by forming a plurality of parallel grooves on both sides or one side of a flat plate, and power is generated by a gas diffusion electrode in the fuel cell. In addition to transmitting the electrodes to the outside, it plays a role of draining the water generated in the groove during the power generation process and securing the groove as a flow path for the reaction gas flowing out to the fuel cell.
  • a battery separator further downsizing is required, and a separator sealing material that is excellent in durability and can be used for a long time is required because a large number of separators are used in an overlapping manner.
  • a liquid silicone rubber excellent in heat resistance, elasticity and high-speed moldability is suitably used (Patent Document 1).
  • the rubber composition using such a liquid silicone rubber may have poor acid resistance after crosslinking.
  • the present invention has been made in view of the above circumstances, and provides a liquid silicone rubber composition from which a sealing part for a polymer electrolyte fuel cell separator having sufficient heat resistance and excellent acid resistance can be obtained. Objective.
  • the present inventors have realized sufficient heat resistance after crosslinking and further improved acid resistance by combining liquid silicone rubber and a predetermined amount of talc. It has been found that a liquid silicone rubber composition can be obtained, and the present invention has been completed based on this finding.
  • the gist configuration of the present invention is as follows. [1] It contains liquid silicone rubber and talc, The content of the talc is 0.5 to 15 parts by weight with respect to 100 parts by weight of the liquid silicone rubber, A liquid silicone rubber composition used for producing a sealing part for a polymer electrolyte fuel cell separator. [2] The liquid silicone rubber composition according to the above [1], which is subjected to addition crosslinking. [3] A sealing component for a polymer electrolyte fuel cell separator, which is a product obtained by crosslinking and molding the liquid silicone rubber composition according to [1] or [2].
  • liquid silicone rubber composition used for producing the sealing part for a polymer electrolyte fuel cell separator of the present invention contains liquid silicone rubber [A] and talc [B] as essential components, but is necessary. Depending on the type, various additives [C] can be contained.
  • liquid silicone rubber is not particularly limited, and for example, a low-viscosity liquid silicone rubber having self-fluidity at room temperature (25 ° C.) can be used.
  • a low-viscosity liquid silicone rubber having self-fluidity at room temperature (25 ° C.) can be used.
  • commercially available products such as the KE-1950 series, which is a liquid silicone rubber manufactured by Shin-Etsu Chemical Co., Ltd., and the LR3004 series manufactured by WACKER can be used as they are.
  • liquid silicone rubber as the LIM molding material preferably has a viscosity at 25 ° C. of 1 to 1000 Pa ⁇ s.
  • the viscosity value can be measured with a rotational viscometer.
  • Talc Talc is used to suppress a decrease in compression set under acidic conditions, and can be used regardless of the presence or absence of firing. From the viewpoint of improving acid resistance, in particular, using fired talc. Is preferred.
  • the content of talc is 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the liquid silicone rubber [A]. By setting it as the said range, it has sufficient heat resistance and can improve especially acid resistance. On the other hand, when the content of talc is less than 0.5 parts by weight, the effect of improving acid resistance is not sufficiently exhibited. Further, if the content of talc exceeds 15 parts by weight, sufficient heat resistance cannot be obtained.
  • reinforcing agents such as carbon black and silica generally used as a rubber compounding agent, clay, graphite, calcium silicate Fillers such as zinc oxide and magnesium oxide, hydrosilylation reaction control agents, colorants, heat resistance improvers, flame retardant improvers, heat conduction improvers, internal mold release agents, adhesion imparting agents, A thixotropic agent or the like is appropriately added and used as necessary.
  • reinforcing agents such as carbon black and silica generally used as a rubber compounding agent, clay, graphite, calcium silicate Fillers such as zinc oxide and magnesium oxide, hydrosilylation reaction control agents, colorants, heat resistance improvers, flame retardant improvers, heat conduction improvers, internal mold release agents, adhesion imparting agents, A thixotropic agent or the like is appropriately added and used as necessary.
  • the liquid silicone rubber composition can be prepared by mixing the above-mentioned [A] and [B] components and, if necessary, the [C] component by a known mixing method. For example, it can be prepared by kneading the predetermined components using a kneader such as an intermix or a three roll.
  • a kneader such as an intermix or a three roll.
  • the liquid silicone rubber composition according to the present invention is a low viscosity silicone rubber composition having self-fluidity at room temperature (25 ° C.), and in particular, a polymer electrolyte fuel cell separator by rim molding (Liquid Injection Molding). It is suitably used when manufacturing a sealing part for a machine.
  • the method for producing a sealing part for a polymer electrolyte fuel cell separator according to the present invention selectively uses a specific liquid silicone rubber composition containing the above-described components [A] and [B]. Preferably, it is subjected to addition crosslinking to form an elastic seal layer made of a crosslinked silicone rubber at the peripheral portion of at least one surface of the polymer electrolyte fuel cell separator component.
  • the crosslinking of the liquid silicone rubber composition can be generally performed by pressure crosslinking at about 100 to 300 ° C. for about 10 seconds to 30 minutes using an injection molding machine or the like.
  • secondary crosslinking post-cure
  • Secondary crosslinking can be performed by oven heating generally at about 100-250 ° C. for about 1-10 hours.
  • the thickness of the elastic seal layer obtained by crosslinking and molding the liquid silicone rubber composition is usually 0.05 to 5 mm, particularly preferably about 0.1 to 2 mm.
  • Example 1 First, 100 parts by weight of liquid silicone rubber (KE-1950-50A / B, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.6 parts by weight of calcined talc (Enstack 24, manufactured by Asada Flour Milling Co., Ltd.), a volume of 2 liters Kneading with a planetary mixer (PLM-2 type, manufactured by Inoue Seisakusho Co., Ltd.), and this is further passed once through a 3-inch ⁇ 3-roll (3-roll mill, Kodaira Seisakusho Co., Ltd.) A silicone rubber composition was obtained.
  • liquid silicone rubber KE-1950-50A / B, manufactured by Shin-Etsu Chemical Co., Ltd.
  • calcined talc Engelhardenetack 24, manufactured by Asada Flour Milling Co., Ltd.
  • PLM-2 type manufactured by Inoue Seisakusho Co., Ltd.
  • Example 2 to 5 and Comparative Examples 1 to 3 liquid silicone rubber compositions were obtained in the same manner as in Example 1, except that the amount of calcined talc was changed as shown in Table 1.
  • Example 6 a liquid silicone rubber composition was obtained in the same manner as in Example 3 except that unsintered talc (Mistrone Vapor, Imeris Specialties Japan Co., Ltd.) was used instead of calcined talc. .
  • the compression set means that the smaller the value, the better the heat resistance (sealability) and the longer the seal life.
  • the compression set in hydrofluoric acid means that the smaller the value, the higher the acid resistance.
  • a product having a compression set of 25% or less in air, 34% or less in water, and 50% or less in hydrofluoric acid was determined as an acceptable level.
  • the talc content is particularly in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the liquid silicone rubber. It was confirmed that a molded article having a sufficient heat resistance and an excellent acid resistance having a small compression set in air, water and hydrofluoric acid can be produced.
  • the liquid silicone compositions according to Comparative Examples 1 and 2 were manufactured using these because the talc content was less than 0.5 parts by weight with respect to 100 parts by weight of the liquid silicone rubber.
  • the molded articles have particularly large compression set in hydrofluoric acid, and sufficient acid resistance can be obtained. Not confirmed.
  • the content of talc in the liquid silicone composition according to Comparative Example 3 exceeds 15 parts by weight with respect to 100 parts by weight of the liquid silicone rubber, a molded product manufactured using the talc is obtained by the present invention. It was confirmed that the compression set in air and water was large and sufficient heat resistance could not be obtained as compared with molded articles produced using the liquid silicone compositions (Examples 1 to 6).
  • liquid silicone composition according to the present invention a rubber molded article excellent in heat resistance and acid resistance can be obtained, and therefore, it is suitable for producing a sealing part for a polymer electrolyte fuel cell separator. It was confirmed.

