JPH0476045A - Lubricating rubber composition - Google Patents
Lubricating rubber compositionInfo
- Publication number
- JPH0476045A JPH0476045A JP19099590A JP19099590A JPH0476045A JP H0476045 A JPH0476045 A JP H0476045A JP 19099590 A JP19099590 A JP 19099590A JP 19099590 A JP19099590 A JP 19099590A JP H0476045 A JPH0476045 A JP H0476045A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- tetrafluoroethylene
- rubber composition
- fluoropolymer
- lubricating rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 title claims description 18
- 230000001050 lubricating effect Effects 0.000 title claims description 13
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 20
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 20
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 16
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 15
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 13
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920001038 ethylene copolymer Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 12
- 238000013016 damping Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- -1 Perfluoro Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229920005560 fluorosilicone rubber Polymers 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 102100027262 Electron transfer flavoprotein subunit beta Human genes 0.000 description 1
- 229920006358 Fluon Polymers 0.000 description 1
- 101001057122 Homo sapiens Electron transfer flavoprotein subunit beta Proteins 0.000 description 1
- 229920006369 KF polymer Polymers 0.000 description 1
- 229920006367 Neoflon Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920006364 Rulon (plastic) Polymers 0.000 description 1
- 101100273965 Solanum lycopersicum HCR9-0 gene Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000370 acceptor Substances 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
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NRNCYVBFPDDJNE-UHFFFAOYSA-N pemoline Chemical compound O1C(N)=NC(=O)C1C1=CC=CC=C1 NRNCYVBFPDDJNE-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 1
Landscapes
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は潤滑性ゴム組成物に関するものである。[Detailed description of the invention] [Industrial application field] This invention relates to a lubricating rubber composition.
従来、潤滑性ゴム材としてウレタン系ゴムおよびジエン
系ゴムが優秀な耐油性、耐摩耗性、ゴム弾性、機械的強
度等を生かして、オイルシール、グラスラン、等速ジヨ
イントなどのダストブーツ、各種バルブ、トナーシール
等その使用される分野は多岐にわたっているが、近年、
機械や自動車の高性能化、高速化などに伴い、摺動部に
使われるものにはさらに優れた潤滑性が要求されるよう
になった。また、複写機、プリンタ、ファクシミリ、コ
ンピュータ等の情報関連機器のように室内で使用するも
のについては、それらが作動するときに発生する音が騒
音として大きい問題となっており、そのため消音機能を
有し摺動特性に優れたゴム成形品の要求が高まって来た
。さらに最近は、半導体レーザを利用したコンパクトデ
ィスク、ビデオディスク、光ファイル等の光関連機器に
おいて、集光レンズによって結ばれるスポットで正しく
ディスク面上のビットの情報を読み取るためには、外部
からこれら機器に加えられる振動に対して良好な制振作
用も兼ね備えた潤滑性に優れた摺動材ば、特公昭５７−
３２９５０号公報に示・されているように、オレフィン
系樹脂を熱融着させる方法（融着法と略記）、造膜性重
合体を溶解した有機溶剤中にフッ素樹脂等の固体潤滑剤
を分散させた液を塗布して焼き付ける方法（塗布法と略
記）またはフッ素樹脂等の固体潤滑剤もしくはシリコー
ンオイル等の潤滑油番別個にまたは同時にゴム弾性体に
配合するなどの方法（ａ！大人法略記）が採られて来た
が、これら方法にはそれぞれつぎのような欠点がある。Conventionally, urethane rubber and diene rubber have been used as lubricating rubber materials, taking advantage of their excellent oil resistance, abrasion resistance, rubber elasticity, mechanical strength, etc., to manufacture oil seals, glass runs, dust boots such as constant velocity joints, and various valves. , toner stickers, etc. They are used in a wide variety of fields, but in recent years,
As machinery and automobiles become more sophisticated and faster, materials used in sliding parts are required to have even better lubricity. Additionally, information-related equipment such as copying machines, printers, facsimile machines, computers, and other information-related equipment used indoors has become a major problem due to the noise they generate when they operate, so it is important to have a noise reduction function. Demand for rubber molded products with excellent sliding properties has increased. Furthermore, recently, in optical-related equipment such as compact discs, video discs, and optical files that use semiconductor lasers, in order to correctly read the information of the bits on the disc surface with a spot focused by a condensing lens, it is necessary to use these equipment externally. A sliding material with excellent lubricity that also has a good damping effect against vibrations applied to
As shown in Japanese Patent No. 32950, a method of thermally fusing an olefin resin (abbreviated as fusing method) involves dispersing a solid lubricant such as a fluororesin in an organic solvent in which a film-forming polymer is dissolved. A method of applying and baking a liquid that has been applied (abbreviated as coating method) or a method of blending a solid lubricant such as fluororesin or a lubricant oil such as silicone oil separately or simultaneously with a rubber elastic body (a! ) have been adopted, but each of these methods has the following drawbacks.
すなわち、晴着法または融着法においては、フッ素樹脂
フィルムもしくはオレフィン系樹脂フィルムの基材に対
する接着性が非常に悪く、特にフッ素樹脂フィルムの場
合は予め表面処理（アルカリ金属もしくはイオンスパッ
タリング等による処理）をする必要があり、たとえ表面
処理が施されているフッ素樹脂フィルムであっても、ま
たオレフィン系樹脂の場合であっても、接着性は不充分
であって、使用中にフィルムはよく剥離するし、複雑な
形状の成形体には利用しにくく、フィルムの膜厚が大き
いため、ゴム状弾性体が本来持って料が要求されるよう
になった。In other words, in the spray deposition method or fusion method, the adhesion of the fluororesin film or olefin resin film to the base material is very poor, and especially in the case of the fluororesin film, it is necessary to pre-surface treatment (treatment with alkali metal or ion sputtering, etc.). Even with fluororesin films that have been surface-treated, or even with olefin resins, the adhesion is insufficient and the film often peels off during use. However, it is difficult to use it for molded bodies with complex shapes, and the film thickness is large, so rubber-like elastic bodies are inherently required to use materials.
