JP2011042714A - Fluororubber composition and rubber member - Google Patents
Fluororubber composition and rubber member Download PDFInfo
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- JP2011042714A JP2011042714A JP2009190348A JP2009190348A JP2011042714A JP 2011042714 A JP2011042714 A JP 2011042714A JP 2009190348 A JP2009190348 A JP 2009190348A JP 2009190348 A JP2009190348 A JP 2009190348A JP 2011042714 A JP2011042714 A JP 2011042714A
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
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- 238000004519 manufacturing process Methods 0.000 claims description 27
- 239000003566 sealing material Substances 0.000 abstract description 27
- 239000000126 substance Substances 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003205 fragrance Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000796 flavoring agent Substances 0.000 description 5
- 235000019634 flavors Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920006169 Perfluoroelastomer Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000001953 sensory effect Effects 0.000 description 4
- -1 vinyl methyl Chemical group 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
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- 239000002304 perfume Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010060 peroxide vulcanization Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 102100021860 Endothelial cell-specific molecule 1 Human genes 0.000 description 1
- 101710153170 Endothelial cell-specific molecule 1 Proteins 0.000 description 1
- YEEGWNXDUZONAA-RYDPDVNUSA-K Gallium Citrate (67 Ga) Chemical compound [67Ga+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YEEGWNXDUZONAA-RYDPDVNUSA-K 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005192 alkyl ethylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 235000015197 apple juice Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- FRIPRWYKBIOZJU-UHFFFAOYSA-N fluorone Chemical compound C1=CC=C2OC3=CC(=O)C=CC3=CC2=C1 FRIPRWYKBIOZJU-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
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- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000013020 steam cleaning Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明はフッ素ゴム組成物に関し、詳しくは、極めて着香しにくく、かつ、耐熱性および耐薬品性に優れ、特に食品の製造機器や製造ラインに使用するゴム部材として有用なフッ素ゴム組成物、並びに、該フッ素ゴム組成物を加硫成形してなるゴム部材に関する。 The present invention relates to a fluororubber composition, and more particularly, a fluororubber composition that is extremely difficult to perfume, has excellent heat resistance and chemical resistance, and is particularly useful as a rubber member for use in food production equipment and production lines, The present invention also relates to a rubber member obtained by vulcanization molding of the fluororubber composition.
現行の食品の製造機器、製造ラインにおいて、使用頻度の高いゴム材料としては、エチレンプロピレンゴム（ＥＰＤＭ）、水素化ニトリルゴム（ＨＮＢＲ）、ビニリデンフルオライド系ゴム（ＦＫＭ）、ビニルメチルシリコーンゴム（ＶＭＱ）などがある。 Rubber materials that are frequently used in current food production equipment and production lines are ethylene propylene rubber (EPDM), hydrogenated nitrile rubber (HNBR), vinylidene fluoride rubber (FKM), vinyl methyl silicone rubber (VMQ). )and so on.
これらのゴム材料は、食品の製造機器や製造ライン中での適用箇所に応じて、機械的強度、耐熱性、耐薬品性、コストなどを考慮しながら使い分けられている。これらのゴム材料による具体的な部材としては、例えば、Ｏリング、ガスケット、パッキンなどのシール材が挙げられる。 These rubber materials are properly used in consideration of mechanical strength, heat resistance, chemical resistance, cost, and the like according to the application location in food production equipment and production lines. Specific examples of these rubber materials include sealing materials such as O-rings, gaskets, and packings.
ところで、食品の製造機器や製造ラインで使用されるシール材等のゴム部材に、食品或いはその原料などの匂いの成分が付着すると、該匂いの成分がゴム部材を介して後の製品（食品）に移行し、該製品の価値を著しく低下させるという問題がある。このため、シール材等を洗浄する洗浄工程を設けたり、また、シール材等の洗浄中に製品製造のための別の製造ラインを設置したりするなどの対策が必要となり、製品（食品）の生産コストが増大する。さらに、シール材等の洗浄を効果的に行うためには洗浄時間を延長することが必要になり、このような場合には製品の生産効率が更に低下するため、生産コストの一層の増大化を招くことになる。 By the way, when an odorous component such as food or its raw material adheres to a rubber member such as a sealing material used in food production equipment or a production line, the odorous component passes through the rubber member to produce a subsequent product (food). There is a problem that the value of the product is remarkably lowered. For this reason, it is necessary to take measures such as providing a cleaning process for cleaning the sealing material, etc., and installing another production line for manufacturing the product during the cleaning of the sealing material, etc. Production costs increase. Furthermore, it is necessary to extend the cleaning time in order to effectively clean the sealing material and the like. In such a case, the production efficiency of the product is further reduced, so that the production cost is further increased. Will be invited.
また、シール材等の洗浄工程では、アルカリ洗浄、酸洗浄、高温スチームによる洗浄などが施されるため、シール材等には低着香性だけでなく、耐熱性、耐薬品性が求められる。 Further, in the cleaning process of the sealing material and the like, alkali cleaning, acid cleaning, high temperature steam cleaning, and the like are performed. Therefore, the sealing material and the like are required to have not only low flavor but also heat resistance and chemical resistance.