Abstract

The purpose of the present invention is to provide a liquid silicone rubber composition from which a sealing component for solid polymer fuel cell separators which has sufficient thermal stability and superior acid resistance can be obtained. The liquid silicone rubber composition includes liquid silicone rubber and talc, and the talc content is 0.5 - 15 parts by weight to 100 parts by weight of the liquid silicone rubber. The liquid silicone rubber composition is used for manufacturing the sealing component for solid polymer fuel cell separators.

Description

液状シリコーンゴム組成物およびこれを用いた固体高分子型燃料電池セパレータ用シール部品Liquid silicone rubber composition and sealing part for polymer electrolyte fuel cell separator using the same
　本発明は、液状シリコーンゴム組成物およびこれを用いた固体高分子型燃料電池セパレータ用シール部品に関する。 The present invention relates to a liquid silicone rubber composition and a sealing component for a polymer electrolyte fuel cell separator using the same.
　燃料電池は、資源の枯渇に留意する必要がある化石燃料を使用する必要が殆どない上に、発電において騒音を殆ど発生せず、エネルギーの回収率も他のエネルギー発電機関と比べて高くできる等の優れた性質を持つために、実用化が始まっている。 Fuel cells rarely require the use of fossil fuels that require attention to resource depletion, generate almost no noise during power generation, and have a higher energy recovery rate than other energy power generation engines. Because of its excellent properties, it has been put into practical use.
　中でも固体高分子型燃料電池は、他のタイプの燃料電池と比べて低温で作動するので、電池を構成する部品について材料面での腐食の心配がないばかりか、低温動作のわりには比較的大電流を放電可能といった特徴を持ち、家庭のコージェネレーション用としてだけではなく、車載用の内燃機関の代替電源として注目を集めている。 In particular, polymer electrolyte fuel cells operate at lower temperatures than other types of fuel cells, so there is no risk of material corrosion of the components that make up the cells, and they are relatively large for low-temperature operation. It has the feature of being able to discharge current, and is attracting attention as an alternative power source for in-vehicle internal combustion engines as well as for home cogeneration.
　この固体高分子型燃料電池を構成する部品の中で、セパレータは一般的に平板の両面または片面に複数の平行する溝を形成してなるもので、燃料電池セル内のガス拡散電極で発電した電極を外部へ伝達すると共に、発電の課程で、上記溝中に生成した水を排水し、当該溝を燃料電池セルへ流出する反応ガスの流路として確保する役割を担っている。このような電池用セパレータとしては、より小型化が要求され、また多数のセパレータを重ね合わせて使用することから耐久性が優れ、長時間使用できるセパレータ用シール材料が要求されている。 Among the components constituting this polymer electrolyte fuel cell, the separator is generally formed by forming a plurality of parallel grooves on both sides or one side of a flat plate, and power is generated by a gas diffusion electrode in the fuel cell. In addition to transmitting the electrodes to the outside, it plays a role of draining the water generated in the groove during the power generation process and securing the groove as a flow path for the reaction gas flowing out to the fuel cell. As such a battery separator, further downsizing is required, and a separator sealing material that is excellent in durability and can be used for a long time is required because a large number of separators are used in an overlapping manner.
　このようなセパレータ用シール材料には、耐熱性、弾性および高速成形性に優れた液状のシリコーンゴムが好適に用いられる（特許文献１）。しかし、このような液状シリコーンゴムを用いたゴム組成物は、架橋後の耐酸性が劣るおそれがあった。 For such a separator sealing material, a liquid silicone rubber excellent in heat resistance, elasticity and high-speed moldability is suitably used (Patent Document 1). However, the rubber composition using such a liquid silicone rubber may have poor acid resistance after crosslinking.
特開２０１５－０２２８００号公報Japanese Patent Laid-Open No. 2015-022800
　本発明は、上記実情に鑑みてなされたものであり、十分な耐熱性および優れた耐酸性を有した固体高分子型燃料電池セパレータ用シール部品が得られる液状シリコーンゴム組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a liquid silicone rubber composition from which a sealing part for a polymer electrolyte fuel cell separator having sufficient heat resistance and excellent acid resistance can be obtained. Objective.
