WO2021019999A1 - Fluorine rubber composition, and rubber formed product and sealing material using same - Google Patents

Fluorine rubber composition, and rubber formed product and sealing material using same Download PDF

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WO2021019999A1
WO2021019999A1 PCT/JP2020/025536 JP2020025536W WO2021019999A1 WO 2021019999 A1 WO2021019999 A1 WO 2021019999A1 JP 2020025536 W JP2020025536 W JP 2020025536W WO 2021019999 A1 WO2021019999 A1 WO 2021019999A1
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fluororubber
mass
parts
fluororubber composition
content
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PCT/JP2020/025536
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French (fr)
Japanese (ja)
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耕生 平野
池原　潤一郎
寛 西村
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三菱電線工業株式会社
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Publication of WO2021019999A1 publication Critical patent/WO2021019999A1/en

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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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen

Definitions

  • the present invention relates to a fluororubber composition, a rubber molded product using the fluororubber composition, and a sealing material.
  • Fluorororubber is excellent in heat resistance, chemical resistance, oil resistance, weather resistance, etc. Therefore, in a wide range of fields such as hydraulic equipment, pneumatic equipment, automobiles, aircraft, semiconductor-related equipment, food-related equipment, O-rings and It is used as a material for forming sealing materials such as packing.
  • Patent Document 1 discloses a composition containing a fluororubber, magnesium oxide, and hydrotalcite.
  • the present invention is a fluororubber composition containing fluororubber, magnesium oxide, hydrotalcite, and barium sulfate, wherein the content of magnesium oxide is 1. with respect to 100 parts by mass of the fluororubber.
  • the mass ratio of the hydrotalcite content to the magnesium oxide content is 0.60 or more and 5.0 or less, and the barium sulfate content is 100 parts by mass of the fluororubber. It is 5 parts by mass or more and 100 parts by mass or less.
  • the present invention is a rubber molded product formed by cross-linking the fluororubber of the fluororubber composition of the present invention. Further, the present invention is a sealing material formed by cross-linking the fluororubber of the fluororubber composition of the present invention.
  • the fluororubber composition according to the embodiment contains fluororubber, magnesium oxide, hydrotalcite, and barium sulfate.
  • the content of magnesium oxide in the fluororubber composition is 1.3 parts by mass or more with respect to 100 parts by mass of the fluororubber.
  • the mass ratio of the content of hydrotalcite to the content of magnesium oxide is 0.60 or more and 5.0 or less.
  • the content of barium sulfate in the fluororubber composition is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fluororubber.
  • the compression set can be suppressed low by increasing the cross-linking density of the fluororubber in the rubber molded product after cross-linking. ..
  • the fluorororubber composition before cross-linking contains magnesium oxide, there is a problem that processability is impaired. Specifically, when the fluororubber composition is kneaded, brown stains may be generated on the roll surface of the open roll of the rubber kneader, and in that case, cleaning is required, so that the work efficiency is lowered. Further, when the rubber molded product is molded, the surface of the molding mold may be contaminated, and in that case, cleaning is required, so that the production efficiency is lowered. This cleaning requires a large number of man-hours as the size of the molding die becomes larger and the shape becomes more complicated. In addition, if the surface of the mold is dirty, the flow of the fluororubber composition is hindered, or the dirt adheres to the rubber, so that the appearance of the rubber molded product is poor, chipped, cracked, or the like.
  • an appropriate amount of magnesium oxide is contained as an acid receiving agent, and the cross-linking density of the fluororubber is increased, so that the compression set of the rubber molded product after cross-linking can be prevented. It can be kept low.
  • excellent processability can be obtained by containing an appropriate amount of hydrotalcite and barium sulfate. This is because the layered structure of hydrotalcite, which also functions as an acid receiver, takes in not only acid but also ions that cause stains, enhances mold releasability, and allows the fluororubber composition to flow with barium sulfate.
  • the fluororubber composition spreads over the molding mold regardless of whether the surface of the molding mold is dirty, so that a rubber kneader or molding can be used. This is because the burden of cleaning the mold is reduced.
  • examples of the fluororubber include a copolymer (binary FKM) of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), vinylidene fluoride (VDF), hexafluoropropylene (HFP), and tetra.
  • Copolymer with fluoroethylene (TFE) (ternary FKM), copolymer with tetrafluoroethylene (TFE) and propylene (Pr) (FEP), vinylidene fluoride (VDF), propylene (Pr) and tetra Copolymer with fluoroethylene (TFE), copolymer with ethylene (E) and tetrafluoroethylene (TFE) (ETFE), ethylene (E), tetrafluoroethylene (TFE) and perfluoromethylvinyl ether (PMVE) Copolymer with vinylidene fluoride (VDF), tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE), tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE) Examples thereof include a polymer (FFKM), a copolymer of vinylidene fluoride (VDF) and perfluoromethyl vinyl ether (PMVE), and the like
  • the powder of magnesium oxide is dispersed in fluororubber.
  • the average particle size of magnesium oxide is preferably 0.3 ⁇ m or more and 40 ⁇ m or less, and more preferably 0.6 ⁇ m or more and 10 ⁇ m or less, from the viewpoint of suppressing the compression set of the rubber molded product to a low level. This average particle size is measured based on the air permeation method.
  • the specific surface area of magnesium oxide, from the viewpoint of suppressing the compression set of the rubber molded article preferably 40 m 2 / g or more 200 meters 2 / g or less, more preferably less 130m 2 / g or more 160 m 2 / g. This specific surface area is measured based on the BET method.
  • the content of magnesium oxide in the fluororubber composition is 1.3 parts by mass or more with respect to 100 parts by mass of fluororubber, but preferably 1.5 parts by mass from the viewpoint of suppressing the compression set of the rubber molded product to a low level. It is 3 parts by mass or less, more preferably 1.8 parts by mass or more and 2.4 parts by mass or less.
  • the powder of hydrotalcite is dispersed in fluororubber.
  • the average particle size of hydrotalcite is preferably 0.2 ⁇ m or more and 100 ⁇ m or less, and more preferably 0.4 ⁇ m or more and 50 ⁇ m or less, from the viewpoint of obtaining excellent processability. This average particle diameter is a median diameter measured based on the laser diffraction / scattering method.
  • the specific surface area of hydrotalcite is preferably 5 m 2 / g or more and 20 m 2 / g or less, and more preferably 8 m 2 / g or more and 15 m 2 / g or less. This specific surface area is measured based on the BET method.
  • the content of hydrotalcite in the fluororubber composition is preferably 1 part by mass or more and 5 parts by mass or less, and more preferably 2 parts by mass or more 4 with respect to 100 parts by mass of fluororubber. It is less than a part by mass.
  • the mass ratio of the hydrotalcite content to the magnesium oxide content is 0.60 or more and 5.0 or less, but preferably 0.70 or more and 2.9 or less from the viewpoint of obtaining excellent processability. It is preferably 1.2 or more and 1.8 or less.
  • the content of hydrotalcite in the fluororubber composition is preferably higher than the content of magnesium oxide from the viewpoint of obtaining excellent processability.
  • the sum of the contents of magnesium oxide and hydrotalcite in the fluororubber composition is preferable with respect to 100 parts by mass of the fluororubber from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. It is 3 parts by mass or more and 7 parts by mass or less, more preferably 4.5 parts by mass or more and 5.5 parts by mass or less.
  • the powder of barium sulfate is dispersed in fluororubber.
  • the average particle size of barium sulfate is preferably 0.1 ⁇ m or more and 15 ⁇ m or less, and more preferably 0.3 ⁇ m or more and 2.0 ⁇ m or less, from the viewpoint of obtaining excellent processability. This average particle diameter is a median diameter measured based on the laser diffraction / scattering method.
  • the specific gravity of barium sulfate is preferably 4.0 or more and 4.6 or less, and more preferably 4.4 or more and 4.6 or less.
