JPWO2018225487A1 - フッ素ゴム組成物及びフッ素ゴム架橋体 - Google Patents
フッ素ゴム組成物及びフッ素ゴム架橋体 Download PDFInfo
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- JPWO2018225487A1 JPWO2018225487A1 JP2018558784A JP2018558784A JPWO2018225487A1 JP WO2018225487 A1 JPWO2018225487 A1 JP WO2018225487A1 JP 2018558784 A JP2018558784 A JP 2018558784A JP 2018558784 A JP2018558784 A JP 2018558784A JP WO2018225487 A1 JPWO2018225487 A1 JP WO2018225487A1
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- fluororubber
- ternary
- silica
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052731 fluorine Inorganic materials 0.000 title claims description 14
- 239000011737 fluorine Substances 0.000 title claims description 14
- 229920001971 elastomer Polymers 0.000 title description 7
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 92
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000376 reactant Substances 0.000 claims abstract description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 17
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 16
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 16
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 16
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 15
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- 230000006835 compression Effects 0.000 abstract description 26
- 238000007906 compression Methods 0.000 abstract description 26
- 238000011156 evaluation Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002156 mixing Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002449 FKM Polymers 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZNHPPXDUJKXBNM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)hexane Chemical compound CC(C)(C)OOC(C)CCC(C)OOC(C)(C)C ZNHPPXDUJKXBNM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る3元系フッ素ゴムポリマーと、
シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物とを含有し、
酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
前記3元系フッ素ゴムポリマー100重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を8〜60重量部含有することを特徴とするフッ素ゴム組成物。
2.
フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る3元系フッ素ゴムポリマーと、
シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物と、
ハイドロタルサイトとを含有し、
酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
前記3元系フッ素ゴムポリマー100重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を2〜55重量部、前記ハイドロタルサイトを0.5〜10重量部含有することを特徴とするフッ素ゴム組成物。
3.
前記3元系フッ素ゴムポリマーは、フッ素含有量が64〜67重量%であることを特徴とする前記1又は2記載のフッ素ゴム組成物。
4.
前記1〜3の何れかに記載のフッ素ゴム組成物を架橋してなることを特徴とするフッ素ゴム架橋体。
1.フッ素ゴム組成物の調製
下記3元系フッ素ゴムポリマーC 100重量部に、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物(ホフマンミネラル社製「アクチジルVM」)10重量部と、MTカーボンブラック(CANCARB LIMITED社製「THERMAX N−990LSR」)3重量部、酸化亜鉛(JIS規格「1種」該当品質)0.1重量部を配合し、更に、有機価酸化物架橋剤(2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン)(日本油脂社製「パーヘキサ25B−40」)2重量部と共に所定の配合剤を配合して混練し、未架橋のフッ素ゴム組成物を得た。
・3元系フッ素ゴムポリマーB:フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る3元系フッ素ゴムポリマー;フッ素含有量64重量%(デュポン社製「バイトンGTL200S」)