これらの諸要求を満たす目的で、摺動性の良い合成樹脂
、たとえばポリアミド、ポリアセタール、ポリオレフィ
ン、フッ素樹脂等を用いるか、またはこれら樹脂に各種
エラストマーを配合するなど多くの試みがなされたが、
従来のゴム自体が有するシール性、追従性、制振性、消
音性等の特性が殆んど生かされず、また従来の配合のジ
エン系ゴム組成物においては摺動特性について決して満
足出来るものとはいえないので、大きい駆動力を必要と
したり、摩擦音を発したり、スティックスリップを起こ
したりするばかりでなく、使用時間の長期化につれて摩
擦抵抗は増大し、摩耗は激しくなり、さらには摺動部に
おける発熱も大きくなって、ゴム状弾性体自体の変形を
も招くなど多くの問題があった。一般にゴム状弾性体を
有する摺動材料の摩擦抵抗を小さくするためには、ゴム
状弾性体の表面に、たとえば、特公昭４６−２３６８１
号公報に示されているように、フッ素樹脂フィルムを貼
り合わせる方法（貼着法と略記）、また、たとえいる優
れたシール性、追従性、制振性などの諸特性に悪影響を
及ぼすなどの欠点がある。そして、つぎの塗布法におい
ては、接着力の点では前記の貼着法、融着法よりは勝っ
ているが、元来潤滑性を有しない重合体を使用するため
に、充分な潤滑性を発揮させることは困難であり、さら
に混入法においては、固体潤滑剤を配合する場合、少量
では潤滑性が劣り、多量のときにはゴム状弾性体本来の
諸特性を妨害し、潤滑油を配合する場合には、摺動時に
潤滑油を浸み出させることにより摺動特性を発現させよ
うとするものであるが、摩擦係数力Ｓ安定しないこと、
温度が高くなると油が浸出してしまうこと、成形性が悪
いこと、成形時もしくは混練時に油が分離しやすいこと
、基材の諸特性が阻害されること、摺動した面が油で汚
染されてほこり等が付着しやすいこと、−旦油が切れる
と異常摩耗を起こすなど非常に多くの問題を抱えている
。このような混入法の具体例としては、フッ素ゴムに低
分子量テトラフルオロエチレンとフッ化カーボンを混練
したもの（特開昭５８−２３８４６号）もあるが、」二
記したように、摩擦特性、耐摩耗性において満足できる
ものでなかった。In order to meet these requirements, many attempts have been made to use synthetic resins with good sliding properties, such as polyamide, polyacetal, polyolefin, fluororesin, etc., or to mix various elastomers with these resins.
The properties of conventional rubber itself, such as sealing properties, conformability, vibration damping properties, and sound deadening properties, are hardly utilized, and diene rubber compositions with conventional formulations are never able to satisfy sliding properties. Not only does this require a large driving force, generate frictional noise, and cause stick-slip, but the longer it is used, the more frictional resistance increases, the wear becomes severe, and the sliding parts become damaged. There were many problems such as increased heat generation and deformation of the rubber-like elastic body itself. Generally, in order to reduce the frictional resistance of a sliding material having a rubber-like elastic body, it is necessary to coat the surface of the rubber-like elastic body with
As shown in the publication, there is a method of laminating fluororesin films (abbreviated as adhesion method), and there are also methods that may adversely affect various properties such as excellent sealing performance, tracking performance, and vibration damping performance. There are drawbacks. The next coating method is superior to the pasting and fusing methods described above in terms of adhesive strength, but since it uses a polymer that does not inherently have lubricity, it is necessary to ensure sufficient lubricity. Furthermore, in the mixing method, when a solid lubricant is blended, the lubricity is poor if it is used in a small amount, and if it is used in a large amount, it interferes with the inherent properties of the rubber-like elastic material. Although this method attempts to develop sliding characteristics by exuding lubricating oil during sliding, the friction coefficient force S is not stable;
When the temperature is high, oil leaches, poor moldability, oil tends to separate during molding or kneading, various properties of the base material are impaired, and sliding surfaces become contaminated with oil. They have many problems, such as the fact that dust and other substances tend to adhere to them, and abnormal wear occurs when the oil runs out. As a specific example of such a mixing method, there is a method in which low molecular weight tetrafluoroethylene and fluorocarbon are kneaded with fluororubber (Japanese Patent Application Laid-Open No. 58-23846), but as mentioned in 2. The wear resistance was not satisfactory.
このように、従来の技術においては、シール性、追従性
、消音性、制振性などのゴム状弾性体が元来有している
機能を低下させず、しかも摩擦係数が経時的に低く安定
し、かつ摩耗係数の小さいゴム状弾性を有する摺動材料
は得られないという問題点があり１．これを解決するこ
とが課題であった。In this way, conventional technology does not reduce the inherent functions of rubber-like elastic bodies such as sealing performance, tracking performance, sound deadening performance, and vibration damping performance, and furthermore, the coefficient of friction remains low and stable over time. However, there is a problem that a sliding material with rubber-like elasticity and a small coefficient of wear cannot be obtained.1. The challenge was to solve this problem.
上記の課題を解決するためにこの発明は、フッ素ゴムと
、熱可塑性フルオロ樹脂と低分子量含フッ素重合体とを
配合して潤滑性ゴム組成物とする手段を採用したもので
ある。以下その詳細を述べる。In order to solve the above problems, the present invention employs a method of blending fluororubber, a thermoplastic fluororesin, and a low molecular weight fluoropolymer to form a lubricating rubber composition. The details will be described below.
まず、この発明におけるフッ素ゴムとは、平均して１個
以上のフッ素原子を含む単位モノマーの重合体または共
重合体であって、ガラス転移点が室温以下であり、室温
でゴム状弾性を有するものであれば、特に限定されるも
のでなく、広範囲のまた、この発明における熱可塑性フ
ルオロ樹脂とは、主鎖に炭素鎖を持ち、側鎖にフッ素の
結合をもつポリマーであって、たとえば、テトラフルオ
ロエチレン重合体（以下ＰＴＦＥと略記する）、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
ル共重合体（以下ＰＦＡと略記する）、テトラフルオロ
エチレン・ヘキサフルオロプロピレン・パーフルオロア
ルキルビニルエーテル共重合体（以下ＥＰＥと略記する
）、テトラフルオロエチレン・ヘキサフルオロプロピレ
ン共重合体（以下Ｆ［ｉＰと略記する）、テトラフルオ
ロエチレン・エチレン共重合体（以下ＥＴＦＥと略記す
る）、トリフルオロクロロエチレン重合体（以下ＣＴＦ
Ｅと略記するＬｌ−リフルオロクロロエチレン・エチレ
ン共重合体（以下ＥＣＴＦＥと略記する）、ポリビニル
フルオライド（以下ＰＶＦと略記する）およびポリビニ
リデンフルオライド（以下ＰＶＤＦと略記する）からな
る群から選ばれる１種以上の重合体であることが好まし
い。First, the fluororubber in this invention is a polymer or copolymer of unit monomers containing on average one or more fluorine atoms, has a glass transition point below room temperature, and has rubber-like elasticity at room temperature. The thermoplastic fluororesin in the present invention is a polymer having a carbon chain in the main chain and a fluorine bond in the side chain, for example, Tetrafluoroethylene polymer (hereinafter abbreviated as PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (hereinafter abbreviated as PFA), tetrafluoroethylene/hexafluoropropylene/perfluoroalkyl vinyl ether copolymer (hereinafter EPE) ), tetrafluoroethylene/hexafluoropropylene copolymer (hereinafter abbreviated as F[iP), tetrafluoroethylene/ethylene copolymer (hereinafter abbreviated as ETFE), trifluorochloroethylene polymer (hereinafter abbreviated as CTF)
Selected from the group consisting of Ll-lifluorochloroethylene/ethylene copolymer (hereinafter abbreviated as ECTFE), abbreviated as E, polyvinyl fluoride (hereinafter abbreviated as PVF), and polyvinylidene fluoride (hereinafter abbreviated as PVDF) Preferably, one or more polymers are used.