  • the content of barium sulfate in the fluororubber composition is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fluororubber, but from the viewpoint of obtaining excellent workability and excellent wear resistance of the rubber molded product. Therefore, it is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less.
  • the content of barium sulfate in the fluororubber composition is preferably higher than any of the magnesium oxide content, the hydrotalcite content, and the sum of these contents from the viewpoint of obtaining excellent processability.
  • the mass ratio of the barium sulfate content to the magnesium oxide content is preferably 4.5 or more and 50 or less, more preferably 10 from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. More than 20 or less.
  • the mass ratio of the barium sulfate content to the hydrotalcite content is preferably 3.0 or more and 35 or less, and more preferably 5 or more and 20 or less from the viewpoint of obtaining excellent processability.
  • the mass ratio of the barium sulfate content to the sum of the magnesium oxide and hydrotalcite contents is preferably 1.0 or more and 20 from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability.
  • it is more preferably 5.0 or more and 8.0 or less.
  • the fluororubber composition according to the embodiment may contain calcium hydroxide.
  • the content of calcium hydroxide in the fluororubber composition is preferably 4 parts by mass or more with respect to 100 parts by mass of the fluororubber from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. It is less than the mass part.
  • the content of calcium hydroxide in the fluororubber composition is preferably higher than the content of either magnesium oxide or hydrotalcite, and is preferably the same as or higher than the sum of the contents thereof.
  • the mass ratio of the calcium hydroxide content to the magnesium oxide content is preferably 2.0 or more and 7.5 or less from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. .. From the same viewpoint, the mass ratio of the calcium hydroxide content to the hydrotalcite content is preferably 1.0 or more and 5.0 or less. From the same viewpoint, the mass ratio of the calcium hydroxide content to the sum of the magnesium oxide and hydrotalcite contents is preferably 1.0 or more and 1.5 or less.
  • the fluororubber composition according to the embodiment may contain carbon black.
  • the carbon black include furnace blacks such as HAF carbon black, MAF carbon black, FEF carbon black, SRF carbon black and GPF carbon black; and thermal blacks such as FT carbon black and MT carbon black.
  • the carbon black preferably contains thermal black, and more preferably MT carbon black, from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability.
  • the content of carbon black in the fluororubber composition is preferably 15 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of fluororubber from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. It is less than a part.
  • the content of carbon black in the fluororubber composition is preferably smaller than the content of barium sulfate.
  • the mass ratio of the carbon black content to the barium sulfate content is preferably 0.5 or more and 0.7 or less.
  • the sum of the contents of barium sulfate and carbon black in the fluororubber composition is preferably 40 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the fluororubber.
  • the fluororubber composition according to the embodiment may also contain a processing aid or the like.
  • the fluororubber composition according to the embodiment is obtained by kneading fluororubber with a rubber kneader such as an open roll, and adding a rubber compounding agent containing magnesium oxide, hydrotalcite, and barium sulfate to the kneading. Obtainable.
  • the fluororubber composition according to the embodiment is filled in the cavity of the molding mold, held at a predetermined temperature for a predetermined time, and the fluororubber is crosslinked to form a rubber molded product.
  • the fluororubber cross-linking system include a polyol cross-linking system, a peroxide cross-linking system, and a polyamine cross-linking system.
  • the polyol cross-linking system is preferable as the fluororubber cross-linking system.
  • a sealing material such as an O-ring or packing is particularly suitable because the compression set is low.
  • the compression set of the crosslinked fluororubber composition forming the rubber molded product is preferably 16% or less, more preferably 13% or less. This compression set is measured based on JIS K6262: 2013 with a test temperature of 200 ° C. and a test time of 22 hours.
  • the rubber hardness measured using a type A durometer of the crosslinked fluororubber composition is preferably 60 or more and 90 or less. This rubber hardness is measured based on JIS K6253-3: 2012.
  • the tensile strength of the crosslinked fluororubber composition is preferably 8.0 MPa or more.
  • the elongation at the time of cutting of the fluororubber composition after cross-linking is preferably 120% or more.
  • Fluororubber composition Fluororubber compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared. Each formulation is also shown in Table 1.
  • Fluorororubber (Daiel G-701 Daikin Co., Ltd., dual FKM) is kneaded with an open roll, and magnesium oxide (Kyowa Mag 150 Kyowa Kagaku Kogyo Co., Ltd., average particle size: 11.7, specific surface area: 144m 2 /g)2.5 parts by weight of hydrotalcite (DHT-4A manufactured by Kyowa chemical industry Co., Ltd., average particle diameter: 0.45 [mu] m, a specific surface area: 10.1m 2 / g) 1 .5 parts by mass, barium sulfate (average particle size: 0.6 ⁇ m, specific surface area: 4.5) 30 parts by mass, calcium hydroxide (manufactured by Calbit Omi Chemical Industry Co., Ltd.) 6 parts by mass, MT carbon black (N990) 20 parts by mass And a fluororubber composition obtained by adding and kneading 1 part by mass of a processing aid (VPA No
  • Example 2 The fluororubber composition obtained in the same manner as in Example 1 except that the blending amount of magnesium oxide and the blending amount of hydrotalcite were 2 parts by mass and 3 parts by mass, respectively, with respect to 100 parts by mass of the fluororubber.
  • Example 2 The fluororubber composition obtained in the same manner as in Example 1 except that the blending amount of magnesium oxide and the blending amount of hydrotalcite were 2 parts by mass and 3 parts by mass, respectively, with respect to 100 parts by mass of the fluororubber.
  • Example 3 It was obtained in the same manner as in Example 1 except that the blending amount of magnesium oxide and the blending amount of hydrotalcite were 1.5 parts by mass and 4.5 parts by mass, respectively, with respect to 100 parts by mass of fluororubber.
  • the fluororubber composition was designated as Example 3.
  • Example 4 The amount of barium sulfate blended was 10 parts by mass with respect to 100 parts by mass of fluororubber, and the fluororubber composition obtained in the same manner as in Example 2 except that MT carbon black was not blended was referred to as Example 4. did.
  • Example 5 was a fluororubber composition obtained in the same manner as in Example 4 except that the amount of barium sulfate blended was 90 parts by mass with respect to 100 parts by mass of fluororubber.
  • the compression set was measured based on JIS K6262: 2013 with a test temperature of 200 ° C. and a test time of 22 hours. Further, the appearance of the rubber molded product after compression was visually confirmed, and those having no abnormality were evaluated as A and those with cracks were evaluated as B.
  • the rubber hardness was measured using a type A durometer based on JIS K6253-3: 2012. Furthermore, the tensile strength and the elongation at the time of cutting were measured based on JIS K6251: 2017.
  • Test results The test results are shown in Table 2. According to Table 2, it can be seen that Examples 1 to 5 have low compression set and excellent workability of the rubber molded product. On the other hand, in Comparative Examples 1 and 2 in which the content of magnesium oxide is low, it can be seen that the compression set is large. Further, in Comparative Example 3 containing no hydrotalcite, stains on the roll surface of the open roll and the mold surface of the sheet molding die were observed, so that it can be seen that the processability is inferior. Similarly, in Comparative Example 4 which does not contain hydrotalcite, stains on the roll surface of the open roll were observed, indicating that the processability was inferior.
  • Comparative Example 5 which contains hydrotalcite but the ratio of the content to the magnesium oxide content is small, stains on the roll surface of the open roll and the mold surface of the sheet molding die were observed. It turns out that the sex is inferior. Further, in Comparative Example 4 which does not contain barium sulfate and Comparative Example 5 in which the content of barium sulfate is low, poor appearance of the rubber molded product was observed, and it can be seen that the processability is also inferior in this respect.
  • the present invention is useful for fluororubber compositions, rubber molded products and sealing materials using the same.

Abstract

The fluorine rubber composition contains fluorine rubber, magnesium oxide, hydrotalcite, and barium sulfate. The magnesium oxide content is 1.3 parts by mass with respect to 100 parts by mass of the fluorine rubber. The mass ratio of the hydrotalcite content relative to the magnesium oxide content is between 0.60 and 5.0 inclusive. The barium sulfate content is between 5 parts by mass and 100 parts by mass inclusive with respect to 100 parts by mass of the fluorine rubber.