現状のシール材において、着香の問題に対処したものとして、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル系共重合体（ＦＦＫＭ）を用いた製品、ゴムにポリテトラフルオロエチレン（ＰＴＦＥ）を被覆した製品、ＰＴＦＥからなる製品が知られている。しかし、ＦＦＫＭはコストが非常に高いという問題があり、また、ゴムにＰＴＦＥを被覆した製品は、ＰＴＦＥのクリープ、ゴムとＰＴＦＥの剥離などが生じることがあり、また、ＰＴＦＥは弾性が少ないことやクリープによってシール性を維持できなくなるなどの技術的問題を抱えている。従って、コスト及び性能面の両方において満足できる低着香性のシール材が求められている。 In the current sealing materials, products that use the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FFKM), products that are coated with polytetrafluoroethylene (PTFE), Products made of PTFE are known. However, FFKM has a problem that the cost is very high, and a product in which PTFE is coated on rubber may cause PTFE creep, separation of rubber and PTFE, etc. It has technical problems such as being unable to maintain the sealing performance due to creep. Therefore, there is a need for a low-flavoring sealing material that is satisfactory in both cost and performance.
このような要求に応えるものとして、特許文献１〜３には、フッ素ゴムにガラス充填剤および／または真球状無孔質シリカ（非晶質二酸化ケイ素）充填剤を配合したフッ素ゴム組成物、フッ素ゴムに窒化ホウ素充填剤を配合してなるフッ素ゴム組成物、フッ素ゴムに表面改質されていてもよい真球状無孔質シリカ（非晶質二酸化ケイ素）充填材と、微粉末フッ素樹脂充填剤、有機過酸化物加硫剤及び共架橋剤を配合したフッ素ゴム組成物等が提案され、これらのフッ素ゴム組成物であればＦＦＫＭよりも低価格で、非着香性、耐熱性および耐薬品性に優れるシール材が得られると謳われている。 In order to meet such requirements, Patent Documents 1 to 3 disclose that a fluororubber composition in which a glass filler and / or a true spherical nonporous silica (amorphous silicon dioxide) filler is blended with fluororubber, fluorine Fluororubber composition in which boron nitride filler is blended with rubber, true spherical nonporous silica (amorphous silicon dioxide) filler which may be surface-modified to fluororubber, and fine powder fluororesin filler , Fluorinated rubber compositions containing organic peroxide vulcanizing agents and co-crosslinking agents have been proposed. These fluorinated rubber compositions are less expensive than FFKM, and are non-flavoring, heat resistant and chemically resistant. It is said that a sealing material with excellent properties can be obtained.
ところで、前記の「着香」には、食品或いはその原料などの匂い成分がゴム部材に付着する着香（Ｉ）と、該匂い成分がゴム部材を介して後の製品（食品）に移行する着香（II）の二種類がある。しかしながら、本発明者等の研究の結果、特許文献１〜３のゴム組成物は、いずれの着香においても十分満足できる低着香性のレベルに達していないことが分かった。 By the way, in the above-mentioned “flavoring”, flavoring (I) in which an odor component such as food or its raw material adheres to the rubber member, and the odor component migrates to a subsequent product (food) through the rubber member. There are two types of flavoring (II). However, as a result of studies by the present inventors, it has been found that the rubber compositions of Patent Documents 1 to 3 have not reached a level of low flavoring that can be satisfactorily satisfied in any flavoring.
本発明は、上記のような事情に鑑みなされたものであり、その解決しようとする課題は、極めて良好な低着香性を有する、耐熱性および耐薬品性に優れるシール材等を実現できるフッ素ゴム組成物及び該フッ素ゴム組成物を用いたゴム部材（例えばシール材等）を提供することにある。 The present invention has been made in view of the circumstances as described above, and a problem to be solved is fluorine that can realize a sealing material having extremely good low flavor and excellent heat resistance and chemical resistance. An object of the present invention is to provide a rubber composition and a rubber member (for example, a sealing material) using the fluororubber composition.
本発明者らは、上記の課題を解決するために鋭意研究した結果、フッ素ゴムに、フッ素系界面活性剤を配合して得られるゴム組成物が極めて着香しにくいゴム組成物となり、かかるゴム組成物を加硫成形して得られるゴム部材は非常に優れた低着香性を有することを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have obtained a rubber composition obtained by blending a fluorosurfactant with a fluororubber, resulting in a rubber composition that is extremely difficult to perfume. It has been found that a rubber member obtained by vulcanization molding of the composition has a very excellent low fragrance property, and the present invention has been completed.
すなわち、本発明は以下の通りである。
（１）フッ素ゴムおよびフッ素系界面活性剤を含むフッ素ゴム組成物。
（２）上記（１）記載のフッ素ゴム組成物を加硫成形してなるゴム部材。
（３）食品製造機器用又は食品製造ライン用である、上記（２）記載のゴム部材。
That is, the present invention is as follows.
(1) A fluororubber composition containing fluororubber and a fluorosurfactant.
(2) A rubber member obtained by vulcanization molding of the fluororubber composition described in (1) above.
(3) The rubber member according to (2) above, which is for food production equipment or food production line.