　本発明者らは、上記目的を達成するため鋭意研究を重ねた結果、液状シリコーンゴムと、所定量のタルクとを組み合わせることによって、架橋後において十分な耐熱性を実現し、さらに耐酸性を向上し得る、液状シリコーンゴム組成物が得られることを見出し、かかる知見に基づき本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventors have realized sufficient heat resistance after crosslinking and further improved acid resistance by combining liquid silicone rubber and a predetermined amount of talc. It has been found that a liquid silicone rubber composition can be obtained, and the present invention has been completed based on this finding.
　すなわち、本発明の要旨構成は、以下のとおりである。
［１］　液状シリコーンゴムと、タルクとを含有してなり、
　前記タルクの含有量が、前記液状シリコーンゴム１００重量部に対して、０．５～１５重量部であり、
　固体高分子型燃料電池セパレータ用シール部品を製造するために用いられる、液状シリコーンゴム組成物。
［２］　付加架橋させる、上記［１］に記載の液状シリコーンゴム組成物。
［３］　上記［１］または［２］に記載の液状シリコーンゴム組成物を架橋成形した物である、固体高分子型燃料電池セパレータ用シール部品。 That is, the gist configuration of the present invention is as follows.
[1] It contains liquid silicone rubber and talc,
The content of the talc is 0.5 to 15 parts by weight with respect to 100 parts by weight of the liquid silicone rubber,
A liquid silicone rubber composition used for producing a sealing part for a polymer electrolyte fuel cell separator.
[2] The liquid silicone rubber composition according to the above [1], which is subjected to addition crosslinking.
[3] A sealing component for a polymer electrolyte fuel cell separator, which is a product obtained by crosslinking and molding the liquid silicone rubber composition according to [1] or [2].
　本発明は、上述した液状シリコーンゴム組成物を用いることによって、十分な耐熱性および優れた耐酸性を有した固体高分子型燃料電池セパレータ用シール部品を得ることができる。 In the present invention, by using the above-described liquid silicone rubber composition, a sealing part for a polymer electrolyte fuel cell separator having sufficient heat resistance and excellent acid resistance can be obtained.
　以下、本発明に係る液状シリコーンゴム組成物、およびその用途について具体的に説明する。
＜液状シリコーンゴム組成物＞
　本発明の固体高分子型燃料電池セパレータ用シール部品を製造するために用いられる液状シリコーンゴム組成物は、液状シリコーンゴム［Ａ］と、タルク［Ｂ］とを必須の含有成分とするが、必要に応じて各種添加剤［Ｃ］を含有させることができる。 Hereinafter, the liquid silicone rubber composition according to the present invention and its use will be specifically described.
<Liquid silicone rubber composition>
The liquid silicone rubber composition used for producing the sealing part for a polymer electrolyte fuel cell separator of the present invention contains liquid silicone rubber [A] and talc [B] as essential components, but is necessary. Depending on the type, various additives [C] can be contained.
［Ａ］液状シリコーンゴム
　液状シリコーンゴムとしては、特に限定はなく、例えば、室温（２５℃）において自己流動性を有する粘度の低い液状のシリコーンゴムを用いることできる。実際には、信越化学工業株式会社製の液状のシリコーンゴムであるＫＥ－１９５０シリーズや、ＷＡＣＫＥＲ社製のＬＲ３００４シリーズ等の市販品をそのまま用いることができる。 [A] Liquid Silicone Rubber The liquid silicone rubber is not particularly limited, and for example, a low-viscosity liquid silicone rubber having self-fluidity at room temperature (25 ° C.) can be used. Actually, commercially available products such as the KE-1950 series, which is a liquid silicone rubber manufactured by Shin-Etsu Chemical Co., Ltd., and the LR3004 series manufactured by WACKER can be used as they are.
　また、ＬＩＭ成形用材料として液状シリコーンゴムの２５℃における粘度は１～１０００Ｐａ・ｓであることが好ましい。なお、粘度値は、回転粘度計で測定することができる。 Further, the liquid silicone rubber as the LIM molding material preferably has a viscosity at 25 ° C. of 1 to 1000 Pa · s. The viscosity value can be measured with a rotational viscometer.
［Ｂ］タルク
　タルクは、酸性下における圧縮永久歪の低下を抑制するために用いられ、焼成の有無にかかわらず用いることができるが、特に耐酸性を向上させる観点からは、焼成タルクを用いることが好ましい。 [B] Talc Talc is used to suppress a decrease in compression set under acidic conditions, and can be used regardless of the presence or absence of firing. From the viewpoint of improving acid resistance, in particular, using fired talc. Is preferred.