Description

フッ素ゴム組成物並びにそれを用いたゴム成形品及びシール材Fluororubber composition and rubber molded products and sealing materials using it
　本発明は、フッ素ゴム組成物並びにそれを用いたゴム成形品及びシール材に関する。 The present invention relates to a fluororubber composition, a rubber molded product using the fluororubber composition, and a sealing material.
　フッ素ゴムは、耐熱性、耐薬品性、耐油性、耐候性等に優れることから、例えば、油圧機器、空気圧機器、自動車、航空機、半導体関連機器、食品関連機器等の幅広い分野において、Ｏリングやパッキン等のシール材の形成材料として用いられている。そして、かかるフッ素ゴムの組成物として、例えば、特許文献１には、フッ素ゴムと、酸化マグネシウムと、ハイドロタルサイトとを含有するものが開示されている。 Fluororubber is excellent in heat resistance, chemical resistance, oil resistance, weather resistance, etc. Therefore, in a wide range of fields such as hydraulic equipment, pneumatic equipment, automobiles, aircraft, semiconductor-related equipment, food-related equipment, O-rings and It is used as a material for forming sealing materials such as packing. As a composition of such a fluororubber, for example, Patent Document 1 discloses a composition containing a fluororubber, magnesium oxide, and hydrotalcite.
特許第５２１８０４８号公報Japanese Patent No. 5218048
　本発明は、フッ素ゴムと、酸化マグネシウムと、ハイドロタルサイトと、硫酸バリウムとを含有するフッ素ゴム組成物であって、前記酸化マグネシウムの含有量が、前記フッ素ゴム１００質量部に対して１．３質量部以上であり、前記ハイドロタルサイトの含有量の前記酸化マグネシウムの含有量に対する質量比が０．６０以上５．０以下であり、前記硫酸バリウムの含有量が、前記フッ素ゴム１００質量部に対して５質量部以上１００質量部以下である。 The present invention is a fluororubber composition containing fluororubber, magnesium oxide, hydrotalcite, and barium sulfate, wherein the content of magnesium oxide is 1. with respect to 100 parts by mass of the fluororubber. The mass ratio of the hydrotalcite content to the magnesium oxide content is 0.60 or more and 5.0 or less, and the barium sulfate content is 100 parts by mass of the fluororubber. It is 5 parts by mass or more and 100 parts by mass or less.
　本発明は、本発明のフッ素ゴム組成物の前記フッ素ゴムが架橋されて形成されたゴム成形品である。また、本発明は、本発明のフッ素ゴム組成物の前記フッ素ゴムが架橋されて形成されたシール材である。 The present invention is a rubber molded product formed by cross-linking the fluororubber of the fluororubber composition of the present invention. Further, the present invention is a sealing material formed by cross-linking the fluororubber of the fluororubber composition of the present invention.
　以下、実施形態について詳細に説明する。 Hereinafter, the embodiment will be described in detail.
　実施形態に係るフッ素ゴム組成物は、フッ素ゴムと、酸化マグネシウムと、ハイドロタルサイトと、硫酸バリウムとを含有する。フッ素ゴム組成物における酸化マグネシウムの含有量は、フッ素ゴム１００質量部に対して１．３質量部以上である。ハイドロタルサイトの含有量の酸化マグネシウムの含有量に対する質量比が０．６０以上５．０以下である。フッ素ゴム組成物における硫酸バリウムの含有量は、フッ素ゴム１００質量部に対して５質量部以上１００質量部以下である。 The fluororubber composition according to the embodiment contains fluororubber, magnesium oxide, hydrotalcite, and barium sulfate. The content of magnesium oxide in the fluororubber composition is 1.3 parts by mass or more with respect to 100 parts by mass of the fluororubber. The mass ratio of the content of hydrotalcite to the content of magnesium oxide is 0.60 or more and 5.0 or less. The content of barium sulfate in the fluororubber composition is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fluororubber.
　ところで、架橋前のフッ素ゴム組成物が酸化マグネシウムを含有していると、それを架橋した後のゴム成形品では、フッ素ゴムの架橋密度が高められることにより、圧縮永久ひずみを低く抑えることができる。 By the way, if the fluororubber composition before cross-linking contains magnesium oxide, the compression set can be suppressed low by increasing the cross-linking density of the fluororubber in the rubber molded product after cross-linking. ..
　その一方、架橋前のフッ素ゴム組成物が酸化マグネシウムを含有していると、加工性が損なわれるという問題がある。具体的には、フッ素ゴム組成物の混練時に、ゴム混練機のオープンロールのロール表面に褐色の汚れが発生することがあり、その場合、その清掃が必要となるため、作業効率が低くなる。また、ゴム成形品の成型時に、成形型表面に汚れが発生することがあり、その場合、その洗浄が必要となるため、生産効率が低くなる。この洗浄は、成形型のサイズの大型化及び形状の複雑化に伴い、多くの工数を必要とするようになってきている。加えて、成形型表面に汚れがあると、フッ素ゴム組成物の流動が阻害されたり、汚れがゴムについてしまったりしてゴム成形品の外観不良、欠け、割れ等が発生しやすくなる。 On the other hand, if the fluororubber composition before cross-linking contains magnesium oxide, there is a problem that processability is impaired. Specifically, when the fluororubber composition is kneaded, brown stains may be generated on the roll surface of the open roll of the rubber kneader, and in that case, cleaning is required, so that the work efficiency is lowered. Further, when the rubber molded product is molded, the surface of the molding mold may be contaminated, and in that case, cleaning is required, so that the production efficiency is lowered. This cleaning requires a large number of man-hours as the size of the molding die becomes larger and the shape becomes more complicated. In addition, if the surface of the mold is dirty, the flow of the fluororubber composition is hindered, or the dirt adheres to the rubber, so that the appearance of the rubber molded product is poor, chipped, cracked, or the like.
　これに対し、実施形態に係るフッ素ゴム組成物によれば、受酸剤として適量の酸化マグネシウムを含有し、フッ素ゴムの架橋密度が高められることにより、架橋後のゴム成形品の圧縮永久ひずみを低く抑えることができる。また、適量のハイドロタルサイト及び硫酸バリウムを含有することにより、優れた加工性を得ることができる。これは、受酸剤としても機能するハイドロタルサイトの層状構造が、酸だけでなく、汚れの原因のイオン等も取り込むとともに、離型性を高め、また、硫酸バリウムによりフッ素ゴム組成物の流動性が高められ、サイズが大型の成形型や形状の複雑な成形型であっても、成形型表面の汚れの有無に関わらず、フッ素ゴム組成物が成形型に行き渡るので、ゴム混練機や成形型の清掃負担が軽減されるためである。 On the other hand, according to the fluororubber composition according to the embodiment, an appropriate amount of magnesium oxide is contained as an acid receiving agent, and the cross-linking density of the fluororubber is increased, so that the compression set of the rubber molded product after cross-linking can be prevented. It can be kept low. In addition, excellent processability can be obtained by containing an appropriate amount of hydrotalcite and barium sulfate. This is because the layered structure of hydrotalcite, which also functions as an acid receiver, takes in not only acid but also ions that cause stains, enhances mold releasability, and allows the fluororubber composition to flow with barium sulfate. Even in a molding mold with enhanced properties and a large size or a complicated shape, the fluororubber composition spreads over the molding mold regardless of whether the surface of the molding mold is dirty, so that a rubber kneader or molding can be used. This is because the burden of cleaning the mold is reduced.