上記いずれの樹脂も触媒乳化重合、懸濁重合、ものを例
示することができる。フッ素ゴムの重合方式としては、
塊状重合、懸濁重合、乳化重合、溶液重合、触媒重合、
電離性放射線重合、レドンクス重合などを挙げることが
できる。また、フッ素ゴムの分子量は、通常５万以上の
ものが望ましく、可及的に高分子量のものが良好な結果
を得ることから、より望ましくは７万以上、特に望まし
くは１０万〜２５万程度のものを用いる。以」二の条件
に該当する代表例としては、テｉ・ラフルオロエチレン
・プロピレン共重合体である旭硝子社製アフラス、フッ
化ビニリデン・ヘキサフルオロプロピレン共重合体であ
るデュポン・昭和電工社製ハイトン、フッ化ビニリデン
・ヘキサフルオロプロピレン・テトラフルオロエチレン
共重合体であるモンテフルオス社製テクノフロン、フル
オロシリコーン系エラストマーであるダウコーニング社
製シラスティックＬＳ、フォスフアゼン系エラストマー
であるファイアストーン社製ＰＮＰ、パーフルオロ系エ
ラストマーであるダイキン工業社製ダイエルパーフロな
どを挙げることができる。Any of the above resins can be exemplified by catalytic emulsion polymerization or suspension polymerization. The polymerization method for fluororubber is
bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, catalytic polymerization,
Examples include ionizing radiation polymerization and redonx polymerization. In addition, the molecular weight of the fluororubber is usually preferably 50,000 or more, and since the highest possible molecular weight will give good results, it is more preferably 70,000 or more, and particularly preferably about 100,000 to 250,000. Use the one. Typical examples that meet the above two conditions include Aflas manufactured by Asahi Glass Co., Ltd., which is a tetrafluoroethylene propylene copolymer, and Hyton manufactured by DuPont and Showa Denko Co., Ltd., which is a vinylidene fluoride hexafluoropropylene copolymer. , Tecnoflon manufactured by Montefluos, a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer, Silastic LS manufactured by Dow Corning, a fluorosilicone elastomer, PNP manufactured by Firestone, a phosphazene elastomer, and Perfluoro Examples include Daiel Perflo, manufactured by Daikin Industries, Ltd., which is a type elastomer.
触媒溶液重合、気相重合および電離性放射線照射重合な
どの各種重合方式が製造段階で採用でき、その分子量は
５００００以下のものが望ましく 、５０００を越えほ
ぼ２００００以下のものが特に望ましい。Various polymerization methods such as catalytic solution polymerization, gas phase polymerization, and ionizing radiation irradiation polymerization can be employed at the production stage, and the molecular weight is preferably 50,000 or less, particularly preferably more than 5,000 and approximately 20,000 or less.
以上の条件に該当する代表例としては、前記したＰＦＡ
の三重・デュポンフロロケミカル社製ＰＦＡＭＰＩＯ１
ＦＥＰである三重・デュポンフロロケミカル社製テフロ
ンＦＥＰ１００ 、ＥＴＦＢである旭硝子社製アフロン
ＣＯＰ、、ＣＴＦＥであるダイキン工業社製ネオフロン
ＣＴＦＥ、、ＰＶＤＦである県別化学社製ＫＦポリマー
ＰＶＦであるデュポン社製Ｔｅｄｌａｒが挙げられる。A typical example that meets the above conditions is the PFA mentioned above.
PFAMPIO1 manufactured by DuPont Fluorochemical Co., Mie
FEP is Teflon FEP100 manufactured by DuPont Mie Fluorochemical Co., Ltd., ETFB is Aflon COP manufactured by Asahi Glass Co., Ltd., CTFE is Neoflon CTFE manufactured by Daikin Industries, Ltd., PVDF is manufactured by Kenbetsu Kagaku Co., Ltd. KF polymer, PVF is manufactured by DuPont Company. An example is Tedlar.
上記したフッ素樹脂および熱可塑性フルオロ樹脂を混合
すると、潤滑性組成物は、弾性体としての特性を得るこ
とができる。そして、優れた摺動特性を付与するために
、低分子置台フン素重合体を配合するのである。When the above-described fluororesin and thermoplastic fluororesin are mixed, the lubricating composition can obtain properties as an elastic body. In order to provide excellent sliding properties, a low molecular weight fluorine polymer is added.
ここで低分子量含フッ素重合体とは、テトラフルオロエ
チレン（ＴＦＥ） 、テトラフルオロエチレン・ヘキサ
フルオロプロピレン共重合体（ＦＥＰ）等のフルオロオ
レフィン重合体、主要構造単位−Ｃ７Ｆ２゜−〇 −（
ｎは１〜４の整数）を有するフルオロポリエーテル、主
要構造単位
ＣＦ＊ （ＣＦ２→−１Ｈ（ＣＦ２ ）Ｔなどを有する
ポリフルオロアルキル基含有化合物（炭素数２〜２０）
のうち分子量５００００以下のものをいうが、前記価れ
た摺動特性を付与するため分子量５０００以下のものが
特に望ましい。そして、これらのうち、平均粒径５ｐｍ
以下の次式で示されるテトラフルオロエチレン低次重合
体が最も好ましく、たとえば、デュポン社製パイダック
スＩｌｌ？、旭硝子社製フルオンルブリカントＬ１６９
などを挙げることができる。Here, the low molecular weight fluoropolymer refers to fluoroolefin polymers such as tetrafluoroethylene (TFE), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), main structural unit -C7F2゜-〇-(
n is an integer of 1 to 4), a polyfluoroalkyl group-containing compound (carbon number 2 to 20) having a main structural unit CF* (CF2→-1H(CF2)T, etc.)
Of these, those with a molecular weight of 50,000 or less are referred to, and those with a molecular weight of 5,000 or less are particularly desirable in order to impart the above-mentioned excellent sliding properties. Of these, the average particle size is 5pm.