　タルクの含有量は、液状シリコーンゴム［Ａ］１００重量部に対して、０．５～１５重量部であり、好ましくは１～１０重量部、より好ましくは２～５重量部である。上記範囲とすることにより、十分な耐熱性を有し、特に耐酸性を向上できる。一方、タルクの含有量が０．５重量部未満となると、耐酸性の向上効果が十分に発揮されない。また、タルクの含有量が１５重量部超となると、十分な耐熱性が得られない。 The content of talc is 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the liquid silicone rubber [A]. By setting it as the said range, it has sufficient heat resistance and can improve especially acid resistance. On the other hand, when the content of talc is less than 0.5 parts by weight, the effect of improving acid resistance is not sufficiently exhibited. Further, if the content of talc exceeds 15 parts by weight, sufficient heat resistance cannot be obtained.
［Ｃ］各種添加剤
　液状シリコーンゴム組成物中には、以上の必須成分以外に、ゴムの配合剤として一般的に用いられているカーボンブラック、シリカ等の補強剤、クレー、グラファイト、ケイ酸カルシウム等の充填剤、酸化亜鉛、酸化マグネシウム等の受酸剤、ヒドロシリル化反応制御剤、着色剤、耐熱向上剤、難燃性向上剤、熱伝導向上剤、内部離型剤、接着性付与剤、チクソ性付与剤等が、必要に応じて適宜添加されて用いられる。 [C] Various additives In the liquid silicone rubber composition, in addition to the above essential components, reinforcing agents such as carbon black and silica generally used as a rubber compounding agent, clay, graphite, calcium silicate Fillers such as zinc oxide and magnesium oxide, hydrosilylation reaction control agents, colorants, heat resistance improvers, flame retardant improvers, heat conduction improvers, internal mold release agents, adhesion imparting agents, A thixotropic agent or the like is appropriately added and used as necessary.
　液状シリコーンゴム組成物の調製は、上記［Ａ］および［Ｂ］成分、および必要に応じて［Ｃ］成分を公知の混合方法で混合することにより行うことができる。例えば、インターミックス等の混練機または３本ロール等を用いて、上記所定の成分を混練することによって調製できる。 The liquid silicone rubber composition can be prepared by mixing the above-mentioned [A] and [B] components and, if necessary, the [C] component by a known mixing method. For example, it can be prepared by kneading the predetermined components using a kneader such as an intermix or a three roll.
　また、本発明に係る液状シリコーンゴム組成物は、室温（２５℃）において自己流動性を有する粘度の低いシリコーンゴム組成物であり、特にリム成形（Ｌｉｑｕｉｄ　Ｉｎｊｅｃｔｉｏｎ　Ｍｏｌｄｉｎｇ）により固体高分子型燃料電池セパレータ用シール部品を製造する場合に、好適に用いられる。 The liquid silicone rubber composition according to the present invention is a low viscosity silicone rubber composition having self-fluidity at room temperature (25 ° C.), and in particular, a polymer electrolyte fuel cell separator by rim molding (Liquid Injection Molding). It is suitably used when manufacturing a sealing part for a machine.
　本発明に係る固体高分子型燃料電池セパレータ用シール部品の製造方法は、上記した［Ａ］および［Ｂ］成分を含有してなる特定の液状シリコーンゴム組成物を選択的に用いて、これを好ましくは付加架橋させて、固体高分子型燃料電池セパレータ部品の少なくとも一方の表面の周縁部に、シリコーンゴム架橋物からなる弾性シール層を形成するものである。 The method for producing a sealing part for a polymer electrolyte fuel cell separator according to the present invention selectively uses a specific liquid silicone rubber composition containing the above-described components [A] and [B]. Preferably, it is subjected to addition crosslinking to form an elastic seal layer made of a crosslinked silicone rubber at the peripheral portion of at least one surface of the polymer electrolyte fuel cell separator component.
　また、液状シリコーンゴム組成物の架橋は、射出成形機などを用いて、一般に約１００～３００℃、約１０秒～３０分間の加圧架橋によって行うことができる。また、上記のような一次架橋（プレスキュア）を施した後、架橋物の内部まで確実に架橋させるため、必要に応じて二次架橋（ポストキュア）を行ってもよい。二次架橋は、一般に約１００～２５０℃、約１～１０時間のオーブン加熱によって行うことができる。 Further, the crosslinking of the liquid silicone rubber composition can be generally performed by pressure crosslinking at about 100 to 300 ° C. for about 10 seconds to 30 minutes using an injection molding machine or the like. In addition, after the above-described primary crosslinking (press cure), secondary crosslinking (post-cure) may be performed as necessary in order to surely crosslink the crosslinked product. Secondary crosslinking can be performed by oven heating generally at about 100-250 ° C. for about 1-10 hours.