　ここで、フッ素ゴムとしては、例えば、ビニリデンフルオライド（ＶＤＦ）とヘキサフルオロプロピレン（ＨＦＰ）との共重合体（二元系ＦＫＭ）、ビニリデンフルオライド（ＶＤＦ）とヘキサフルオロプロピレン（ＨＦＰ）とテトラフルオロエチレン（ＴＦＥ）との共重合体（三元系ＦＫＭ）、テトラフルオロエチレン（ＴＦＥ）とプロピレン（Ｐｒ）との共重合体（ＦＥＰ）、ビニリデンフルオライド（ＶＤＦ）とプロピレン（Ｐｒ）とテトラフルオロエチレン（ＴＦＥ）との共重合体、エチレン（Ｅ）とテトラフルオロエチレン（ＴＦＥ）との共重合体（ＥＴＦＥ）、エチレン（Ｅ）とテトラフルオロエチレン（ＴＦＥ）とパーフルオロメチルビニルエーテル（ＰＭＶＥ）との共重合体、ビニリデンフルオライド（ＶＤＦ）とテトラフルオロエチレン（ＴＦＥ）とパーフルオロメチルビニルエーテル（ＰＭＶＥ）との共重合体、テトラフルオロエチレン（ＴＦＥ）とパーフルオロメチルビニルエーテル（ＰＭＶＥ）との共重合体（ＦＦＫＭ）、ビニリデンフルオライド（ＶＤＦ）とパーフルオロメチルビニルエーテル（ＰＭＶＥ）との共重合体等が挙げられる。フッ素ゴムは、これらのうちの１種又は２種以上を含むことが好ましく、優れた加工性を得る観点から、二元系フッ素ゴムを含むことがより好ましく、二元系ＦＫＭを含むことが更に好ましい。 Here, examples of the fluororubber include a copolymer (binary FKM) of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), vinylidene fluoride (VDF), hexafluoropropylene (HFP), and tetra. Copolymer with fluoroethylene (TFE) (ternary FKM), copolymer with tetrafluoroethylene (TFE) and propylene (Pr) (FEP), vinylidene fluoride (VDF), propylene (Pr) and tetra Copolymer with fluoroethylene (TFE), copolymer with ethylene (E) and tetrafluoroethylene (TFE) (ETFE), ethylene (E), tetrafluoroethylene (TFE) and perfluoromethylvinyl ether (PMVE) Copolymer with vinylidene fluoride (VDF), tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE), tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE) Examples thereof include a polymer (FFKM), a copolymer of vinylidene fluoride (VDF) and perfluoromethyl vinyl ether (PMVE), and the like. The fluororubber preferably contains one or more of these, and from the viewpoint of obtaining excellent processability, it is more preferable to contain a binary fluororubber, and further to include a binary FKM. preferable.
　酸化マグネシウムは、その粉状体がフッ素ゴムに分散している。酸化マグネシウムの平均粒子径は、ゴム成形品の圧縮永久ひずみを低く抑える観点から、好ましくは０．３μｍ以上４０μｍ以下、より好ましくは０．６μｍ以上１０μｍ以下である。この平均粒子径は、空気透過法に基づいて測定されるものである。酸化マグネシウムの比表面積は、ゴム成形品の圧縮永久ひずみを低く抑える観点から、好ましくは４０ｍ２／ｇ以上２００ｍ２／ｇ以下、より好ましくは１３０ｍ２／ｇ以上１６０ｍ２／ｇ以下である。この比表面積は、ＢＥＴ法に基づいて測定されるものである。フッ素ゴム組成物における酸化マグネシウムの含有量は、フッ素ゴム１００質量部に対して１．３質量部以上であるが、ゴム成形品の圧縮永久ひずみを低く抑える観点から、好ましくは１．５質量部以上３質量部以下、より好ましくは１．８質量部以上２．４質量部以下である。 The powder of magnesium oxide is dispersed in fluororubber. The average particle size of magnesium oxide is preferably 0.3 μm or more and 40 μm or less, and more preferably 0.6 μm or more and 10 μm or less, from the viewpoint of suppressing the compression set of the rubber molded product to a low level. This average particle size is measured based on the air permeation method. The specific surface area of magnesium oxide, from the viewpoint of suppressing the compression set of the rubber molded article, preferably 40 m 2 / g or more 200 meters 2 / g or less, more preferably less 130m 2 / g or more 160 m 2 / g. This specific surface area is measured based on the BET method. The content of magnesium oxide in the fluororubber composition is 1.3 parts by mass or more with respect to 100 parts by mass of fluororubber, but preferably 1.5 parts by mass from the viewpoint of suppressing the compression set of the rubber molded product to a low level. It is 3 parts by mass or less, more preferably 1.8 parts by mass or more and 2.4 parts by mass or less.
　本出願の「ハイドロタルサイト」とは、
　［Ｍ(1)２＋ １－ｘＭ(2)３＋ ｘ（ＯＨ）２］［Ａｎ－ ｘ／ｎ・ｍＨ２Ｏ］
　Ｍ(1)２＋：Ｍｇ２＋、Ｆｅ２＋、Ｚｎ２＋、Ｃａ２＋、Ｌｉ２＋、Ｎｉ２＋、Ｃｏ２＋、Ｃｕ２＋
　Ｍ(2)３＋：Ａｌ３＋、Ｆｅ３＋、Ｍｎ３＋
　Ａｎ－：ｎ価のアニオン
　０．２０≦ｘ≦０．３３
で表される層状の結晶構造体をいう。 What is "hydrotalcite" in this application?
[M (1) 2+ 1-x M (2) 3+ x (OH) 2 ] [An - x / n · mH 2 O]
M (1) 2+ : Mg 2+ , Fe 2+ , Zn 2+ , Ca 2+ , Li 2+ , Ni 2+ , Co 2+ , Cu 2+
M (2) 3+ : Al 3+ , Fe 3+ , Mn 3+
A n-: n-valent anion 0.20 ≦ x ≦ 0.33
Refers to a layered crystal structure represented by.
　ハイドロタルサイトは、その粉状体がフッ素ゴムに分散している。ハイドロタルサイトの平均粒子径は、優れた加工性を得る観点から、好ましくは０．２μｍ以上１００μｍ以下、より好ましくは０．４μｍ以上５０μｍ以下である。この平均粒子径は、レーザー回折・散乱法に基づいて測定されるメディアン径である。ハイドロタルサイトの比表面積は、好ましくは５ｍ２／ｇ以上２０ｍ２／ｇ以下、より好ましくは８ｍ２／ｇ以上１５ｍ２／ｇ以下である。この比表面積は、ＢＥＴ法に基づいて測定されるものである。 The powder of hydrotalcite is dispersed in fluororubber. The average particle size of hydrotalcite is preferably 0.2 μm or more and 100 μm or less, and more preferably 0.4 μm or more and 50 μm or less, from the viewpoint of obtaining excellent processability. This average particle diameter is a median diameter measured based on the laser diffraction / scattering method. The specific surface area of hydrotalcite is preferably 5 m 2 / g or more and 20 m 2 / g or less, and more preferably 8 m 2 / g or more and 15 m 2 / g or less. This specific surface area is measured based on the BET method.
　フッ素ゴム組成物におけるハイドロタルサイトの含有量は、優れた加工性を得る観点から、フッ素ゴム１００質量部に対して、好ましくは１質量部以上５質量部以下、より好ましくは２質量部以上４質量部以下である。ハイドロタルサイトの含有量の酸化マグネシウムの含有量に対する質量比は、０．６０以上５．０以下であるが、優れた加工性を得る観点から、好ましくは０．７０以上２．９以下、より好ましくは１．２以上１．８以下である。フッ素ゴム組成物におけるハイドロタルサイトの含有量は、優れた加工性を得る観点から、酸化マグネシウムの含有量よりも多いことが好ましい。 From the viewpoint of obtaining excellent processability, the content of hydrotalcite in the fluororubber composition is preferably 1 part by mass or more and 5 parts by mass or less, and more preferably 2 parts by mass or more 4 with respect to 100 parts by mass of fluororubber. It is less than a part by mass. The mass ratio of the hydrotalcite content to the magnesium oxide content is 0.60 or more and 5.0 or less, but preferably 0.70 or more and 2.9 or less from the viewpoint of obtaining excellent processability. It is preferably 1.2 or more and 1.8 or less. The content of hydrotalcite in the fluororubber composition is preferably higher than the content of magnesium oxide from the viewpoint of obtaining excellent processability.