Most preferred are tetrafluoroethylene low-order polymers represented by the following formula, such as PIDAX Ill? manufactured by DuPont. , Fluon Lubricant L169 manufactured by Asahi Glass Co., Ltd.
etc. can be mentioned.
つぎに、−Ｃ１，Ｆ、１．−０− （ｎは１〜４の整数
）の主要構造単位を有する平均分子量５００００以下の
フルオロポリエーテルとしては、
が挙げられ、これらを単独使用しても併用してもよい。Next, -C1,F, 1. Examples of the fluoropolyether having an average molecular weight of 50,000 or less and having a main structural unit of -0- (n is an integer of 1 to 4) include the following, and these may be used alone or in combination.
また、官能基に活性化水素が含まれているフルオロポリ
エーテルとポリフルオロポリエーテル基を含有しないイ
ソシアナート化合物とを併用しても、また、イソシアネ
ート基を有するフルオロポリエーテルと、各種のフルオ
ロポリエーテル基を含有しないジアミン類、トリアミン
類または各種のフルオロポリエーテル基を含有しないジ
オール類、トリオール類を併用するなどの方法を採用し
てもよい。特に官能基同志が反応して分子量の増大が起
こるようなフルオロポリエーテルを組み合わせて使用す
ることが好ましく、たとえばイソシアネート基を含む単
位を有するものと、水酸基を含む単位を有するものとを
組み合わせるなど伊国モンテフルオス社製：フォンブリ
ンＺ２５ＣＦ、Ｏ＋−Ｃ２Ｆ４０ ＋ｆ−＋ＣＦ２０→
１ＣＦ、、同上社製：フォンブリンＹ２５
ＣＦ、Ｏ（−ＣＦ２− ＣＦ−０→−Ｔ＋−ＣＦ２０
ｈ ＣＦ３、 Ｆ ３
ダイキン工業社製：デムナム
ＣＦ、 ←ＣＦ ＣＦ２ ０−＋−ｒ−ｆ−ＣＦ２
０→−ＣＦ３、ＣＦ３
などを例示することができる。そしてこのような重合体
について他の配合材料および添加材に対する親和性（密
着性）の向上のためムこ、イソシアネート基、水酸基、
カルボキシル基、エステル等の官能基を含む単位を有す
るものが望ましい。したがって、このようなフルオロポ
リエーテルの具体例としては、
ＨＯＯＣ−ＣＦ２ｏ（ｃ２ＦＪ ０−）ｒ（−ＣＦ２０
＋−ＣＦ２ Ｃ０ＯＨ。Furthermore, even if a fluoropolyether containing activated hydrogen in its functional group is used in combination with an isocyanate compound that does not contain a polyfluoropolyether group, fluoropolyethers having an isocyanate group and various fluoropolyethers can be used together. A method may be adopted in which diamines and triamines that do not contain ether groups or diols and triols that do not contain various fluoropolyether groups are used in combination. In particular, it is preferable to use a combination of fluoropolyethers whose functional groups react with each other to increase the molecular weight. Manufactured by Montefluos: Fomblin Z25CF, O+-C2F40 +f-+CF20→
1CF,, manufactured by the same company: Fomblin Y25 CF, O (-CF2- CF-0→-T+-CF20
h CF3, F 3 Manufactured by Daikin Industries: Demnum CF, ←CF CF2 0-+-r-f-CF2
Examples include 0→-CF3 and CF3. In order to improve the affinity (adhesion) of such polymers to other compounding materials and additives, muco, isocyanate groups, hydroxyl groups,
It is desirable to have a unit containing a functional group such as a carboxyl group or an ester. Therefore, specific examples of such fluoropolyethers include HOOC-CF2o(c2FJ0-)r(-CF20
+-CF2C0OH.
Ｈ，Ｃ００Ｃ−ＣＦ２０（Ｃ２Ｆ４０−）−（−ＣＦ２
０−）−ＣＦ２．Ｃ０ＯＨ。H, C00C-CF20(C2F40-)-(-CF2
0-)-CF2. C0OH.
ＨＯＣＨ２ＣＦ２０（Ｃｚ Ｆ４０ ＋−＋ＣＦｚ ０
−）−ＣＦｚ −ＣＨｔ ＯＨ。HOCH2CF20(Cz F40 +-+CFz 0
-)-CFz-CHtOH.
は同じように望ましい。is equally desirable.
また、ポリフルオロアルキル基含有化合物としては、た
とえば
ＣＦ＋（ＣＦｚ）ｔ−１Ｈ（ＣＦ２）６−１ＣＦｚ Ｃ
１（ＣＦ２）Ｉ＋ＣＦｚＣＩ ８
ＣＦ３、。Ｆ３．−ＣＦ （ＣＦ２）？−１、−ＣＦ
（ＣＦ、）？−１Ｆ ｘ
の、ようなポリフルオロアルキル基（炭素数２〜２０）
を有し、平均分子量が５００００以下のものが挙げられ
る。具体的には、
Ｃｂ ＦＩ３Ｃ２Ｈａ ０ＣＮＩ４
（ＣＨ２）６ ＮＣ０１Ｃ６Ｆ、３ＣＯＯＨ１Ｃ３Ｆ
１７Ｃ２Ｈａ ＳＨ，Ｃｂ Ｆ＋：＋５ＣＨｚ ＣＨｚ
ＯＣ（ＣＨｚ）ｓ ＮＨｚ、Ｃ＋＋ Ｆ＋ｗＣｚ Ｈ
ａ ０ＣＨｚ ＣＨＣＨ２、Ｃ＋ｏＦｚ＋ＳＯ＋ Ｈ。In addition, examples of polyfluoroalkyl group-containing compounds include CF+(CFz)t-1H(CF2)6-1CFz C
1(CF2)I+CFzCI 8
CF3. F3. -CF (CF2)? -1, -CF
(CF,)? -1Fx, such as a polyfluoroalkyl group (2 to 20 carbon atoms)
and an average molecular weight of 50,000 or less. Specifically, Cb FI3C2Ha 0CNI4 (CH2)6 NC01C6F, 3COOH1C3F
17C2Ha SH, Cb F+: +5CHz CHz
OC(CHz)s NHz, C++ F+wCz H
a 0CHZ CHCH2, C+oFz+SO+H.