本発明のフッ素ゴム組成物によれば、加硫成形により、極めて高いレベルの低着香性を有し、かつ、耐熱性及び耐薬品性に優れるゴム部材を得ることができる。従って、これを食品製造機器・食品製造ラインのシール材に適用することにより、匂い成分の移行の極めて低い製品（食品）を極めて効率よく製造することができる。また、付着した微量の匂い成分を除去する洗浄操作の頻度を著しく低減でき、かつ、洗浄操作によるシール材の劣化が小さいため、シール材の交換なしに、長期間、食品製造機器・食品製造ラインを連続稼動できる。
なお、本発明でいう「食品」とは「飲料」を含む概念である。また、「食品製造機器」とは単一の独立した機器だけでなく、食品製造ラインの一部に組み込まれた装置（機器）も含む概念である。
According to the fluororubber composition of the present invention, a rubber member having an extremely high level of low flavor and excellent in heat resistance and chemical resistance can be obtained by vulcanization molding. Therefore, by applying this to a sealing material for food production equipment and food production lines, it is possible to produce a product (food) with extremely low odor component migration very efficiently. In addition, the frequency of the cleaning operation to remove a small amount of attached odorous components can be significantly reduced, and the deterioration of the sealing material due to the cleaning operation is small, so there is no need to replace the sealing material for a long period of time. Can be operated continuously.
In the present invention, “food” is a concept including “beverage”. The “food production equipment” is a concept including not only a single independent equipment but also an apparatus (equipment) incorporated in a part of the food production line.
以下、本発明をその好適な実施形態に即して詳細に説明する。
本発明のフッ素ゴム組成物は、フッ素ゴム、およびフッ素系界面活性剤を含む。
Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
The fluororubber composition of the present invention contains a fluororubber and a fluorosurfactant.
フッ素ゴムとしては、フッ素原子を含有するゴム状物質であれば特に制限なく使用でき、２種類以上のものを混合して使用してもよく、例えば、ビニリデンフルオライド系ゴム（ＦＫＭ）、テトラフルオロエチレン−プロピレン系共重合体（ＦＥＰＭ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル系共重合体（ＦＦＫＭ）およびこれらの組み合わせなどが挙げられる。すなわち、より詳細には、ビニリデンフルオライド−ヘキサフルオロプロピレン−テトラフルオロエチレン系共重合体、ビニリデンフルオライド−ヘキサフルオロプロピレン系共重合体、ビニリデンフルオライド−テトラフルオロエチレン−パーフルオロアルキルビニルエーテル系共重合体、テトラフルオロエチレン−プロピレン系共重合体、エチレン−テトラフルオロエチレン−パーフルオロアルキルビニルエーテル系共重合体などが例示される。中でも、成形性、シール材等に成形した際のシール性、及びシール材に好適な強度などの観点から、ビニリデンフルオライド系ゴム（ＦＫＭ）が好適に使用される。 As the fluororubber, any rubber-like substance containing a fluorine atom can be used without particular limitation, and two or more kinds may be mixed and used. For example, vinylidene fluoride rubber (FKM), tetrafluoro Examples include ethylene-propylene copolymer (FEPM), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FFKM), and combinations thereof. More specifically, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Examples thereof include a copolymer, a tetrafluoroethylene-propylene copolymer, and an ethylene-tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. Among these, vinylidene fluoride rubber (FKM) is preferably used from the viewpoints of moldability, sealability when molded into a sealant, and strength suitable for the sealant.
本発明において、フッ素ゴムは、通常の重合手段によって製造することができ、その手段は特に制限されない。また、市販品を使用することができる。 In the present invention, the fluororubber can be produced by ordinary polymerization means, and the means is not particularly limited. Moreover, a commercial item can be used.
後述の比較例に示されるように、フッ素ゴムに架橋剤と共架橋剤を配合して得られるフッ素ゴム組成物はある程度良好な低着香性を示すが、フッ素ゴムに架橋剤と共架橋剤とともにフッ素系界面活性剤を配合することで、低着香性が著しく向上して、高度の低着香性を示すフッ素ゴム組成物を実現できる。 As shown in Comparative Examples described later, the fluororubber composition obtained by blending a fluororubber with a cross-linking agent and a co-crosslinking agent shows good low fragrance to some extent, In addition, by blending a fluorosurfactant, low fragrance properties are remarkably improved, and a fluororubber composition exhibiting high low fragrance properties can be realized.