・3元系フッ素ゴムポリマーC:フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る3元系フッ素ゴムポリマー;フッ素含有量64重量%(ソルベイソレクシス社製「テクノフロンPL855」)
上記フッ素ゴム組成物を用いて、接着性評価用の試験片、スチーム環境下での圧縮永久歪み評価用の試験片、スチーム環境下での硬さ変化防止評価用の試験片を、以下の方法により作製した。
上記フッ素ゴム組成物をφ85mmのオイルシールの形状に成形し、これを鋼板に対して180℃で3分間プレス架橋接着することによって、接着性評価用の試験片を得た。
上記フッ素ゴム組成物を線径3.1mmのOリングの形状に成形し、これを180℃で3分間プレス架橋し、その後、200℃の雰囲気下で5時間保持することによって、スチーム環境下での圧縮永久歪み評価用の試験片を得た。
上記フッ素ゴム組成物を2mm厚のシートに成形し、これを180℃で3分間プレス架橋し、その後、200℃の雰囲気下で5時間保持することによって、スチーム環境下での硬さ変化防止評価用の試験片を得た。
(1)接着性
上記接着性評価用の試験片において、接着されているオイルシールをペンチで剥離し、ゴムが残留した面積率として、R残率(%)を測定した。測定されたR残率(%)に基づいて以下の評価基準で評価した。
<評価基準>
AA:R残率(%)が80%以上、100%以下である。
A:R残率(%)が60%以上、80%未満である。
B:R残率(%)が45%以上、60%未満である。
C:R残率(%)が0%以上、45%未満である。
スチーム環境下での圧縮永久歪み(%)を、JIS K6262:2013に準拠して測定した。試験環境は、湿度95%のスチーム環境、試験温度は80℃、試験時間は96時間とした。測定された圧縮永久歪み(%)に基づいて以下の評価基準で評価した。
<評価基準>
AA:圧縮永久歪み(%)が0%以上、25%以下である。
A:圧縮永久歪み(%)が25%超、28%以下である。
B:圧縮永久歪み(%)が28%超、31%以下である。
C:圧縮永久歪み(%)が31%超、100%以下である。
スチーム環境下での硬さ変化を、JIS K6258:2010に準拠して測定した。試験環境は、湿度95%のスチーム環境、試験温度は80℃、試験時間は192時間とした。測定された硬さ変化(Hw)(Points)に基づいて以下の評価基準で評価した。
<評価基準>
AA:硬さ変化(Hw)(Points)が±0である。
A:硬さ変化(Hw)(Points)が−5以上、−1以下である。
B:硬さ変化(Hw)(Points)が+1以上、+5以下である。
C:硬さ変化(Hw)(Points)が+5超、+10以下である。
上記(1)〜(3)の評価結果に基づいて以下の評価基準で総合評価を行った。
<評価基準>
AA:上記(1)〜(3)の評価がA以上のみである。
A:上記(1)〜(3)の評価としてA以上を含み、Cを含まない。
B:上記(1)〜(3)の評価がBのみである。
C:上記(1)〜(3)の評価としてCを含む。
実施例1において、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を15重量部に代えたこと以外は、実施例1と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表1に示す。
実施例1において、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を30重量部に代えたこと以外は、実施例1と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表1に示す。
実施例3において、MTカーボンブラックに代えて、FEFカーボンブラック(東海カーボン社製「シーストGS−O」)2重量部を配合し、酸化亜鉛の配合を省略したこと以外は、実施例3と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表1に示す。
実施例1において、上記3元系フッ素ゴムポリマーCに代えて、3元系フッ素ゴムポリマーA 50重量部、及び、上記3元系フッ素ゴムポリマーB 50重量部からなるポリマー100重量部を用い、更に、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を5重量部に代え、更に、ハイドロタルサイト(Mg4.3Al2(OH)12.6CO3・mH2O)(協和化学工業社製「DHT−4A」)を3重量部と、酸化マグネシウム(協和化学工業社製「キョーワマグ150」)6重量部と、水酸化カルシウム(近江化学工業社製「CALDIC 2000」)3重量部とを配合したこと以外は、実施例1と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表1に示す。
比較例1において、酸化マグネシウムの配合を省略したこと以外は、比較例1と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表1に示す。
比較例1において、ハイドロタルサイト、酸化マグネシウム及び水酸化カルシウムの配合を省略したこと以外は、比較例1と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表1に示す。
実施例1において、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を5重量部に代えたこと以外は、実施例1と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表1に示す。
表1より、本発明の第1態様に係るフッ素ゴム組成物(実施例1〜4)によれば、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れる効果が得られることがわかる。
下記3元系フッ素ゴムポリマーA 50重量部、及び、下記3元系フッ素ゴムポリマーB 50重量部からなるポリマー100重量部に、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物(ホフマンミネラル社製「アクチジルVM」)5重量部と、ハイドロタルサイト(Mg4.3Al2(OH)12.6CO3・mH2O)(協和化学工業社製「DHT−4A」)6重量部、MTカーボンブラック(CANCARB LIMITED社製「THERMAX N−990LSR」)3重量部、酸化亜鉛(JIS規格「1種」該当品質)0.1重量部を配合し、更に、有機過酸化物架橋剤(2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン)(日本油脂社製「パーヘキサ25B−40」)2重量部と共に所定の配合剤を配合して混練し、未架橋のフッ素ゴム組成物を得た。得られたフッ素ゴム組成物を用いて、実施例1と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表2に示す。