など、反応性基およびポリフルオロアルキル基を有する
化合物と、その反応性基と反応する基を有するエチレン
性不飽和化合物との反応物（たとえば、フルオロアルキ
ルアクリレートなど）の重合体や、前記反応性基および
ポリフルオロアルキル基を有する化合物とその反応性基
と反応する基を有する各種重合体との反応物、または前
記化合物の重縮合物などが挙げられる。このようにポリ
フルオロアルキル基含有化合物は、前記フルオロポリエ
ーテルと同様に他の配合材料および添加剤の親和性（密
着性）の向上のために親和性の高い官能基、たとえばイ
ソシアネート基、水酸基、メルカプト基、カルボキシル
基、エポキシ基、アミノ基、スルフォン基等を含む単位
を有する化合物が好ましい。Polymers of reactants (such as fluoroalkyl acrylates) of compounds having a reactive group and polyfluoroalkyl groups and ethylenically unsaturated compounds having groups that react with the reactive groups, such as Examples include reaction products of compounds having a group and polyfluoroalkyl groups with various polymers having a group that reacts with the reactive group, and polycondensates of the aforementioned compounds. In this way, polyfluoroalkyl group-containing compounds, like the above-mentioned fluoropolyethers, are used with highly compatible functional groups, such as isocyanate groups, hydroxyl groups, etc., in order to improve the affinity (adhesion) of other compounding materials and additives. Compounds having units containing a mercapto group, a carboxyl group, an epoxy group, an amino group, a sulfone group, etc. are preferred.
なお、これらのポリフルオロアルキル基含有化合物は、
単独使用または併用のいずれでもよく、また、活性化水
素を有する反応基を有するポリフルオロアルキル基含有
化合物と、ポリフルオロアルキル基を有しないイソシア
ナート化合物とを併用してもよい。また、イソシア７、
− ｌ−Ｔｉを有するポリフルオロアルキル基含有化合
物と、各種のポリフルオロアルキル基を含有しないジア
ミン類、び低分子量含フッ素重合体の配合比は、フッ素
ゴムと熱可塑性フルオロ樹脂の重量比にて５０ ： ５
０から９５＝５が望ましい。なぜならば熱可塑性フルオ
ロ樹脂の配合重量比が５０／１００を越える多量では目
的の組成物に充分な弾性特性が得られず、５／１００未
満の少量では充分な耐摩耗性が得られないからである。In addition, these polyfluoroalkyl group-containing compounds are
They may be used alone or in combination, and a polyfluoroalkyl group-containing compound having a reactive group having activated hydrogen and an isocyanate compound having no polyfluoroalkyl group may be used together. Also, Isocia 7,
- The compounding ratio of the polyfluoroalkyl group-containing compound having l-Ti, various diamines that do not contain polyfluoroalkyl groups, and low molecular weight fluoropolymers is based on the weight ratio of fluororubber and thermoplastic fluororesin. 50:5
0 to 95=5 is desirable. This is because if the weight ratio of the thermoplastic fluororesin exceeds 50/100, the target composition will not have sufficient elastic properties, and if the weight ratio is less than 5/100, sufficient wear resistance will not be obtained. be.
また、フッ素ゴムと熱可塑性フルオロ樹脂の合計１００
重量部に対して低分子量含フッ素重合体５〜５０重量部
が好ましい。なぜならば、低分子量含フッ素重合体の配
合比が５重量部未満では充分な摺動特性が得られず、５
０重量部を越えるとゴム状弾性特性が損なわれるからで
ある。In addition, a total of 100% of fluororubber and thermoplastic fluororesin
The amount of the low molecular weight fluoropolymer is preferably 5 to 50 parts by weight. This is because if the blending ratio of the low molecular weight fluoropolymer is less than 5 parts by weight, sufficient sliding properties cannot be obtained;
This is because if the amount exceeds 0 parts by weight, the rubber-like elastic properties will be impaired.
なお、この発明の目的を損なわない範囲で上記成分の他
に各種添加剤が配合されていてもよい。In addition, various additives may be blended in addition to the above-mentioned components within a range that does not impair the purpose of the present invention.
たとえば、フッ素ゴムの加硫材としてイソシアヌレイト
、有機過酸化物等、ステアリン酸ナトリウム、酸化マグ
ネシウム、水酸化カルシウムなどの酸化防止剤または受
酸剤、カーボンなどの帯電防止剤、シリカ、アルミナな
どの充填剤、その他金属酸化物、着色剤、難燃剤などを
便宜加えてもよトリアミン類または各種のポリフルオロ
アルキル基を含有しないジオール類、トリオール類を併
用するなどの方法を採用してもよい。官能基同志の組み
合わせは強度増加のうえから好ましく、具体的には炭素
数２〜２０のポリフルオロアルキル基を有し、かつ、水
酸基、メルカプト基、カルボキシル基、アミノ基から選
ばれる少なくとも１種類を含む含フッ素重合体との組み
合わせ、または炭素数２〜２０のポリフルオロアルキル
基を有し、かつ、イソシアネート基を含む単位を有する
含フッ素重合体と、炭素数２〜２０のポリフルオロアル
キル基を有し、さらに活性化水素を有する反応基を含む
単位を有する含フッ素重合体との組み合わせを挙げるこ
とができる。For example, as vulcanizing materials for fluororubber, isocyanurates, organic peroxides, etc., antioxidants or acid acceptors such as sodium stearate, magnesium oxide, calcium hydroxide, antistatic agents such as carbon, silica, alumina, etc. Fillers, other metal oxides, colorants, flame retardants, etc. may be added as needed.Methods such as the combined use of triamines or various diols and triols that do not contain polyfluoroalkyl groups may be adopted. . A combination of functional groups is preferred from the viewpoint of increasing strength, and specifically, a combination of functional groups having a polyfluoroalkyl group having 2 to 20 carbon atoms and at least one type selected from a hydroxyl group, a mercapto group, a carboxyl group, and an amino group. or a combination of a fluoropolymer containing a polyfluoroalkyl group having 2 to 20 carbon atoms and a fluoropolymer having a unit containing an isocyanate group and a polyfluoroalkyl group having 2 to 20 carbon atoms. and a combination with a fluorine-containing polymer having a unit containing a reactive group having activated hydrogen.
これら低分子量含フッ素重合体のうち、フルオロオレフ
ィン重合体またはフルオロポリエーテルを用いると、潤
滑性において優れた結果が得られ、特にフルオロオレフ
ィン重合体を用いると最も望ましい結果を得ることが判
明している。Among these low molecular weight fluoropolymers, it has been found that excellent results in lubricity can be obtained by using fluoroolefin polymers or fluoropolyethers, and in particular, the most desirable results can be obtained by using fluoroolefin polymers. There is.
上記のフッ素ゴム、熱可塑性フルオロ樹脂およいことは
いうまでもない。Needless to say, the above-mentioned fluororubber and thermoplastic fluororesin are suitable.