　また、液状シリコーンゴム組成物を架橋成形して得られる弾性シール層の厚さは、通常０．０５～５ｍｍ、特に０．１～２ｍｍ程度とすることが好ましい。 Further, the thickness of the elastic seal layer obtained by crosslinking and molding the liquid silicone rubber composition is usually 0.05 to 5 mm, particularly preferably about 0.1 to 2 mm.
　以上、本発明の実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、本発明の概念および特許請求の範囲に含まれるあらゆる態様を含み、本発明の範囲内で種々に改変することができる。 As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, All the aspects included in the concept of this invention and a claim are included, and various within the scope of this invention. Can be modified.
　次に、本発明の効果をさらに明確にするために、実施例および比較例について説明するが、本発明はこれら実施例に限定されるものではない。 Next, in order to further clarify the effects of the present invention, examples and comparative examples will be described, but the present invention is not limited to these examples.
（実施例１）
　まず、液状シリコーンゴム（ＫＥ－１９５０－５０Ａ／Ｂ、信越化学工業株式会社製）１００重量部と、焼成タルク（エンスタック２４、浅田製粉株式会社製）０．６重量部とを、容量２リットルのプラネタリーミキサー（ＰＬＭ－２型、株式会社井上製作所製）で混練し、これをさらに３インチφの３本ロ－ル（３本ロールミル、株式会社小平製作所製）に１回通して、液状シリコーンゴム組成物を得た。 Example 1
First, 100 parts by weight of liquid silicone rubber (KE-1950-50A / B, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.6 parts by weight of calcined talc (Enstack 24, manufactured by Asada Flour Milling Co., Ltd.), a volume of 2 liters Kneading with a planetary mixer (PLM-2 type, manufactured by Inoue Seisakusho Co., Ltd.), and this is further passed once through a 3-inch φ 3-roll (3-roll mill, Kodaira Seisakusho Co., Ltd.) A silicone rubber composition was obtained.
（実施例２～５および比較例１～３）
　実施例２～５および比較例１～３は、焼成タルクの配合量を表１のように変更した以外は、実施例１と同様の方法により液状シリコーンゴム組成物を得た。 (Examples 2 to 5 and Comparative Examples 1 to 3)
In Examples 2 to 5 and Comparative Examples 1 to 3, liquid silicone rubber compositions were obtained in the same manner as in Example 1, except that the amount of calcined talc was changed as shown in Table 1.
（実施例６）
　実施例６は、焼成タルクに替えて、未焼成のタルク（ミストロンベーパー、イメリス スペシャリティーズ ジャパン株式会社製）を用いた以外は、実施例３と同様の方法により液状シリコーンゴム組成物を得た。 (Example 6)
In Example 6, a liquid silicone rubber composition was obtained in the same manner as in Example 3 except that unsintered talc (Mistrone Vapor, Imeris Specialties Japan Co., Ltd.) was used instead of calcined talc. .
［評価］
　上記実施例および比較例で得られた液状シリコーンゴム組成物を用いて、成形品として架橋ゴムシートを作製し、これを用いて特性評価を行った。その結果を表１に示す。
　なお、架橋ゴムシートの作製と、各種評価は、以下の手順で行った。 [Evaluation]
Using the liquid silicone rubber compositions obtained in the above Examples and Comparative Examples, a crosslinked rubber sheet was produced as a molded article, and the characteristics were evaluated using this. The results are shown in Table 1.
In addition, preparation of a crosslinked rubber sheet and various evaluations were performed in the following procedures.
［１］架橋ゴムシートの作製
　上記３本ロールで混練後の液状シリコーンゴム組成物を、５０トンプレス成形機を用いて、１２０℃の温度で、１０分間プレスキュアし、次いで２００℃の温度で、４時間ポストキュアして、厚さ２ｍｍの架橋ゴムシートを作製した。 [1] Production of crosslinked rubber sheet The liquid silicone rubber composition kneaded with the above three rolls is press-cured at a temperature of 120 ° C. for 10 minutes using a 50-ton press molding machine, and then at a temperature of 200 ° C. After curing for 4 hours, a crosslinked rubber sheet having a thickness of 2 mm was produced.
［２］硬さ（デュロメータＡ）の測定
　上記架橋ゴムシートを３枚積層して試験片を作製し、ＪＩＳ　Ｋ６２５３－３：２０１２の規定に従い、硬さを測定した。測定は、上記架橋ゴムシート毎に、３つの試験片で行い、その平均値（Ｎ＝３）を表１に示した。 [2] Measurement of hardness (durometer A) Three cross-linked rubber sheets were laminated to prepare a test piece, and the hardness was measured in accordance with JIS K6253-3: 2012. The measurement was performed with three test pieces for each crosslinked rubber sheet, and the average value (N = 3) is shown in Table 1.
［３］圧縮永久歪の測定
　上記架橋ゴムシートを３枚積層して試験片を作製し、ＪＩＳ　Ｋ６２６２：２０１３の規定に従い、圧縮率２５％、試験温度１５０℃、試験時間７０時間の耐熱老化後の、圧縮永久歪（％）を測定した。測定は、空気中、水中およびフッ酸（濃度５００質量ｐｐｍ）中の３つの条件下で行った。なお、水中およびフッ酸中での測定は、これらの環境に調整されたオートグレーブ内で行った。また、測定は、上記シリコーンゴム組成物毎に、３つの試験片で行い、その平均値（Ｎ＝３）を表１に示した。