本発明で使用するフッ素系界面活性剤は、特に限定されず、各種コーティング材料や成形材料等に、浸透・濡れ性、レベリング性、表面機能性等を高めるための添加剤として使用されている公知のフッ素原子を含有する界面活性剤を制限なく使用でき、カチオン性、アニオン性、ノニオン性のいずれも使用できるが、ノニオン性が好ましい。中でも、パーフルオロアルキル基を有するフッ素系界面活性剤が好ましく、具体例としては、たとえば、パーフルオロブチルスルホン酸塩、パーフルオロアルキル基含有カルボン酸塩、パーフルオロアルキル基含有リン酸エステル、パーフルオロアルキルエチレンオキシド付加物、パーフルオロアルキルトリメチルアンモニウム塩、パーフルオロアルキル基・親油性基含有オリゴマー、パーフルオロアルキル基・親水性基・親油性基含有オリゴマー、パーフルオロアルキル基含有オリゴマーなどが挙げられ、これらはいずれかを単独で使用するか、あるいは、２種以上併用して用いられる。これらの中でも、低着香性の点から、パーフルオロアルキル基・親油性基含有オリゴマー、パーフルオロアルキル基・親水性基・親油性基含有オリゴマーが好ましく、加硫への影響の点から、パーフルオロアルキル基・親油性基含有オリゴマーが、特に好ましい。 The fluorosurfactant used in the present invention is not particularly limited, and is known as an additive for improving penetration, wettability, leveling properties, surface functionality, etc., in various coating materials and molding materials. The surfactant containing a fluorine atom can be used without limitation, and any of cationic, anionic and nonionic properties can be used, but nonionic properties are preferred. Of these, fluorosurfactants having a perfluoroalkyl group are preferred. Specific examples include perfluorobutyl sulfonate, perfluoroalkyl group-containing carboxylate, perfluoroalkyl group-containing phosphate ester, and perfluoro. Examples include alkylethylene oxide adducts, perfluoroalkyltrimethylammonium salts, perfluoroalkyl group / lipophilic group-containing oligomers, perfluoroalkyl group / hydrophilic group / lipophilic group-containing oligomers, perfluoroalkyl group-containing oligomers, etc. Are used either alone or in combination of two or more. Among these, perfluoroalkyl group / lipophilic group-containing oligomers and perfluoroalkyl group / hydrophilic group / lipophilic group-containing oligomers are preferred from the viewpoint of low fragrance, and perfluoroalkyl group / hydrophilic group / lipophilic group-containing oligomers are preferred. A fluoroalkyl group / lipophilic group-containing oligomer is particularly preferred.
本発明において、フッ素系界面活性剤は特に限定されず、市販品をそのまま使用することができる。例えば、ＤＩＣ社製の「メガファック」、住友スリーエム社製の「ノベック」、ダイキン工業社製の「ユニダイン」、ネオス社製の「フタージェント」として入手することができる。パーフルオロアルキル基・親油性基含有オリゴマーとしては、メガファックＦ−４８０ＳＦ、Ｆ−４８７、Ｆ−４８９、Ｆ−１７２Ｄ、Ｆ−１７８ＲＭ、ＥＳＭ−１等が挙げられ、パーフルオロアルキル基・親水性基・親油性基含有オリゴマーとしては、メガファックＦ−４７０、Ｒ−０８、Ｆ−４７１、Ｆ−４７２ＳＦ、Ｆ−４７４、Ｆ−４７５、Ｒ−３０、Ｆ−４７７、Ｆ−４７９、ＭＣＦ−３５０ＳＦ等が挙げられる。 In the present invention, the fluorosurfactant is not particularly limited, and a commercially available product can be used as it is. For example, “Mega Fuck” manufactured by DIC, “Novec” manufactured by Sumitomo 3M, “Unidyne” manufactured by Daikin Industries, Ltd., and “Futgent” manufactured by Neos can be obtained. Examples of the perfluoroalkyl group / lipophilic group-containing oligomer include Megafac F-480SF, F-487, F-489, F-172D, F-178RM, ESM-1, and the like. As the group / lipophilic group-containing oligomer, Megafac F-470, R-08, F-471, F-472SF, F-474, F-475, R-30, F-477, F-479, MCF- 350SF etc. are mentioned.
本発明のフッ素ゴム組成物において、フッ素系界面活性剤の含有量は、フッ素ゴム１００質量部に対して、好ましくは０．１〜３０質量部、より好ましくは０．５〜１０質量部、さらに好ましくは１．０〜８質量部である。フッ素系界面活性剤の含有量が０．１質量部未満では、低着香性の顕著な改善効果が得られないおそれがあり、また３０質量部を超えると、フッ素系界面活性剤の配合による低着香性の改善効果が頭打ちになるだけでなく、ロール加工性や圧縮永久ひずみが悪化する傾向となり、好ましくない。 In the fluororubber composition of the present invention, the content of the fluorosurfactant is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and more preferably 100 parts by mass of the fluororubber. Preferably it is 1.0-8 mass parts. If the content of the fluorosurfactant is less than 0.1 parts by mass, there is a possibility that a remarkable improvement effect of low flavor is not obtained, and if it exceeds 30 parts by mass, it depends on the blending of the fluorosurfactant. Not only does the effect of improving the low fragrance reach a peak, but roll processability and compression set tend to deteriorate, which is not preferable.
本発明のフッ素ゴム組成物には、硬度調整や強度確保のために、本発明の効果を損なわない範囲で充填剤を配合することができる。特に、ＰＴＦＥはフッ素ゴム組成物に対する補強効果が大きく、ＰＴＦＥを配合したフッ素ゴム組成物の加硫成形物は、圧縮永久ひずみおよび耐薬品性に優れているため、本発明組成物に対して、好適に配合できる。また、ＰＴＦＥを配合することにより、加硫成形物は用途に適した硬度（例えば、シール材用途の場合、ショアＡ５５〜Ａ９０（瞬間値）程度）の対応が可能になる。 In the fluororubber composition of the present invention, a filler can be blended within a range that does not impair the effects of the present invention in order to adjust hardness and secure strength. In particular, PTFE has a large reinforcing effect on the fluororubber composition, and the vulcanized molded product of the fluororubber composition blended with PTFE is excellent in compression set and chemical resistance. It can mix | blend suitably. Further, by blending PTFE, the vulcanized molded product can cope with a hardness suitable for the application (for example, in the case of a sealing material, about Shore A55 to A90 (instantaneous value)).