　フッ素ゴム組成物における酸化マグネシウム及びハイドロタルサイトの含有量の和は、ゴム成形品の圧縮永久ひずみを低く抑えるとともに、優れた加工性を得る観点から、フッ素ゴム１００質量部に対して、好ましくは３質量部以上７質量部以下、より好ましくは４．５質量部以上５．５質量部以下である。 The sum of the contents of magnesium oxide and hydrotalcite in the fluororubber composition is preferable with respect to 100 parts by mass of the fluororubber from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. It is 3 parts by mass or more and 7 parts by mass or less, more preferably 4.5 parts by mass or more and 5.5 parts by mass or less.
　硫酸バリウムは、その粉状体がフッ素ゴムに分散している。硫酸バリウムの平均粒子径は、優れた加工性を得る観点から、好ましくは０．１μｍ以上１５μｍ以下、より好ましくは０．３μｍ以上２．０μｍ以下である。この平均粒子径は、レーザー回折・散乱法に基づいて測定されるメディアン径である。硫酸バリウムの比重は、好ましくは４．０以上４．６以下、より好ましくは４．４以上４．６以下である。 The powder of barium sulfate is dispersed in fluororubber. The average particle size of barium sulfate is preferably 0.1 μm or more and 15 μm or less, and more preferably 0.3 μm or more and 2.0 μm or less, from the viewpoint of obtaining excellent processability. This average particle diameter is a median diameter measured based on the laser diffraction / scattering method. The specific gravity of barium sulfate is preferably 4.0 or more and 4.6 or less, and more preferably 4.4 or more and 4.6 or less.
　フッ素ゴム組成物における硫酸バリウムの含有量は、フッ素ゴム１００質量部に対して５質量部以上１００質量部以下であるが、優れた加工性とともに、ゴム成形品の優れた耐摩耗性を得る観点から、好ましくは１０質量部以上９０質量部以下、より好ましくは２０質量部以上４０質量部以下である。フッ素ゴム組成物における硫酸バリウムの含有量は、優れた加工性を得る観点から、酸化マグネシウムの含有量、ハイドロタルサイトの含有量、及びそれらの含有量の和のいずれよりも多いことが好ましい。 The content of barium sulfate in the fluororubber composition is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fluororubber, but from the viewpoint of obtaining excellent workability and excellent wear resistance of the rubber molded product. Therefore, it is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less. The content of barium sulfate in the fluororubber composition is preferably higher than any of the magnesium oxide content, the hydrotalcite content, and the sum of these contents from the viewpoint of obtaining excellent processability.
　硫酸バリウムの含有量の酸化マグネシウムの含有量に対する質量比は、ゴム成形品の圧縮永久ひずみを低く抑えるとともに、優れた加工性を得る観点から、好ましくは４．５以上５０以下、より好ましくは１０以上２０以下である。 The mass ratio of the barium sulfate content to the magnesium oxide content is preferably 4.5 or more and 50 or less, more preferably 10 from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. More than 20 or less.
　硫酸バリウムの含有量のハイドロタルサイトの含有量に対する質量比は、優れた加工性を得る観点から、好ましくは３．０以上３５以下、より好ましくは５以上２０以下である。 The mass ratio of the barium sulfate content to the hydrotalcite content is preferably 3.0 or more and 35 or less, and more preferably 5 or more and 20 or less from the viewpoint of obtaining excellent processability.
　硫酸バリウムの含有量の酸化マグネシウム及びハイドロタルサイトの含有量の和に対する質量比は、ゴム成形品の圧縮永久ひずみを低く抑えるとともに、優れた加工性を得る観点から、好ましくは１．０以上２０以下、より好ましくは５．０以上８．０以下である。 The mass ratio of the barium sulfate content to the sum of the magnesium oxide and hydrotalcite contents is preferably 1.0 or more and 20 from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. Hereinafter, it is more preferably 5.0 or more and 8.0 or less.
　実施形態に係るフッ素ゴム組成物は、水酸化カルシウムを含有していてもよい。フッ素ゴム組成物における水酸化カルシウムの含有量は、ゴム成形品の圧縮永久ひずみを低く抑えるとともに、優れた加工性を得る観点から、フッ素ゴム１００質量部に対して、好ましくは４質量部以上８質量部以下である。フッ素ゴム組成物における水酸化カルシウムの含有量は、酸化マグネシウム及びハイドロタルサイトのいずれの含有量よりも多いことが好ましく、それらの含有量の和と同一又はそれよりも多いことが好ましい。 The fluororubber composition according to the embodiment may contain calcium hydroxide. The content of calcium hydroxide in the fluororubber composition is preferably 4 parts by mass or more with respect to 100 parts by mass of the fluororubber from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. It is less than the mass part. The content of calcium hydroxide in the fluororubber composition is preferably higher than the content of either magnesium oxide or hydrotalcite, and is preferably the same as or higher than the sum of the contents thereof.
　水酸化カルシウムの含有量の酸化マグネシウムの含有量に対する質量比は、ゴム成形品の圧縮永久ひずみを低く抑えるとともに、優れた加工性を得る観点から、好ましくは２．０以上７．５以下である。水酸化カルシウムの含有量のハイドロタルサイトの含有量に対する質量比は、同様の観点から、好ましくは１．０以上５．０以下である。水酸化カルシウムの含有量の酸化マグネシウム及びハイドロタルサイトの含有量の和に対する質量比は、同様の観点から、好ましくは１．０以上１．５以下である。 The mass ratio of the calcium hydroxide content to the magnesium oxide content is preferably 2.0 or more and 7.5 or less from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. .. From the same viewpoint, the mass ratio of the calcium hydroxide content to the hydrotalcite content is preferably 1.0 or more and 5.0 or less. From the same viewpoint, the mass ratio of the calcium hydroxide content to the sum of the magnesium oxide and hydrotalcite contents is preferably 1.0 or more and 1.5 or less.
　実施形態に係るフッ素ゴム組成物は、カーボンブラックを含有していてもよい。カーボンブラックとしては、例えば、例えば、ＨＡＦカーボンブラック、ＭＡＦカーボンブラック、ＦＥＦカーボンブラック、ＳＲＦカーボンブラック、ＧＰＦカーボンブラックなどのファーネスブラック；ＦＴカーボンブラック、ＭＴカーボンブラックなどのサーマルブラック等が挙げられる。カーボンブラックは、ゴム成形品の圧縮永久ひずみを低く抑えるとともに、優れた加工性を得る観点から、サーマルブラックを含むことが好ましく、ＭＴカーボンブラックを含むことがより好ましい。 The fluororubber composition according to the embodiment may contain carbon black. Examples of the carbon black include furnace blacks such as HAF carbon black, MAF carbon black, FEF carbon black, SRF carbon black and GPF carbon black; and thermal blacks such as FT carbon black and MT carbon black. The carbon black preferably contains thermal black, and more preferably MT carbon black, from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability.
　フッ素ゴム組成物におけるカーボンブラックの含有量は、ゴム成形品の圧縮永久ひずみを低く抑えるとともに、優れた加工性を得る観点から、フッ素ゴム１００質量部に対して、好ましくは１５質量部以上２５質量部以下である。フッ素ゴム組成物におけるカーボンブラックの含有量は、同様の観点から、硫酸バリウムの含有量よりも少ないことが好ましい。カーボンブラックの含有量の硫酸バリウムの含有量に対する質量比は、同様の観点から、好ましくは０．５以上０．７以下である。フッ素ゴム組成物における硫酸バリウム及びカーボンブラックの含有量の和は、同様の観点から、フッ素ゴム１００質量部に対して、好ましくは４０質量部以上６０質量部以下である。 The content of carbon black in the fluororubber composition is preferably 15 parts by mass or more and 25 parts by mass with respect to 100 parts by mass of fluororubber from the viewpoint of suppressing the compression set of the rubber molded product to a low level and obtaining excellent processability. It is less than a part. From the same viewpoint, the content of carbon black in the fluororubber composition is preferably smaller than the content of barium sulfate. From the same viewpoint, the mass ratio of the carbon black content to the barium sulfate content is preferably 0.5 or more and 0.7 or less. From the same viewpoint, the sum of the contents of barium sulfate and carbon black in the fluororubber composition is preferably 40 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the fluororubber.