　圧縮永久歪は、その値が小さいほど、耐熱性（シール性）がよく、シール寿命が長いことを意味する。また、特にフッ酸中での圧縮永久歪は、その値が小さいほど、耐酸性が高いことを意味する。
　本実施例では、圧縮永久歪が、空気中で２５％以下、水中で３４％以下、フッ酸中で５０％以下となる物を、それぞれ合格レベルとした。 [3] Measurement of compression set Three pieces of the above-mentioned crosslinked rubber sheets were laminated to prepare a test piece, and after heat aging at a compression rate of 25%, a test temperature of 150 ° C., and a test time of 70 hours in accordance with JIS K6262: 2013. The compression set (%) was measured. The measurement was performed under three conditions in air, water and hydrofluoric acid (concentration: 500 ppm by mass). In addition, the measurement in water and hydrofluoric acid was performed in an auto grave adjusted to these environments. Moreover, the measurement was performed with three test pieces for each silicone rubber composition, and the average value (N = 3) is shown in Table 1.
The compression set means that the smaller the value, the better the heat resistance (sealability) and the longer the seal life. In particular, the compression set in hydrofluoric acid means that the smaller the value, the higher the acid resistance.
In this example, a product having a compression set of 25% or less in air, 34% or less in water, and 50% or less in hydrofluoric acid was determined as an acceptable level.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示されるように、実施例１～６に係る液状シリコーン組成物は、特にタルクの含有量が液状シリコーンゴム１００重量部に対して０．５～１５重量部の範囲内にあるため、空気中、水中およびフッ酸中のそれぞれで圧縮永久歪が小さい、十分な耐熱性および優れた耐酸性を有する成形品を製造できることが確認された。 As shown in Table 1, in the liquid silicone compositions according to Examples 1 to 6, the talc content is particularly in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the liquid silicone rubber. It was confirmed that a molded article having a sufficient heat resistance and an excellent acid resistance having a small compression set in air, water and hydrofluoric acid can be produced.
　これに対して、比較例１および２に係る液状シリコーン組成物はタルクの含有量が、液状シリコーンゴム１００重量部に対して、０．５重量部に満たないため、これらを用いて製造された成形品は、本発明の液状シリコーン組成物（実施例１～６）を用いて製造された成形品に比べて、特に、フッ酸中での圧縮永久歪が大きく、十分な耐酸性が得られないことが確認された。また、比較例３に係る液状シリコーン組成物はタルクの含有量が、液状シリコーンゴム１００重量部に対して、１５重量部を超えているため、これを用いて製造された成形品は、本発明の液状シリコーン組成物（実施例１～６）を用いて製造された成形品に比べて、空気中および水中での圧縮永久歪が大きく、十分な耐熱性が得られないことが確認された。 In contrast, the liquid silicone compositions according to Comparative Examples 1 and 2 were manufactured using these because the talc content was less than 0.5 parts by weight with respect to 100 parts by weight of the liquid silicone rubber. Compared to molded articles produced using the liquid silicone compositions of the present invention (Examples 1 to 6), the molded articles have particularly large compression set in hydrofluoric acid, and sufficient acid resistance can be obtained. Not confirmed. Moreover, since the content of talc in the liquid silicone composition according to Comparative Example 3 exceeds 15 parts by weight with respect to 100 parts by weight of the liquid silicone rubber, a molded product manufactured using the talc is obtained by the present invention. It was confirmed that the compression set in air and water was large and sufficient heat resistance could not be obtained as compared with molded articles produced using the liquid silicone compositions (Examples 1 to 6).
　以上から、本発明に係る液状シリコーン組成物によれば、耐熱性および耐酸性に優れたゴム成形品が得られるため、固体高分子型燃料電池セパレータ用シール部品を製造するために、好適であることが確認された。 From the above, according to the liquid silicone composition according to the present invention, a rubber molded article excellent in heat resistance and acid resistance can be obtained, and therefore, it is suitable for producing a sealing part for a polymer electrolyte fuel cell separator. It was confirmed.