前記ＰＴＦＥは、任意の形態のものを使用できるが、フッ素ゴム組成物の均質性、および成形性を得る観点から、微粉末が好ましい。また、微粉末の場合、フッ素ゴム組成物の加硫成形物への補強効果が得られ、強度や圧縮永久ひずみが向上する傾向にある。ＰＴＦＥ微粉末の平均粒径は、好ましくは０．０５〜２００μｍであり、より好ましくは１〜１００μｍであり、さらに好ましくは３〜３０μｍである。なお、平均粒径は次の方法で測定される。 The PTFE can be used in any form, but fine powder is preferable from the viewpoint of obtaining homogeneity and moldability of the fluororubber composition. Moreover, in the case of fine powder, the reinforcement effect to the vulcanization molding of a fluororubber composition is acquired, and there exists a tendency for an intensity | strength and a compression set to improve. The average particle diameter of the PTFE fine powder is preferably 0.05 to 200 μm, more preferably 1 to 100 μm, and further preferably 3 to 30 μm. The average particle size is measured by the following method.
測定対象物（粒状物）を水またはエタノールなどの有機液体に投入し、３５ｋＨｚ〜４０ｋＨｚ程度の超音波を付与した状態にて約２分間分散処理して得た分散液を用い、かつその場合の粒状物の量は該分散液のレーザ透過率（入射光量に対する出力光量の比）が７０％〜９５％となる量とし、次いで該分散液について、マイクロトラック粒度分析計にかけてレーザー光の散乱により個々の粒状物の粒径（Ｄ１、Ｄ２、Ｄ３、…）、および各粒径ごとの存在個数（Ｎ１、Ｎ２、Ｎ３、…）を計測する（個々の粒状物の粒径（Ｄ）は、マイクロトラック粒度分析計によれば種々の形状の粒状物ごとに球相当径が自動的に測定される。）。視野内に存在する個々の粒子の個数（Ｎ）と各粒径（Ｄ）とから、下記式（１）にて平均粒径を算出する。
平均粒径＝（ΣＮＤ3／ΣＮ）1/3（１）
A measurement object (granular material) is put into an organic liquid such as water or ethanol, and a dispersion obtained by dispersing for about 2 minutes in a state of applying an ultrasonic wave of about 35 kHz to 40 kHz is used. The amount of the particulate matter is such that the laser transmittance of the dispersion (ratio of the amount of output light to the amount of incident light) is 70% to 95%, and then the dispersion is individually subjected to scattering by laser light on a microtrack particle size analyzer. , And the number of particles (N1, N2, N3,...) For each particle size are measured (the particle size (D) of each granular material is micro According to the track particle size analyzer, the equivalent sphere diameter is automatically measured for each granular material of various shapes. From the number (N) of individual particles present in the field of view and each particle size (D), the average particle size is calculated by the following formula (1).
Average particle size = (ΣND 3 / ΣN) 1/3 (1)
本発明のゴム組成物において、ＰＴＦＥの含有量は、フッ素ゴム１００質量部に対して、好ましくは１〜１００質量部、より好ましくは１０〜９０質量部、さらに好ましくは２０〜８０質量部である。ＰＴＦＥの含有量が１質量部未満である場合、硬度調整を所望した場合、硬度変化が小さい傾向にある。また１００質量部を超えると、ロール加工性が悪くなるとともに、組成物を加硫成形して得られるゴム製品（ゴム部材）の圧縮永久ひずみも悪くなり、また、一般的なシール材に必要な伸び（１００％以上）を維持できなくなる。 In the rubber composition of the present invention, the PTFE content is preferably 1 to 100 parts by mass, more preferably 10 to 90 parts by mass, and still more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the fluororubber. . When the content of PTFE is less than 1 part by mass, the hardness change tends to be small when hardness adjustment is desired. On the other hand, when it exceeds 100 parts by mass, the roll processability is deteriorated, and the compression set of the rubber product (rubber member) obtained by vulcanization molding of the composition is also deteriorated, which is necessary for a general sealing material. Elongation (100% or more) cannot be maintained.
本発明のフッ素ゴム組成物には、通常、フッ素ゴムの加硫（架橋）処理に使用される公知の架橋剤、共架橋剤などが配合され、加硫（架橋）処理して使用され得る。加硫系としては、例えば、過酸化物加硫、ポリオール加硫、アミン加硫などが例示されるが、用いる加硫系、加硫方法は特に限定されず、加硫方法として知られている公知の加硫系（例えば、公知のフッ素ゴムの加硫系）、加硫方法を使用することができる。また、本発明の効果を損なわない範囲で、老化防止剤、安定化剤、可塑剤、架橋助剤などの各種の添加剤を必要に応じて配合することができる。これら架橋剤、共架橋剤、添加剤等は、常法に従って適当量を配合すればよい。 The fluororubber composition of the present invention is usually blended with a known crosslinking agent, co-crosslinking agent and the like used for vulcanization (crosslinking) treatment of fluororubber, and can be used after vulcanization (crosslinking) treatment. Examples of the vulcanization system include peroxide vulcanization, polyol vulcanization, and amine vulcanization, but the vulcanization system and vulcanization method used are not particularly limited and are known as vulcanization methods. A known vulcanization system (for example, a known fluororubber vulcanization system) or a vulcanization method can be used. Moreover, various additives, such as an anti-aging agent, a stabilizer, a plasticizer, and a crosslinking aid, can be blended as necessary within a range not impairing the effects of the present invention. These crosslinking agents, co-crosslinking agents, additives and the like may be blended in appropriate amounts according to a conventional method.