　実施形態に係るフッ素ゴム組成物は、その他に加工助剤等を含有していてもよい。 The fluororubber composition according to the embodiment may also contain a processing aid or the like.
　実施形態に係るフッ素ゴム組成物は、オープンロール等のゴム混練機でフッ素ゴムを素練りし、そこに酸化マグネシウム、ハイドロタルサイト、及び硫酸バリウムを含むゴム配合剤を投入して混練することにより得ることができる。 The fluororubber composition according to the embodiment is obtained by kneading fluororubber with a rubber kneader such as an open roll, and adding a rubber compounding agent containing magnesium oxide, hydrotalcite, and barium sulfate to the kneading. Obtainable.
　そして、実施形態に係るフッ素ゴム組成物は、成形型のキャビティに充填され、所定温度に所定時間保持されてフッ素ゴムが架橋されることによりゴム成形品が形成される。フッ素ゴムの架橋系としては、ポリオール架橋系、パーオキサイド架橋系、ポリアミン架橋系が挙げられる。フッ素ゴムの架橋系は、これらのうちのポリオール架橋系が好ましい。得られるゴム成形品としては、例えば、圧縮永久ひずみが低いことから、特にＯリングやパッキン等のシール材が好適である。 Then, the fluororubber composition according to the embodiment is filled in the cavity of the molding mold, held at a predetermined temperature for a predetermined time, and the fluororubber is crosslinked to form a rubber molded product. Examples of the fluororubber cross-linking system include a polyol cross-linking system, a peroxide cross-linking system, and a polyamine cross-linking system. Of these, the polyol cross-linking system is preferable as the fluororubber cross-linking system. As the obtained rubber molded product, for example, a sealing material such as an O-ring or packing is particularly suitable because the compression set is low.
　ゴム成形品を形成する架橋フッ素ゴム組成物の圧縮永久ひずみは、好ましくは１６％以下、より好ましくは１３％以下である。この圧縮永久ひずみは、ＪＩＳ Ｋ６２６２：２０１３に基づき、試験温度を２００℃及び試験時間を２２時間として測定されるものである。 The compression set of the crosslinked fluororubber composition forming the rubber molded product is preferably 16% or less, more preferably 13% or less. This compression set is measured based on JIS K6262: 2013 with a test temperature of 200 ° C. and a test time of 22 hours.
　架橋フッ素ゴム組成物のタイプＡデュロメータを用いて測定されるゴム硬さは、好ましくは６０以上９０以下である。このゴム硬さは、ＪＩＳ Ｋ６２５３－３：２０１２に基づいて測定されるものである。 The rubber hardness measured using a type A durometer of the crosslinked fluororubber composition is preferably 60 or more and 90 or less. This rubber hardness is measured based on JIS K6253-3: 2012.
　架橋フッ素ゴム組成物の引張強さは、好ましくは８．０ＭＰａ以上である。架橋後のフッ素ゴム組成物の切断時伸びは、好ましくは１２０％以上である。これらの引張強さ及び切断時伸びは、ＪＩＳ Ｋ６２５１：２０１７に基づいて測定されるものである。 The tensile strength of the crosslinked fluororubber composition is preferably 8.0 MPa or more. The elongation at the time of cutting of the fluororubber composition after cross-linking is preferably 120% or more. These tensile strengths and elongations at the time of cutting are measured based on JIS K6251: 2017.
　（フッ素ゴム組成物）
　実施例１～５及び比較例１～５のフッ素ゴム組成物を調製した。各配合は表１にも示す。 (Fluororubber composition)
Fluororubber compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared. Each formulation is also shown in Table 1.
　＜実施例１＞
　オープンロールでフッ素ゴム（ダイエルＧ－７０１　ダイキン社製、二元系ＦＫＭ）を素練りし、そこにフッ素ゴム１００質量部に対して、酸化マグネシウム（キョーワマグ１５０　協和化学工業社製、平均粒子径：１１．７μｍ、比表面積：１４４ｍ２／ｇ）２．５質量部、ハイドロタルサイト（ＤＨＴ－４Ａ　協和化学工業社製、平均粒子径：０．４５μｍ、比表面積：１０．１ｍ２／ｇ）１．５質量部、硫酸バリウム（平均粒子径：０．６μｍ、比重：４．５）３０質量部、水酸化カルシウム（カルビット　近江化学工業社製）６質量部、ＭＴカーボンブラック（Ｎ９９０）２０質量部、及び加工助剤（ＶＰＡ Ｎｏ．２　バイトン社製）１質量部を投入配合して混練することにより得たフッ素ゴム組成物を実施例１とした。 <Example 1>
Fluororubber (Daiel G-701 Daikin Co., Ltd., dual FKM) is kneaded with an open roll, and magnesium oxide (Kyowa Mag 150 Kyowa Kagaku Kogyo Co., Ltd., average particle size: 11.7, specific surface area: 144m 2 /g)2.5 parts by weight of hydrotalcite (DHT-4A manufactured by Kyowa chemical industry Co., Ltd., average particle diameter: 0.45 [mu] m, a specific surface area: 10.1m 2 / g) 1 .5 parts by mass, barium sulfate (average particle size: 0.6 μm, specific surface area: 4.5) 30 parts by mass, calcium hydroxide (manufactured by Calbit Omi Chemical Industry Co., Ltd.) 6 parts by mass, MT carbon black (N990) 20 parts by mass And a fluororubber composition obtained by adding and kneading 1 part by mass of a processing aid (VPA No. 2 manufactured by Byton Co., Ltd.) as Example 1.
　＜実施例２＞
　酸化マグネシウムの配合量及びハイドロタルサイトの配合量を、フッ素ゴム１００質量部に対して、それぞれ２質量部及び３質量部としたことを除いて実施例１と同様にして得たフッ素ゴム組成物を実施例２とした。 <Example 2>
The fluororubber composition obtained in the same manner as in Example 1 except that the blending amount of magnesium oxide and the blending amount of hydrotalcite were 2 parts by mass and 3 parts by mass, respectively, with respect to 100 parts by mass of the fluororubber. Was referred to as Example 2.
　＜実施例３＞
　酸化マグネシウムの配合量及びハイドロタルサイトの配合量を、フッ素ゴム１００質量部に対して、それぞれ１．５質量部及び４．５質量部としたことを除いて実施例１と同様にして得たフッ素ゴム組成物を実施例３とした。 <Example 3>
It was obtained in the same manner as in Example 1 except that the blending amount of magnesium oxide and the blending amount of hydrotalcite were 1.5 parts by mass and 4.5 parts by mass, respectively, with respect to 100 parts by mass of fluororubber. The fluororubber composition was designated as Example 3.
　＜実施例４＞
　硫酸バリウムの配合量を、フッ素ゴム１００質量部に対して１０質量部とし、ＭＴカーボンブラックを配合しなかったことを除いて実施例２と同様にして得たフッ素ゴム組成物を実施例４とした。 <Example 4>
The amount of barium sulfate blended was 10 parts by mass with respect to 100 parts by mass of fluororubber, and the fluororubber composition obtained in the same manner as in Example 2 except that MT carbon black was not blended was referred to as Example 4. did.
　＜実施例５＞
　硫酸バリウムの配合量を、フッ素ゴム１００質量部に対して９０質量部としたことを除いて実施例４と同様にして得たフッ素ゴム組成物を実施例５とした。 <Example 5>
Example 5 was a fluororubber composition obtained in the same manner as in Example 4 except that the amount of barium sulfate blended was 90 parts by mass with respect to 100 parts by mass of fluororubber.