Claims (3)

  1. 　液状シリコーンゴムと、タルクとを含有してなり、
    　前記タルクの含有量が、前記液状シリコーンゴム１００重量部に対して、０．５～１５重量部であり、
    　固体高分子型燃料電池セパレータ用シール部品を製造するために用いられる、液状シリコーンゴム組成物。     It contains liquid silicone rubber and talc,
    The content of the talc is 0.5 to 15 parts by weight with respect to 100 parts by weight of the liquid silicone rubber,
    A liquid silicone rubber composition used for producing a sealing part for a polymer electrolyte fuel cell separator.
  2. 　付加架橋させる、請求項１に記載の液状シリコーンゴム組成物。 The liquid silicone rubber composition according to claim 1, which is subjected to addition crosslinking.
  3. 　請求項１または２に記載の液状シリコーンゴム組成物を架橋成形した物である、固体高分子型燃料電池セパレータ用シール部品。 A sealing part for a polymer electrolyte fuel cell separator, which is a product obtained by crosslinking the liquid silicone rubber composition according to claim 1 or 2.
PCT/JP2017/015577 2016-04-28 2017-04-18 Liquid silicone rubber composition and sealing component for solid polymer fuel cell separator WO2017188059A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018514512A JPWO2017188059A1 (en) 2016-04-28 2017-04-18 Liquid silicone rubber composition and sealing part for polymer electrolyte fuel cell separator using the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016089982 2016-04-28
JP2016-089982 2016-04-28

Publications (1)

Publication Number Publication Date
WO2017188059A1 true WO2017188059A1 (en) 2017-11-02

Family

ID=60161482

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/015577 WO2017188059A1 (en) 2016-04-28 2017-04-18 Liquid silicone rubber composition and sealing component for solid polymer fuel cell separator