本発明のフッ素ゴム組成物を、従来公知のインタミックス、ニーダ、バンバリーミキサ等の混練機、オープンロール又は二軸混練押出機等を用いて混練した後、適当な形に予備成形し、射出成形機、圧縮成形機、加熱プレス機又は押出成形機等を用いて所望の形状に成形してゴム部材を得ることができる。 The fluororubber composition of the present invention is kneaded using a kneader such as a conventionally known intermix, kneader or Banbury mixer, an open roll or a twin-screw kneading extruder, and then pre-molded into an appropriate shape and injection molded. A rubber member can be obtained by molding into a desired shape using a machine, a compression molding machine, a heating press machine or an extrusion molding machine.
混練及び成形の条件は特に限定されないが、混練は例えばＪＩＳ Ｋ６２９９を参考にして実施すればよい。
また、加硫成形においては、本発明では過酸化物加硫を含むので、例えば１４０℃〜２００℃で２分間〜３０分間の一次加硫を施した後、必要に応じて１５０〜２３０℃で１時間〜２４時間の二次加硫を施すというような条件で行うのが好ましい。
The conditions for kneading and molding are not particularly limited, but kneading may be performed with reference to, for example, JIS K6299.
Further, in vulcanization molding, since the present invention includes peroxide vulcanization, for example, after performing primary vulcanization at 140 to 200 ° C. for 2 to 30 minutes, and at 150 to 230 ° C. as necessary. It is preferable to carry out under such conditions that secondary vulcanization is performed for 1 hour to 24 hours.
例えば、パッキンなどのリング状のシール材を得る場合は、フッ素ゴム組成物を調製後、それをロールにて圧延し（予備成形）、紐状に切断し、ついで、この紐状のゴム組成物をリング状の金型に入れ、加熱プレス（一次加硫）することで、リング状のシール材を作製することができ、このリング状のシール材を電気炉等に入れ、熱処理（二次加硫）を行うことで最終製品とする。 For example, when obtaining a ring-shaped sealing material such as packing, after preparing a fluororubber composition, it is rolled with a roll (preliminary molding), cut into a string, and then the string-shaped rubber composition Is put into a ring-shaped mold and heated and pressed (primary vulcanization) to produce a ring-shaped sealing material. The ring-shaped sealing material is placed in an electric furnace or the like and subjected to heat treatment (secondary vulcanization). To make the final product.
本発明のフッ素ゴム組成物は極めて着香しにくいため、食品製造機器、食品製造ラインの部品として使用されるシール材、ガスケット、ダイヤフラム等の種々のゴム部材（ゴム製品）に好適に使用できる。特に、高いレベルの低着香性を示すため、低着香性が長期間持続する低着香性シール材を実現できる。なお、シール材とする場合、その形状は、Ｏリング、Ｄリング、Ｕパッキン、Ｙパッキン、リップシール（軸シール）などその目的に応じて従来公知の形状より適宜選ばれる。またシール材の大きさも特に限定はなく、目的に応じて適宜選ばれる。 Since the fluororubber composition of the present invention is extremely difficult to perfume, it can be suitably used for various rubber members (rubber products) such as sealing materials, gaskets, diaphragms and the like used as parts in food production equipment and food production lines. In particular, since it exhibits a high level of low fragrance, a low fragrance sealing material that maintains low fragrance for a long period of time can be realized. In addition, when using it as a sealing material, the shape is suitably selected from conventionally well-known shapes according to the objectives, such as O ring, D ring, U packing, Y packing, and a lip seal (shaft seal). Further, the size of the sealing material is not particularly limited, and is appropriately selected according to the purpose.
以下、実施例と比較例を示して本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to a following example.
（実施例１〜６、比較例１〜４）
＜ゴム試料の調製＞
下記表１、２に記載の配合をオープンロールでＪＩＳ Ｋ６２９９を参考として混練し、フッ素ゴム組成物とした（表１、２中の数値は質量部である）。フッ素ゴム組成物を１６５℃、１０分間でプレス加硫成形（一次加硫）し、２００℃、４時間のオーブン加硫（二次加硫）を行い、ゴム試料を調製した。
(Examples 1-6, Comparative Examples 1-4)
<Preparation of rubber sample>
The formulations shown in Tables 1 and 2 were kneaded with an open roll with reference to JIS K6299 to obtain fluororubber compositions (the numerical values in Tables 1 and 2 are parts by mass). The fluororubber composition was press vulcanized (primary vulcanization) at 165 ° C. for 10 minutes, and oven vulcanized (secondary vulcanization) at 200 ° C. for 4 hours to prepare a rubber sample.