　＜比較例１＞
　酸化マグネシウムを配合せず、ハイドロタルサイトの配合量を、フッ素ゴム１００質量部に対して９質量部としたことを除いて実施例１と同様にして得たフッ素ゴム組成物を比較例１とした。 <Comparative example 1>
The fluororubber composition obtained in the same manner as in Example 1 except that magnesium oxide was not blended and the amount of hydrotalcite blended was 9 parts by mass with respect to 100 parts by mass of the fluororubber was compared with Comparative Example 1. did.
　＜比較例２＞
　酸化マグネシウムの配合量及びハイドロタルサイトの配合量を、フッ素ゴム１００質量部に対して、それぞれ１質量部及び６質量部としたことを除いて実施例１と同様にして得たフッ素ゴム組成物を比較例２とした。 <Comparative example 2>
The fluororubber composition obtained in the same manner as in Example 1 except that the blending amount of magnesium oxide and the blending amount of hydrotalcite were 1 part by mass and 6 parts by mass, respectively, with respect to 100 parts by mass of the fluororubber. Was designated as Comparative Example 2.
　＜比較例３＞
　酸化マグネシウムの配合量を、フッ素ゴム１００質量部に対して３質量部とし、ハイドロタルサイトを配合しなかったことを除いて実施例１と同様にして得たフッ素ゴム組成物を比較例３とした。 <Comparative example 3>
The amount of magnesium oxide blended was 3 parts by mass with respect to 100 parts by mass of the fluororubber, and the fluororubber composition obtained in the same manner as in Example 1 except that hydrotalcite was not blended was compared with Comparative Example 3. did.
　＜比較例４＞
　ハイドロタルサイト及び硫酸バリウムを配合せず、水酸化カルシウムの配合量及びＭＴカーボンブラックの配合量を、フッ素ゴム１００質量部に対して、それぞれ３質量部及び４５質量部としたことを除いて実施例２と同様にして得たフッ素ゴム組成物を比較例４とした。 <Comparative example 4>
It was carried out without adding hydrotalcite and barium sulfate, except that the amount of calcium hydroxide and MT carbon black was 3 parts by mass and 45 parts by mass, respectively, with respect to 100 parts by mass of fluororubber. The fluororubber composition obtained in the same manner as in Example 2 was designated as Comparative Example 4.
　＜比較例５＞
　酸化マグネシウムの配合量、ハイドロタルサイトの配合量、及び硫酸バリウムの配合量を、フッ素ゴム１００質量部に対して、それぞれ９質量部、５質量部、及び５質量部としたことを除いて実施例１と同様にして得たフッ素ゴム組成物を比較例５とした。 <Comparative example 5>
The amount of magnesium oxide, the amount of hydrotalcite, and the amount of barium sulfate were 9 parts by mass, 5 parts by mass, and 5 parts by mass, respectively, with respect to 100 parts by mass of fluororubber. The fluororubber composition obtained in the same manner as in Example 1 was designated as Comparative Example 5.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（試験方法）
　＜物理特性＞
　実施例１～５及び比較例１～５のそれぞれのフッ素ゴム組成物について、シート成形金型を用いた１７０℃で１０分間のプレス成型による１次架橋を行った後、オーブンを用いた２３０℃で２４時間の２次架橋を行ってシート状のゴム成形品を作製した。 (Test method)
<Physical characteristics>
Each of the fluororubber compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was subjected to primary cross-linking by press molding at 170 ° C. for 10 minutes using a sheet molding die, and then 230 ° C. using an oven. A sheet-shaped rubber molded product was produced by performing secondary cross-linking for 24 hours.
　各シート状のゴム成形品を用い、ＪＩＳ Ｋ６２６２：２０１３に基づき、試験温度を２００℃及び試験時間を２２時間として圧縮永久ひずみを測定した。また、圧縮後のゴム成形品の外観を目視確認し、異常の無いものをＡ評価及び割れが認められたものをＢ評価とした。 Using each sheet-shaped rubber molded product, the compression set was measured based on JIS K6262: 2013 with a test temperature of 200 ° C. and a test time of 22 hours. Further, the appearance of the rubber molded product after compression was visually confirmed, and those having no abnormality were evaluated as A and those with cracks were evaluated as B.
　また、ＪＩＳ Ｋ６２５３－３：２０１２に基づき、タイプＡデュロメータを用いてゴム硬さを測定した。さらに、ＪＩＳ Ｋ６２５１：２０１７に基づいて、引張強さ及び切断時伸びを測定した。 In addition, the rubber hardness was measured using a type A durometer based on JIS K6253-3: 2012. Furthermore, the tensile strength and the elongation at the time of cutting were measured based on JIS K6251: 2017.
　＜加工性＞
　実施例１～５及び比較例１～５のそれぞれについて、フッ素ゴム組成物を混練して取り出した後のオープンロールのロール表面を目視確認し、汚れの認められないものをＡ評価及び汚れが認められたものをＢ評価とした。 <Workability>
For each of Examples 1 to 5 and Comparative Examples 1 to 5, the roll surface of the open roll after the fluororubber composition was kneaded and taken out was visually confirmed, and those without stains were evaluated as A and stains were observed. The result was given a B rating.
　実施例１～５及び比較例１～５のそれぞれについて、プレス成型したゴム成形品を取り出した後のシート成形金型の金型表面を目視確認し、汚れの認められないものをＡ評価及び汚れが認められたものをＢ評価とした。 For each of Examples 1 to 5 and Comparative Examples 1 to 5, the surface of the sheet molding die after taking out the press-molded rubber molded product was visually checked, and those with no stain were evaluated as A and soiled. Was evaluated as B.
　実施例１～５及び比較例１～５のそれぞれについて、シート成形金型上のプレス成型したゴム成形品を目視確認し、フッ素ゴム組成物の流動不足による外観不良が全く認められないものをＡ評価、外観不良が僅かに認められたものをＢ評価、及び外観不良が顕著に認められたものをＣ評価とした。 For each of Examples 1 to 5 and Comparative Examples 1 to 5, the press-molded rubber molded product on the sheet molding die was visually confirmed, and the one in which no appearance defect due to insufficient flow of the fluororubber composition was observed was A. The evaluation, the one in which a slight appearance defect was observed was evaluated as B, and the one in which a remarkable appearance defect was observed was evaluated as C evaluation.
　（試験結果）
　試験結果を表２に示す。表２によれば、実施例１～５は、ゴム成形品の圧縮永久ひずみが低く、且つ加工性が優れることが分かる。一方、酸化マグネシウムの含有量が少ない比較例１及び２では、圧縮永久歪みが大きいことが分かる。また、ハイドロタルサイトを含有しない比較例３では、オープンロールのロール表面及びシート成形金型の金型表面の汚れが認められたことから、加工性が劣ることが分かる。同じくハイドロタルサイトを含有しない比較例４でも、オープンロールのロール表面の汚れが認められたことから、加工性が劣ることが分かる。ハイドロタルサイトを含有するものの、その含有量の酸化マグネシウムの含有量に対する比が小さい比較例５でも、オープンロールのロール表面及びシート成形金型の金型表面の汚れが認められたことから、加工性が劣ることが分かる。さらに、硫酸バリウムを含有しない比較例４及び硫酸バリウムの含有量が少ない比較例５では、ゴム成形品の外観不良が認められたことから、この点でも加工性が劣ることが分かる。 (Test results)
The test results are shown in Table 2. According to Table 2, it can be seen that Examples 1 to 5 have low compression set and excellent workability of the rubber molded product. On the other hand, in Comparative Examples 1 and 2 in which the content of magnesium oxide is low, it can be seen that the compression set is large. Further, in Comparative Example 3 containing no hydrotalcite, stains on the roll surface of the open roll and the mold surface of the sheet molding die were observed, so that it can be seen that the processability is inferior. Similarly, in Comparative Example 4 which does not contain hydrotalcite, stains on the roll surface of the open roll were observed, indicating that the processability was inferior. Even in Comparative Example 5, which contains hydrotalcite but the ratio of the content to the magnesium oxide content is small, stains on the roll surface of the open roll and the mold surface of the sheet molding die were observed. It turns out that the sex is inferior. Further, in Comparative Example 4 which does not contain barium sulfate and Comparative Example 5 in which the content of barium sulfate is low, poor appearance of the rubber molded product was observed, and it can be seen that the processability is also inferior in this respect.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明は、フッ素ゴム組成物並びにそれを用いたゴム成形品及びシール材について有用である。 The present invention is useful for fluororubber compositions, rubber molded products and sealing materials using the same.