Country Status (2)

Country Link
JP (1) JPWO2017188059A1 (en)
WO (1) WO2017188059A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021054113A1 (en) * 2019-09-18 2021-03-25 Nok株式会社 Method for manufacturing fuel battery cell separator gasket

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001335654A (en) * 2000-05-26 2001-12-04 Otsuka Chem Co Ltd Foaming agent for silicone, foaming silicone composition, and silicone foaming material
JP2003257456A (en) * 2002-02-28 2003-09-12 Shin Etsu Chem Co Ltd Rubber component for sealing solid high polymer type fuel cell separator, sealing material by use of the same, and solid high polymer type fuel cell separator
WO2009122487A1 (en) * 2008-03-31 2009-10-08 Nok株式会社 Rubber composition and use thereof
JP2014209438A (en) * 2013-03-29 2014-11-06 本田技研工業株式会社 Fuel battery separator, and method for manufacturing the same
JP2015022800A (en) * 2013-07-16 2015-02-02 信越化学工業株式会社 Method for manufacturing seal for solid polymer type fuel battery separators, and silicone rubber composition used therein

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001335654A (en) * 2000-05-26 2001-12-04 Otsuka Chem Co Ltd Foaming agent for silicone, foaming silicone composition, and silicone foaming material
JP2003257456A (en) * 2002-02-28 2003-09-12 Shin Etsu Chem Co Ltd Rubber component for sealing solid high polymer type fuel cell separator, sealing material by use of the same, and solid high polymer type fuel cell separator
WO2009122487A1 (en) * 2008-03-31 2009-10-08 Nok株式会社 Rubber composition and use thereof
JP2014209438A (en) * 2013-03-29 2014-11-06 本田技研工業株式会社 Fuel battery separator, and method for manufacturing the same
JP2015022800A (en) * 2013-07-16 2015-02-02 信越化学工業株式会社 Method for manufacturing seal for solid polymer type fuel battery separators, and silicone rubber composition used therein

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021054113A1 (en) * 2019-09-18 2021-03-25 Nok株式会社 Method for manufacturing fuel battery cell separator gasket
JPWO2021054113A1 (en) * 2019-09-18 2021-03-25
CN113767490A (en) * 2019-09-18 2021-12-07 Nok株式会社 Method for manufacturing gasket of separator for fuel cell
JP7385668B2 (en) 2019-09-18 2023-11-22 Nok株式会社 Gasket manufacturing method for fuel cell separator
US11973246B2 (en) 2019-09-18 2024-04-30 Nok Corporation Method for manufacturing fuel battery cell separator gasket

Also Published As

Publication number Publication date
JPWO2017188059A1 (en) 2019-02-28

Similar Documents

Publication Publication Date Title
JP6914771B2 (en) Fluororubber composition for peroxide cross-linking
WO2014024698A1 (en) Nbr composition
EP3113271B1 (en) Sealing material for solid polymer fuel cell separator, separator seal and separator
WO2017188059A1 (en) Liquid silicone rubber composition and sealing component for solid polymer fuel cell separator
JP2019199549A (en) Rubber composition and seal material
US20100233580A1 (en) Fluororubber composition for cell seals of fuel cells
WO2019087788A1 (en) Ethylene-acrylate rubber composition and molded article thereof
JP2006193559A (en) Fuel oil-resistant acrylic rubber composition, and automotive seal part
JP2018080754A (en) Gasket around engine and manufacturing method thereof
KR20180068976A (en) Method for producing crosslinkable rubber composition
JP2002069254A (en) Peroxide crosslinkable rubber composition
KR101373121B1 (en) Rubber composition of gasket for inverter case of a hybrid vehicle
JP2005140196A (en) Gasket for fuel cell
WO2003074625A1 (en) Sealing material
JP3093579B2 (en) Gasket for phosphoric acid type fuel cell and method for producing the same
KR101637849B1 (en) Blend gasket for fuel cells
JP6474054B1 (en) Fluororubber composition and crosslinked fluororubber
KR101601380B1 (en) Blend gasket for fuel cells
WO2017150192A1 (en) Fluororubber composition and crosslinked fluororubber
JP2003301072A (en) Blend rubber composition
JP2004051728A (en) Fluororubber composition
JPWO2019058908A1 (en) Diaphragm and bladder for accumulator made of crosslinked epichlorohydrin rubber
KR20200073070A (en) Rubber composition of oil seal for cooling water opener of fuel cell vehicle
JP4526515B2 (en) Butyl rubber composition
CN110799585A (en) Rubber composition and sealing material for fuel cell separator

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2018514512

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17789344

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17789344

Country of ref document: EP

Kind code of ref document: A1