・3元系フッ素ゴムポリマーB:フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る3元系フッ素ゴムポリマー;フッ素含有量64重量%(デュポン社製「バイトンGTL200S」)
実施例5において、ハイドロタルサイトの配合量を9重量部に代えたこと以外は、実施例5と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表2に示す。
実施例5において、ハイドロタルサイトの配合量を3重量部に代え、更に、酸化マグネシウム(協和化学工業社製「キョーワマグ150」)6重量部と、水酸化カルシウム(近江化学工業社製「CALDIC 2000」)3重量部を配合したこと以外は、実施例5と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表2に示す。
実施例5において、ハイドロタルサイトの配合量を3重量部に代え、更に、水酸化カルシウム3重量部を配合したこと以外は、実施例5と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表2に示す。
実施例5において、ハイドロタルサイトの配合量を12重量部に代えたこと以外は、実施例5と同様にして各試験片を作製し、実施例1と同様にして評価した。結果を表2に示す。
表2より、本発明の第2態様に係るフッ素ゴム組成物(実施例5、6)によれば、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れる効果が得られることがわかる。
Claims (4)
- フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る3元系フッ素ゴムポリマーと、
シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物とを含有し、
酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
前記3元系フッ素ゴムポリマー100重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を8〜60重量部含有することを特徴とするフッ素ゴム組成物。 - フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る3元系フッ素ゴムポリマーと、
シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物と、
ハイドロタルサイトとを含有し、
酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
前記3元系フッ素ゴムポリマー100重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を2〜55重量部、前記ハイドロタルサイトを0.5〜10重量部含有することを特徴とするフッ素ゴム組成物。 - 前記3元系フッ素ゴムポリマーは、フッ素含有量が64〜67重量%であることを特徴とする請求項1又は2記載のフッ素ゴム組成物。
- 請求項1〜3の何れかに記載のフッ素ゴム組成物を架橋してなることを特徴とするフッ素ゴム架橋体。
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ATE179440T1 (de) * | 1991-03-25 | 1999-05-15 | Ecc Int Ltd | Mineralische füllstoffe |
DE4331995A1 (de) * | 1993-09-21 | 1995-03-23 | Huels Chemische Werke Ag | Verfahren zur Herstellung von Verbundgegenständen aus Polyestern und Elastomeren |
JP4780589B2 (ja) * | 2004-07-08 | 2011-09-28 | 内山工業株式会社 | フッ素ゴム組成物 |
JP4539510B2 (ja) * | 2005-03-22 | 2010-09-08 | Nok株式会社 | フッ素ゴム組成物 |
ATE547471T1 (de) * | 2006-09-26 | 2012-03-15 | Nok Corp | Fluorkautschukzusammensetzung, vernetzter fluorkautschuk, herstellungsverfahren dafür und vernetzter fluorkautschuk für o-ringe |
CN101412835B (zh) * | 2008-11-28 | 2011-01-19 | 华南理工大学 | 氟橡胶与硅橡胶共混物及其制备方法 |
DE102010009146B4 (de) * | 2010-02-24 | 2012-12-27 | TDH - GmbH Technischer Dämmstoffhandel | Plastische feuerfeste Masse und feuerfester Mörtel und deren Verwendung |
JP5418683B2 (ja) | 2011-04-06 | 2014-02-19 | Nok株式会社 | フッ素ゴム組成物 |
US20130281598A1 (en) * | 2012-04-18 | 2013-10-24 | E I Du Pont De Nemours And Company | Cured fluoroelastomer compositions containing magnesium silicate filler |
JP6052160B2 (ja) | 2013-12-26 | 2016-12-27 | 株式会社デンソー | Egrバルブ装置 |
EA035294B1 (ru) * | 2015-06-15 | 2020-05-26 | Бизон Интернэшнл Б.В. | Высокопрочный и влагостойкий адгезив |
CN107778734B (zh) * | 2016-08-25 | 2019-09-24 | 中昊晨光化工研究院有限公司 | 一种氟橡胶混炼胶及制备方法 |
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US20200109262A1 (en) | 2020-04-09 |
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