Claims (15)

  1. 　フッ素ゴムと、酸化マグネシウムと、ハイドロタルサイトと、硫酸バリウムと、を含有するフッ素ゴム組成物であって、
    　前記酸化マグネシウムの含有量が、前記フッ素ゴム１００質量部に対して１．３質量部以上であり、
    　前記ハイドロタルサイトの含有量の前記酸化マグネシウムの含有量に対する質量比が０．６０以上５．０以下であり、
    　前記硫酸バリウムの含有量が、前記フッ素ゴム１００質量部に対して５質量部以上１００質量部以下であるフッ素ゴム組成物。     A fluororubber composition containing fluororubber, magnesium oxide, hydrotalcite, and barium sulfate.
    The content of the magnesium oxide is 1.3 parts by mass or more with respect to 100 parts by mass of the fluororubber.
    The mass ratio of the hydrotalcite content to the magnesium oxide content is 0.60 or more and 5.0 or less.
    A fluororubber composition having a barium sulfate content of 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fluororubber.
  2. 　請求項１に記載されたフッ素ゴム組成物において、
    　前記フッ素ゴムが二元系フッ素ゴムを含むフッ素ゴム組成物。     In the fluororubber composition according to claim 1,
    A fluororubber composition in which the fluororubber contains a dual fluororubber.
  3. 　請求項１又は２に記載されたフッ素ゴム組成物において、
    　前記酸化マグネシウムの平均粒子径が０．３μｍ以上４０μｍ以下であるフッ素ゴム組成物。     In the fluororubber composition according to claim 1 or 2.
    A fluororubber composition having an average particle size of magnesium oxide of 0.3 μm or more and 40 μm or less.
  4. 　請求項１乃至３のいずれかに記載されたフッ素ゴム組成物において、
    　前記ハイドロタルサイトの含有量が、前記フッ素ゴム１００質量部に対して１質量部以上５質量部以下であるフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 3.
    A fluororubber composition in which the content of the hydrotalcite is 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the fluororubber.
  5. 　請求項１乃至４のいずれかに記載されたフッ素ゴム組成物において、
    　前記ハイドロタルサイトの平均粒子径が０．２μｍ以上１００μｍ以下であるフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 4.
    A fluororubber composition having an average particle size of the hydrotalcite of 0.2 μm or more and 100 μm or less.
  6. 　請求項１乃至５のいずれかに記載されたフッ素ゴム組成物において、
    　前記ハイドロタルサイトの含有量が前記酸化マグネシウムの含有量よりも多いフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 5.
    A fluororubber composition in which the content of the hydrotalcite is higher than the content of the magnesium oxide.
  7. 　請求項１乃至６のいずれかに記載されたフッ素ゴム組成物において、
    　前記酸化マグネシウム及び前記ハイドロタルサイトの含有量の和が、前記フッ素ゴム１００質量部に対して３質量部以上７質量部以下であるフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 6.
    A fluororubber composition in which the sum of the contents of magnesium oxide and hydrotalcite is 3 parts by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the fluororubber.
  8. 　請求項１乃至７のいずれかに記載されたフッ素ゴム組成物において、
    　前記硫酸バリウムの平均粒子径が０．１μｍ以上１５μｍ以下であるフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 7.
    A fluororubber composition having an average particle size of barium sulfate of 0.1 μm or more and 15 μm or less.
  9. 　請求項１乃至８のいずれかに記載されたフッ素ゴム組成物において、
    　前記硫酸バリウムの含有量の前記酸化マグネシウムの含有量に対する質量比が４．５以上５０以下であるフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 8.
    A fluororubber composition in which the mass ratio of the barium sulfate content to the magnesium oxide content is 4.5 or more and 50 or less.
  10. 　請求項１乃至９のいずれかに記載されたフッ素ゴム組成物において、
    　前記硫酸バリウムの含有量の前記ハイドロタルサイトの含有量に対する質量比が３．０以上３５以下であるフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 9.
    A fluororubber composition in which the mass ratio of the barium sulfate content to the hydrotalcite content is 3.0 or more and 35 or less.
  11. 　請求項１乃至１０のいずれかに記載されたフッ素ゴム組成物において、
    　前記硫酸バリウムの含有量の前記酸化マグネシウム及び前記ハイドロタルサイトの含有量の和に対する質量比が１．０以上２０以下であるフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 10.
    A fluororubber composition in which the mass ratio of the barium sulfate content to the sum of the contents of the magnesium oxide and the hydrotalcite is 1.0 or more and 20 or less.
  12. 　請求項１乃至１１のいずれかに記載されたフッ素ゴム組成物において、
    　前記硫酸バリウムの含有量が、前記酸化マグネシウムの含有量、前記ハイドロタルサイトの含有量、及びそれらの含有量の和のいずれよりも多いフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 11.
    A fluororubber composition in which the content of barium sulfate is higher than any of the content of magnesium oxide, the content of hydrotalcite, and the sum of these contents.
  13. 　請求項１乃至１２のいずれかに記載されたフッ素ゴム組成物において、
    　水酸化カルシウムを含有するフッ素ゴム組成物。     In the fluororubber composition according to any one of claims 1 to 12.
    Fluororubber composition containing calcium hydroxide.
  14. 　請求項１乃至１３のいずれかに記載されたフッ素ゴム組成物の前記フッ素ゴムが架橋されて形成されたゴム成形品。 A rubber molded product formed by cross-linking the fluororubber of the fluororubber composition according to any one of claims 1 to 13.
  15. 　請求項１乃至１３のいずれかに記載されたフッ素ゴム組成物の前記フッ素ゴムが架橋されて形成されたシール材。 A sealing material formed by cross-linking the fluororubber of the fluororubber composition according to any one of claims 1 to 13.
PCT/JP2020/025536 2019-07-31 2020-06-29 Fluorine rubber composition, and rubber formed product and sealing material using same WO2021019999A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0782449A (en) * 1993-09-17 1995-03-28 Nok Corp Polyol-vulcanizable fluororubber composition
JP2002265733A (en) * 2001-03-15 2002-09-18 Nippon Mektron Ltd Vulcanizable fluororubber composition and its use
WO2007135937A1 (en) * 2006-05-19 2007-11-29 Daikin Industries, Ltd. Fluoroelastomer composition and molded article comprising the composition
JP2011132315A (en) * 2009-12-22 2011-07-07 Nok Corp Fluororubber composition and seal material
JP2017095592A (en) * 2015-11-24 2017-06-01 ダイキン工業株式会社 Member for air control system and fluororubber composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0782449A (en) * 1993-09-17 1995-03-28 Nok Corp Polyol-vulcanizable fluororubber composition
JP2002265733A (en) * 2001-03-15 2002-09-18 Nippon Mektron Ltd Vulcanizable fluororubber composition and its use
WO2007135937A1 (en) * 2006-05-19 2007-11-29 Daikin Industries, Ltd. Fluoroelastomer composition and molded article comprising the composition
JP2011132315A (en) * 2009-12-22 2011-07-07 Nok Corp Fluororubber composition and seal material
JP2017095592A (en) * 2015-11-24 2017-06-01 ダイキン工業株式会社 Member for air control system and fluororubber composition

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