表１、２中、「ダイエルＧ−９０２」はビニリデンフルオライド−ヘキサフルオロプロピレン−テトラフルオロエチレン系共重合体、ルブロンＬ−５（ＰＴＦＥ微粉末）の平均粒径は５μｍ、フルオンＬ１６９Ｊ（ＰＴＦＥ微粉末）の平均粒径は１７μｍ、ダイニオンＴＦ９２０７（ＰＴＦＥ微粉末）の平均粒径は４μｍである。 In Tables 1 and 2, “Daiel G-902” is a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, Lubron L-5 (PTFE fine powder) has an average particle size of 5 μm, and Fluorone L169J (PTFE fine). The average particle size of the powder) is 17 μm, and the average particle size of Dyneon TF9207 (PTFE fine powder) is 4 μm.
実施例１〜６及び比較例１〜４のゴム試料について以下の試験を行った。
＜物性評価試験＞
ａ）常態物性（デュロメータ硬さ、引張強さ、伸び、１００％引張応力）
硬さについては、ＪＩＳ Ｋ ６２５３：１９９７により、タイプＡデュロメータ試験機でゴム試料について瞬間値を測定した。引張強さ、伸び、１００％引張応力については、ＪＩＳ Ｋ ６２５１により、ダンベル状３号形としたゴム試料を測定した。
ｂ）圧縮永久歪試験
圧縮永久歪率は、ＪＩＳ Ｋ ６２６２により、大形試験片としたゴム試料を圧縮率２５％で圧縮し、２００℃で７０時間放置後、ひずみを取り除き規定時間後に試験片の厚さを測定して求めた。
The following tests were performed on the rubber samples of Examples 1 to 6 and Comparative Examples 1 to 4.
<Physical property evaluation test>
a) Normal properties (durometer hardness, tensile strength, elongation, 100% tensile stress)
About hardness, the instantaneous value was measured about the rubber sample with the type A durometer testing machine by JISK6253: 1997. Regarding the tensile strength, elongation, and 100% tensile stress, a rubber sample having a dumbbell shape No. 3 was measured according to JIS K 6251.
b) Compression set test The compression set was measured according to JIS K 6262 by compressing a rubber sample as a large test piece at a compression rate of 25%, leaving it at 200 ° C for 70 hours, removing the strain, and then a test piece after a specified time. The thickness of was measured.
＜官能試験による着香評価＞
ａ）試験方法
１）りんご果汁入り飲料「なっちゃん！ダブルりんご」（「なっちゃん」はサントリーホールディングス（株）の登録商標）５００ｍｌをビーカーに入れた。
２）ゴム試料（２５×４５×２ｔ（ｍｍ））をその中に２４時間浸漬した。
３）ゴム試料を取り出した。
４）ゴム試料を精製水１Ｌ（室温）で５分間洗浄した。
５）ゴム試料を２％ＮａＯＨ水溶液１Ｌ（８０℃）で５分間洗浄した。
６）ゴム試料を精製水１Ｌ（室温）で５分間洗浄した。
７）ゴム試料を２％硝酸水溶液１Ｌ（８０℃）で５分間洗浄した。
８）ゴム試料を精製水１Ｌ（室温）で５分間洗浄した。
９）ゴム試料を１０００ｐｐｍ次亜塩素酸ナトリウム水溶液１Ｌ（８０℃）で５分間洗浄した。
１０）ゴム試料を精製水１Ｌ（室温）で５分間洗浄した。
１１）ゴム試料を取り出し、水分を除去してから、袋に入れた。
１２）ゴム試料の臭気を確認した。
１３）ゴム試料を精製水１００ｍｌに浸漬し、１０分間煮沸した。
１４）煮沸した精製水を放冷した。
１５）冷却後、精製水の臭気を確認した。
１６）以上の各洗浄工程の順序、洗浄液、および温度について下記表３にまとめて示した。
<Aroma evaluation by sensory test>
a) Test Method 1) 500 ml of beverage “Nacchan! Double apple” (registered trademark of Suntory Holdings Co., Ltd.), a beverage containing apple juice, was placed in a beaker.
2) A rubber sample (25 × 45 × 2 t (mm)) was immersed therein for 24 hours.
3) A rubber sample was taken out.
4) The rubber sample was washed with 1 L of purified water (room temperature) for 5 minutes.
5) The rubber sample was washed with 1 L of 2% NaOH aqueous solution (80 ° C.) for 5 minutes.
6) The rubber sample was washed with 1 L of purified water (room temperature) for 5 minutes.
7) The rubber sample was washed with 1 L of a 2% nitric acid aqueous solution (80 ° C.) for 5 minutes.
8) The rubber sample was washed with 1 L of purified water (room temperature) for 5 minutes.
9) The rubber sample was washed for 5 minutes with 1 L of a 1000 ppm sodium hypochlorite aqueous solution (80 ° C.).
10) The rubber sample was washed with 1 L of purified water (room temperature) for 5 minutes.
11) A rubber sample was taken out and water was removed, and then put into a bag.
12) The odor of the rubber sample was confirmed.
13) The rubber sample was immersed in 100 ml of purified water and boiled for 10 minutes.
14) Boiled purified water was allowed to cool.
15) After cooling, the odor of purified water was confirmed.
16) The order of the above cleaning steps, the cleaning liquid, and the temperature are summarized in Table 3 below.