以上の各種原材料を混合する方法は特に限定するもので
はなく、通常広く用いられている方法、例えば、主原料
になるエラストマー、その他諸原料をそれぞれ個別に順
次、または同時にロール混合機その他混合機により混合
すればよい。なお、このとき摩擦による発熱を防止する
意味で温調器を設けることが望ましい。また、ロール混
合機を使用する場合には、仕上げの混合として、ロール
間隔を３ｍｍ以下程度に締めて薄通しを行なうとさらに
良い。The method of mixing the various raw materials mentioned above is not particularly limited, and any commonly used method may be used, such as mixing the elastomer, which is the main raw material, and other raw materials individually, sequentially, or simultaneously using a roll mixer or other mixer. Just mix. At this time, it is desirable to provide a temperature controller to prevent heat generation due to friction. Further, when using a roll mixer, it is even better to tighten the roll spacing to about 3 mm or less and perform thin threading as the final mixing.
以上述べたこの発明の組成物はフッ素ゴム、熱可塑性フ
ルオロ樹脂および低分子量台フ・ノ素重合体を併用する
ことにより、弾性体の特性と同時に良好な摺動特性を有
することができる。The above-described composition of the present invention can have good sliding properties as well as elastic properties by using a fluororubber, a thermoplastic fluororesin, and a low-molecular-weight monopolymer in combination.
まず、実施例および比較例に用いた諸原料を一括して示
すと以下のとおりである。なお、各成分の配合割合はす
べて重量％であるが、■〜■に示す原料については■〜
■に示す原料の総重量１００に対する重量％である。First, the raw materials used in the Examples and Comparative Examples are listed below. The blending ratio of each component is all weight%, but for the raw materials shown in ■~■
It is weight % based on 100 of the total weight of the raw materials shown in (2).
■フルオロシリコーン系エラストマー（ダウコーニング
社製ニジラスティックＬＳ）
■パーフルオロ系エラストマー（ダイキン社製：ダイエ
ルパーフロにＡ−５（１）
■フッ化ビニリデン・ヘキサフルオロプロピレン共重合
体（モンテフルオス社製：テクノフロンＦＯＲ５３５１
）
■ＰＦＡ （三井・デュポンフロロケミカル社製：ＰＦ
Ａ ＭＰＩＯ）
■Ｆ［！Ｐ （三井・デュポンフロロケミカル社製：Ｐ
ＥＰ １００ ）
■低分子量含フッ素重合体（旭硝子社製ニルーブリカン
トＬ１６９）
■低分子量含フッ素重合体（日本モンテジソン社製：フ
ォンブリンＺ−Ｄｏｌｌ）
■フッ化カーボン（旭硝子社製ニアキュフロア■カーボ
ン（キャンカーブ社製＝ＭＴカーボン）［相］ステアリ
ン酸ナトリウム（一般工業材）■有機過酸化物〔α、α
ビス（ｔブチルペルオキシ）ジイソプロピルベンゼン〕
＠酸化マグネシウム（試薬）
■水酸化カルシウム（試薬）
実施例１〜３
まず、ロール間隔５〜１０錘程度に調整したロール混合
機にフルオロシリコーン系エラストマー■をそれぞれ巻
き付け、第１表に示した割合でステアリン酸ナトリウム
、ＭＴカーボン、酸化マグネシウム、水酸化カルシウム
、熱可塑性フルオロ重合体を混合した。その後、ロール
間隔を約１ｍｍに調整し、清適しを１０回行なった。な
お、この時の摩擦熱を防止する目的で、常時、ロール内
に冷却水を通し、ロール温度を６０°Ｃ以下に保った。■Fluorosilicone elastomer (Nigilastik LS manufactured by Dow Corning) ■Perfluorinated elastomer (manufactured by Daikin: Daiel Perflo A-5 (1)) ■Vinylidene fluoride/hexafluoropropylene copolymer (manufactured by Montefluos) :Technoflon FOR5351
) ■PFA (manufactured by Mitsui DuPont Fluorochemical Company: PF
A MPIO) ■F[! P (manufactured by Mitsui DuPont Fluorochemical Company: P
EP 100) ■Low molecular weight fluoropolymer (Nillubricant L169 manufactured by Asahi Glass Co., Ltd.) ■Low molecular weight fluoropolymer (manufactured by Nippon Montageson Co., Ltd.: Fomblin Z-Doll) ■Fluorinated carbon (Niacufloor manufactured by Asahi Glass Co., Ltd. ■Carbon ( Made by Can Carb = MT carbon) [Phase] Sodium stearate (general industrial material) ■Organic peroxide [α, α
Bis(t-butylperoxy)diisopropylbenzene] @ Magnesium oxide (reagent) ■ Calcium hydroxide (reagent) Examples 1 to 3 First, each fluorosilicone elastomer ■ was placed in a roll mixer adjusted to have a roll spacing of about 5 to 10 spindles. Sodium stearate, MT carbon, magnesium oxide, calcium hydroxide, and thermoplastic fluoropolymer were mixed in the proportions shown in Table 1. Thereafter, the roll interval was adjusted to about 1 mm, and cleaning was performed 10 times. In addition, in order to prevent frictional heat at this time, cooling water was constantly passed through the roll to maintain the roll temperature at 60°C or less.
つぎに冷却水を止め、ロール内にスチームを通し、ゴム
温度が７０℃以上９０°Ｃ以下になるように調整し、そ
の後、ロール間隔を５〜１０ｍｍ程度に戻し、低分子量
含フッ素重合体を少量ずつ添加しながら混合した。その
後、再びロール間隔をｌ ｍｍに狭めて清適第 ２
表
しを１０回行なった。Next, the cooling water is turned off and steam is passed through the rolls to adjust the rubber temperature to 70°C or higher and 90°C or lower.Then, the roll spacing is returned to approximately 5 to 10 mm and the low molecular weight fluoropolymer is heated. Mix while adding in small portions. After that, the roll spacing was again narrowed to 1 mm and the second
The representation was performed 10 times.
縦３００ＩＩｌ＋１１．横３００ｍｍ、厚み１ｍｍのシ
ート状に形成された各コンパウンドに対して、１次加硫
（１７０°Ｃ１１０分間、プレス圧７ｋｇｆ／ｃｗｔ）
および２次加硫（フリー加熱２３０°Ｃ１６時間）を行
い、加硫を終わった各シートについて摩擦・摩耗特性、
弾性体特性を求めた。各試験方法は以下のとおりである
。Vertical 300IIl+11. Each compound formed into a sheet with a width of 300 mm and a thickness of 1 mm was subjected to primary vulcanization (170°C for 110 minutes, press pressure of 7 kgf/cwt).
Then, secondary vulcanization (free heating at 230°C for 16 hours) was performed, and the friction and wear characteristics of each sheet after vulcanization were determined.
The properties of the elastic body were determined. Each test method is as follows.
Ｉ）摩擦試験：
得られたシートを外径２１ｍｍ、内径１７ｍｍ、厚み１
ｍｍの環状に打ち抜き、外径２１ｍｍ、内径１７ｍｍ、
厚み１０＋ｎｍの環状アルミ製治具に接着し、摩擦試験
片とした。条件として滑り速度１ｍ／分、面圧３ｋｇｆ
／Ｃイにてスラスト型摩擦摩耗試験機（自社製）で摩擦
係数の経時変化（１００時間）を測定した。相手材とな
るディスクの材質は軸受鋼（ＳＵＪ２）とした。I) Friction test: The obtained sheet had an outer diameter of 21 mm, an inner diameter of 17 mm, and a thickness of 1.
Punched into a ring shape of mm, outer diameter 21mm, inner diameter 17mm,
It was adhered to a ring-shaped aluminum jig with a thickness of 10+ nm to obtain a friction test piece. Conditions are sliding speed 1m/min, surface pressure 3kgf
Changes in the friction coefficient over time (100 hours) were measured using a thrust type friction and wear tester (manufactured in-house) at /Ci. The material of the mating disk was bearing steel (SUJ2).
得られた結果は第２表に示した。ここで、摩擦係数の経
時変化が０．１以内のものを○印、０．１を越えて変化
量の大きいものを×印とする二段階評価を行ない第２表
中に併記した。The results obtained are shown in Table 2. Here, a two-level evaluation was carried out in which cases in which the change in friction coefficient over time was within 0.1 were marked with a circle, and cases with a large change exceeding 0.1 were marked with an x, and are also listed in Table 2.
２）摩耗試験：
得られたシートを外径２１ｍｍ、内径１７肛、厚み１ｍ
ｍの環状に打ち抜き、外径２１ｍｍ、内径１７ｍｍ、厚
み１０ｍｍの環状アルミ製治具に接着し、摩擦試験片と
した。条件として滑り速度３０ｍ／分、面圧３．３ｋｇ
原料を配合し、実施例１〜５と全く同様な方法にて混合
、シート成形、加硫を行なった。また、試験片の調整お
よび試験方法も実施例１〜５と全く同様な方法を用いた
。それらの結果を第２表に示した。2) Abrasion test: The obtained sheet had an outer diameter of 21 mm, an inner diameter of 17 mm, and a thickness of 1 m.
A friction test piece was punched out into an annular shape of m in diameter and adhered to an annular aluminum jig with an outer diameter of 21 mm, an inner diameter of 17 mm, and a thickness of 10 mm. Conditions are sliding speed 30m/min, surface pressure 3.3kg
The raw materials were blended, mixed, sheet-formed, and vulcanized in exactly the same manner as in Examples 1 to 5. Further, the preparation of the test piece and the testing method were completely the same as those in Examples 1 to 5. The results are shown in Table 2.
第２表から明らかなように、比較例１ （フルオロシリ
コーンエラストマー単体）では摩擦係数が試験開始時に
０．９あり、１０時間後には本試験機の測定限界である
１、５を越えた。比較例２（■ＰＦＡ３０部充填）、比
較例３（■Ｌ１６９３０部充填）も経時的に摩擦係数が
上昇する傾向があった。比較例４ （■Ｌ１６９３０部
、■フッ化カーボン１０部充填）は比較例３に比べて摩
擦係数の上昇する割合は小さかったが、１００時間後に
は測定限界を越えた。As is clear from Table 2, in Comparative Example 1 (fluorosilicone elastomer alone), the friction coefficient was 0.9 at the start of the test, and after 10 hours, it exceeded the measurement limit of 1.5 with this tester. Comparative Example 2 (■ Filled with 30 parts of PFA) and Comparative Example 3 (■ Filled with 16,930 parts of L) also had a tendency for the coefficient of friction to increase over time. Comparative Example 4 (16,930 parts of L, 10 parts of fluorocarbon filled) had a smaller increase in friction coefficient than Comparative Example 3, but exceeded the measurement limit after 100 hours.
摩耗係数については比較例中、最も低い比較例４で摩耗
係数８００であり、いずれも実施例に比べてきわめて高
い値を示した。Regarding the abrasion coefficient, Comparative Example 4 had the lowest abrasion coefficient of 800 among the comparative examples, and both exhibited extremely high values compared to the examples.
しかし、フッ素樹脂、熱可塑性フルオロ樹脂および低分
子量フルオロ重合体を併用した実施例１〜５では、いず
れも試験開始時から］００時間経過ｆ／ｃ＋Ｍにてスラ
スト型摩擦摩耗試験機（自社製）で測定した。相手材と
なるディスクの材質は軸受鋼（ＳＵＪ２）とした。得ら
れた結果は第２表に示した。However, in Examples 1 to 5 in which a fluororesin, a thermoplastic fluororesin, and a low molecular weight fluoropolymer were used in combination, all tests were performed using a thrust type friction and wear tester (manufactured in-house) at f/c+M after 00 hours from the start of the test. It was measured with The material of the mating disk was bearing steel (SUJ2). The results obtained are shown in Table 2.
３）弾性体特性
得られたシートに対して、ＪＩＳ−に６３０１に準じ、
引っ張り破断強度、引っ張り破断伸び、表面硬度（ＪＩ
Ｓ−Ａ）を調べ、それらの結果を第２表に示した。3) For the sheet with elastic properties, according to JIS-6301,
Tensile strength at break, tensile elongation at break, surface hardness (JI
S-A) was investigated and the results are shown in Table 2.
実施例４および５
実施例４においてはフッ素ゴムをパーフルオロ系エラス
トマー■とじ、実施例５においては同じくフン素ゴムを
フッ化ビニリデン・ヘキサフルオロプロピレン共重合体
とし、それぞれ第１表に示す原料の配合割合にて実施例
１〜３と全く同様な方法にて混合、シート成形、加硫を
行なった。また、試験片の調整および試験方法も実施例
１〜３と全く同様な方法を用いた。それらの結果を第２
表に示した。Examples 4 and 5 In Example 4, the fluororubber was bound with perfluoro-based elastomer ■, and in Example 5, the fluorine rubber was similarly made of vinylidene fluoride/hexafluoropropylene copolymer, and each of the raw materials shown in Table 1 was used. Mixing, sheet molding, and vulcanization were carried out in exactly the same manner as in Examples 1 to 3 at the blending ratio. Further, the preparation of the test piece and the testing method were completely the same as in Examples 1 to 3. those results as a second
Shown in the table.