ｂ）対照試験および評価の指標
下記の表６の配合をオープンロールで混練し、１６５℃、２０分間でプレス加硫成形し、１７０℃、１時間のオーブン加硫を行って、エチレンプロピレンゴム（ＥＰＤＭ）の試料（２５×４５×２ｔ（ｍｍ））を調製し、このＥＰＤＭ試料を用いたことの他は、上記実施例及び比較例と同じ手順に従い、同様に官能試験による着香評価を行い、試料の臭気、精製水の臭気を確認した。
このときの臭気の度合いを試料、煮沸した水ともに５とし、何も操作をしなかったＥＰＤＭの試料を０、何ら処理していない精製水を０とし、実施例１〜６及び比較例１〜４の試料につき、０〜５の６段階でヒト臭覚による官能評価を行った。各評価は７〜１０人で実施し、平均を取って下記表４及び５に示した。なお、表４、５には物性評価試験の結果も示した。
b) Index of control test and evaluation The composition shown in Table 6 below was kneaded with an open roll, press vulcanized at 165 ° C. for 20 minutes, and oven vulcanized at 170 ° C. for 1 hour to produce ethylene propylene rubber ( EPDM) sample (25 × 45 × 2t (mm)) was prepared, and except that this EPDM sample was used, the same procedure as in the above Examples and Comparative Examples was followed, and the flavor evaluation was performed by the sensory test in the same manner. The odor of the sample and the odor of purified water were confirmed.
The degree of odor at this time was set to 5 for both the sample and the boiled water, the sample for EPDM that had not been operated at all was set to 0, the purified water that had not been treated at all was set to 0, and Examples 1 to 6 and Comparative Examples 1 to Sensory evaluation by human olfaction was performed on 6 samples from 0 to 5 for 4 samples. Each evaluation was carried out by 7 to 10 people, and the averages are shown in Tables 4 and 5 below. Tables 4 and 5 also show the results of physical property evaluation tests.
実施例１〜６、比較例１〜４のフッ素ゴム組成物の常態物性、圧縮永久歪率は、通常のフッ素ゴムのものと同等であり、調製したゴム試料は良好な物性を有していた。 The normal physical properties and compression set of the fluororubber compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were equivalent to those of ordinary fluororubber, and the prepared rubber samples had good physical properties. .
官能試験の評価結果は、実施例１〜６においては、５としたＥＰＤＭの臭気の度合いに対して、ゴム試料、精製水とも１．０未満であり、本発明のフッ素ゴム組成物により優れた低着香性を示すゴム部材及びシール材が得られることが示された。
このように、本発明の低着香性フッ素ゴム組成物は、耐熱性及び耐薬品性に優れる低着香性のゴム部材を与え得る。従って、種々の用途に好適に使用することができ、中でも、食品製造機器・食品製造ラインにおけるシール材として、特に好適に使用することができる。なお、食品製造機器・食品製造ラインは、具体的には、例えば、スクリューコンベアー、ロータリーバルブ、モーノポンプ、ヘンシェルミキサー、計量充填機、遠心分離機又はサニタリータンク、清涼飲料水ボトリングシステム等が挙げられる。
In Examples 1 to 6, the evaluation results of the sensory test were less than 1.0 for both the rubber sample and the purified water with respect to the degree of odor of EPDM set to 5, which was superior to the fluororubber composition of the present invention. It was shown that a rubber member and a sealing material exhibiting low flavoring properties can be obtained.
Thus, the low fragrance fluororubber composition of the present invention can provide a low fragrance rubber member excellent in heat resistance and chemical resistance. Therefore, it can be suitably used for various applications, and among them, it can be particularly suitably used as a sealing material in food production equipment and food production lines. Specific examples of food production equipment and food production lines include screw conveyors, rotary valves, Mono pumps, Henschel mixers, metering and filling machines, centrifuges or sanitary tanks, soft drink bottling systems, and the like.
本発明の低着香性フッ素ゴム組成物は、下水処理施設やトイレ関連機器、水関連機器等への使用も期待できる。 The low fragrance fluororubber composition of the present invention can be expected to be used for sewage treatment facilities, toilet-related equipment, water-related equipment, and the like.
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| JP2013181050A (en) * | 2012-02-29 | 2013-09-12 | Mitsubishi Chemicals Corp | Interlayer filler composition for three dimensional integrated circuit, coating liquid, and method of manufacturing three dimensional integrated circuit |
| US9441101B2 (en) | 2012-12-07 | 2016-09-13 | Nok Corporation | Fluororubber composition |
| WO2018062235A1 (en) * | 2016-09-27 | 2018-04-05 | ダイキン工業株式会社 | Fluororubber molded article |
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| JPH11172232A (en) * | 1997-12-09 | 1999-06-29 | Asahi Glass Co Ltd | Sealing material composition |
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| JP2013181050A (en) * | 2012-02-29 | 2013-09-12 | Mitsubishi Chemicals Corp | Interlayer filler composition for three dimensional integrated circuit, coating liquid, and method of manufacturing three dimensional integrated circuit |
| US9441101B2 (en) | 2012-12-07 | 2016-09-13 | Nok Corporation | Fluororubber composition |
| WO2018062235A1 (en) * | 2016-09-27 | 2018-04-05 | ダイキン工業株式会社 | Fluororubber molded article |
| JP2018070864A (en) * | 2016-09-27 | 2018-05-10 | 山陽色素株式会社 | Fluorine rubber molding |
| CN109790348A (en) * | 2016-09-27 | 2019-05-21 | 大金工业株式会社 | Fluorubber molded product |
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