比較例１〜４
比較例においてはフルオロシリコーン系エラストマーに
対して、それぞれ第１表に示す割合にてまでの摩擦係数
が０，２６から０．３２で安定しており、摩耗係数も耐
摩耗性グレードとして通常目安とされる１００以下であ
り、しかもこれら各実施例は、弾性体として引張り強度
、伸び、硬度いずれも充分な特性を有していた。Comparative Examples 1 to 4 In the comparative examples, the friction coefficients of the fluorosilicone elastomers at the ratios shown in Table 1 were stable at 0.26 to 0.32, and the wear coefficients also showed wear resistance. The grade is usually 100 or less, and each of these Examples had sufficient properties as an elastic body in terms of tensile strength, elongation, and hardness.
以上述べたように、この発明の潤滑性ゴム組成物は充分
な弾性体特性を有し、また優れた摺動特性をも持つもの
であるから、シール性、追従性、消音性、および制振性
などのゴム特性の機能とともに低摩擦係数、耐摩耗性が
要求される摺動材料として良好なものである。したがっ
て、この発明の意義はきわめて大きいといえる。As mentioned above, the lubricating rubber composition of the present invention has sufficient elastic properties and also has excellent sliding properties, so it has excellent sealing properties, followability, sound deadening properties, and vibration damping properties. It is suitable as a sliding material that requires not only rubber properties such as elasticity but also low coefficient of friction and wear resistance. Therefore, it can be said that the significance of this invention is extremely large.
特許出廓人 工ヌティエヌ・ルーロン株式会社 同Patent distributor: Nutienne Rulon Co., Ltd. same
Claims (1)
量含フッ素重合体とを配合してなる潤滑性ゴム組成物。 （２）フッ素ゴムの分子量が１０万から２５万である請
求項１記載の潤滑性ゴム組成物。（３）熱可塑性フルオ
ロ樹脂がテトラフルオロエチレン重合体、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共重
合体、テトラフルオロエチレン・ヘキサフルオロプロピ
レン・パーフルオロアルキルビニルエーテル共重合体、
テトラフルオロエチレン・ヘキサフルオロプロピレン共
重合体、テトラフルオロエチレン・エチレン共重合体、
トリフルオロクロロエチレン重合体、トリフルオロクロ
ロエチレン・エチレン共重合体、ポリビニルフルオライ
ドおよびポリビニリデンフルオライドからなる群から選
ばれる１種以上の重合体である請求項１記載の潤滑性ゴ
ム組成物。 （４）低分子量含フッ素重合体が分子量５０００以下の
重合体である請求項１記載の潤滑性ゴム組成物。 （５）低分子量含フッ素重合体がフルオロオレフィン重
合体、フルオロポリエーテルおよびポリフルオロアルキ
ル基含有化合物からなる群から選ばれる少なくとも１種
以上の重合体である請求項１または４記載の潤滑性ゴム
組成物。 （６）低分子量含フッ素重合体がテトラフルオロエチレ
ン低次重合体である請求項１または４記載の潤滑性ゴム
組成物。 （７）フッ素ゴムと熱可塑性フルオロ樹脂の重量比が５
０：５０から９５：５の範囲であり、かつその合計１０
０重量部当りの低分子量含フッ素重合体が５〜５０重量
部である請求項１記載の潤滑性ゴム組成物。[Scope of Claims] (1) A lubricating rubber composition comprising a fluororubber, a thermoplastic fluororesin, and a low molecular weight fluoropolymer. (2) The lubricating rubber composition according to claim 1, wherein the fluororubber has a molecular weight of 100,000 to 250,000. (3) The thermoplastic fluororesin is a tetrafluoroethylene polymer, a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, a tetrafluoroethylene/hexafluoropropylene/perfluoroalkyl vinyl ether copolymer,
Tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer,
The lubricating rubber composition according to claim 1, which is one or more polymers selected from the group consisting of trifluorochloroethylene polymer, trifluorochloroethylene/ethylene copolymer, polyvinyl fluoride, and polyvinylidene fluoride. (4) The lubricating rubber composition according to claim 1, wherein the low molecular weight fluoropolymer has a molecular weight of 5,000 or less. (5) The lubricating rubber according to claim 1 or 4, wherein the low molecular weight fluorine-containing polymer is at least one polymer selected from the group consisting of fluoroolefin polymers, fluoropolyethers, and polyfluoroalkyl group-containing compounds. Composition. (6) The lubricating rubber composition according to claim 1 or 4, wherein the low molecular weight fluoropolymer is a tetrafluoroethylene low-order polymer. (7) The weight ratio of fluororubber and thermoplastic fluororesin is 5
range from 0:50 to 95:5, and a total of 10
The lubricating rubber composition according to claim 1, wherein the low molecular weight fluoropolymer is contained in an amount of 5 to 50 parts by weight per 0 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19099590A JP3059465B2 (en) | 1990-07-17 | 1990-07-17 | Lubricating rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19099590A JP3059465B2 (en) | 1990-07-17 | 1990-07-17 | Lubricating rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0476045A true JPH0476045A (en) | 1992-03-10 |
| JP3059465B2 JP3059465B2 (en) | 2000-07-04 |
Family
ID=16267115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19099590A Expired - Fee Related JP3059465B2 (en) | 1990-07-17 | 1990-07-17 | Lubricating rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3059465B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06228536A (en) * | 1993-01-29 | 1994-08-16 | Ntn Corp | O-ring of glove box damper mechanism |
| JPH08193197A (en) * | 1994-08-12 | 1996-07-30 | Ntn Corp | V ring |
| JP2003096438A (en) * | 2001-09-25 | 2003-04-03 | Mitsubishi Cable Ind Ltd | Seal |
| JP6166448B1 (en) * | 2016-10-18 | 2017-07-19 | 株式会社ハーベス | Lubricant composition, grease composition, diluted lubricant solution, sliding member |
-
1990
- 1990-07-17 JP JP19099590A patent/JP3059465B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06228536A (en) * | 1993-01-29 | 1994-08-16 | Ntn Corp | O-ring of glove box damper mechanism |
| JPH08193197A (en) * | 1994-08-12 | 1996-07-30 | Ntn Corp | V ring |
| JP2003096438A (en) * | 2001-09-25 | 2003-04-03 | Mitsubishi Cable Ind Ltd | Seal |
| JP6166448B1 (en) * | 2016-10-18 | 2017-07-19 | 株式会社ハーベス | Lubricant composition, grease composition, diluted lubricant solution, sliding member |
| JP2018065910A (en) * | 2016-10-18 | 2018-04-26 | 株式会社ハーベス | Lubricant composition, grease composition, diluted solution for lubricant, and sliding member |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3059465B2 (en) | 2000-07-04 |
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