JP7351526B2 - Base oil diffusion inhibitor and grease containing it - Google Patents
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Description
本発明は、グリースの基油の拡散を防止するために用いる基油拡散防止剤に関し、特にフッ素油を基油とするグリースの基油の拡散を防止するために用いる基油拡散防止剤に関するものである。 The present invention relates to a base oil diffusion inhibitor used to prevent the diffusion of base oil in grease, and particularly to a base oil diffusion inhibitor used to prevent the diffusion of base oil in grease containing fluorine oil as a base oil. It is.
各種機器の急速な高性能化及び小型化に伴って、その機械的な回転部や摺動部等に使用されるグリースに対して、従来よりも優れた特性が求められている。たとえば、小型化された各種機構部、モーター類、各種ベアリング類、接点類又はスイッチ類等に使用するグリースでは、特に、耐熱性、低温安定性及び軽トルク性等の特性が求められている。 BACKGROUND OF THE INVENTION With the rapid improvement in performance and miniaturization of various types of equipment, the grease used for mechanical rotating parts, sliding parts, etc., is required to have better properties than before. For example, greases used in miniaturized mechanical parts, motors, bearings, contacts, switches, etc. are particularly required to have properties such as heat resistance, low-temperature stability, and light torque.
これらの性能を満足するために、従来からフッ素系グリースが用いられてきた。市販されている一般的なフッ素系グリースは、基油としてフッ素油、増ちょう剤としてフッ素樹脂が用いられている。しかるに、かかる市販のグリースは、時間の経過と共の基油が塗布面から拡散してしまうという問題があった。特に、小型化された機器に適用されるグリースでは、基油の拡散は防止されるべき事項である。このため、特許文献１には、基油拡散防止剤として、パーフルオロアルキル基及び／又はパーフルオロポリエーテル基と含窒素基とが結合されてなる化合物を用いることが提案されている。 In order to satisfy these performance requirements, fluorine-based grease has been used conventionally. Commercially available general fluorine-based grease uses fluorine oil as the base oil and fluororesin as the thickener. However, such commercially available greases have a problem in that the base oil diffuses from the coated surface over time. Particularly in greases applied to miniaturized equipment, diffusion of base oil must be prevented. For this reason, Patent Document 1 proposes the use of a compound formed by bonding a perfluoroalkyl group and/or a perfluoropolyether group with a nitrogen-containing group as a base oil diffusion inhibitor.
本発明の課題は、特許文献１には開示されていない別異のフッ素含有化合物を採用することにより、基油拡散防止性能の向上した基油拡散防止剤を提供することにある。 An object of the present invention is to provide a base oil diffusion inhibitor with improved base oil diffusion prevention performance by employing a different fluorine-containing compound that is not disclosed in Patent Document 1.
本発明は、特定のパーフルオロポリエーテル基と含窒素複素環を含む基とを、－Ｃ（Ｏ）－又は－ＣＨ2ＯＣＨ2ＣＨ（ＯＨ）ＣＨ2－なる基で結合させたフッ素含有化合物を基油拡散防止剤とすることにより、上記課題を解決したものである。すなわち、本発明は、フッ素油よりなる基油の拡散防止剤であって、化１で表されるフッ素含有化合物を含む基油拡散防止剤及びこの基油拡散防止剤を含有するグリースに関するものである。
［化１］
Ｒ1（ＯＣＦＲ2ＣＦ2）n1（ＯＣＦＲ3）n2－Ｚ－Ｙ
（式中、Ｒ1は炭素数１～５のパーフルオロアルキル基であり、Ｒ2及びＲ3はフッ素原子又はトリフルオロメチル基であり、ｎ１は０～４の整数であり、ｎ２は１以上の整数であり、ｎ１＋ｎ２は１～１０の整数である。ＺはＣ（Ｏ）又はＣＨ2ＯＣＨ2ＣＨ（ＯＨ）ＣＨ2であり、Ｙは含窒素複素環を含む基である。なお、（ＯＣＦＲ2ＣＦ2）と（ＯＣＦＲ3）の出現順序は無作為である。）
The present invention provides a fluorine-containing compound in which a specific perfluoropolyether group and a group containing a nitrogen-containing heterocycle are bonded through a -C(O)- or -CH 2 OCH 2 CH(OH)CH 2 - group. By using this as a base oil diffusion inhibitor, the above problem has been solved. That is, the present invention relates to a base oil diffusion inhibitor comprising a fluorine oil, which is a base oil diffusion inhibitor containing a fluorine-containing compound represented by Chemical Formula 1, and a grease containing this base oil diffusion inhibitor. be.
[Chemical formula 1]
R 1 (OCFR 2 CF 2 ) n1 (OCFR 3 ) n2 -Z-Y
(In the formula, R 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, R 2 and R 3 are a fluorine atom or a trifluoromethyl group, n1 is an integer of 0 to 4, and n2 is 1 or more. n1+n2 is an integer of 1 to 10. Z is C(O) or CH 2 OCH 2 CH(OH)CH 2 , and Y is a group containing a nitrogen-containing heterocycle. The order of appearance of OCFR 2 CF 2 ) and (OCFR 3 ) is random.)
化１中のＲ1（ＯＣＦＲ2ＣＦ2）n1（ＯＣＦＲ3）n2－は、以下の化２又は化３で表される基であるのが好ましい。
［化２］
Ｒ1（ＯＣＦ2ＣＦ2）n1（ＯＣＦ2）n2－
［化３］
Ｃ3Ｆ7－ＯＣＦ（ＣＦ3）ＣＦ2－ＯＣＦ（ＣＦ3）－
また、化２は以下の化４、化５又は化６であるのが、より好ましい。
［化４］
ＣＦ3－（ＯＣＦ2ＣＦ2）2－ＯＣＦ2－
［化５］
Ｃ4Ｆ3－（ＯＣＦ2ＣＦ2）2－ＯＣＦ2－
［化６］
ＣＦ3－（ＯＣＦ2）4－
R 1 (OCFR 2 CF 2 ) n1 (OCFR 3 ) n2 - in Formula 1 is preferably a group represented by Formula 2 or Formula 3 below.
[Chemical 2]
R 1 (OCF 2 CF 2 ) n1 (OCF 2 ) n2 -
[Chemical 3]
C 3 F 7 -OCF(CF 3 )CF 2 -OCF(CF 3 )-
Moreover, it is more preferable that Chemical Formula 2 is the following Chemical Formula 4, Chemical Formula 5, or Chemical Formula 6.
[C4]
CF 3 -(OCF 2 CF 2 ) 2 -OCF 2 -
[C5]
C 4 F 3 - (OCF 2 CF 2 ) 2 - OCF 2 -
[Case 6]
CF 3 - (OCF 2 ) 4 -
化１中のＹは、ピロール、ピロリジン、イミダゾール、トリアゾール、ピペリジン、ピペラジン、モルホリン及びインドールよりなる群から選ばれた含窒素複素環化合物の誘導体であるのが好ましく、特にイミダゾール、トリアゾール及びピペリジンよりなる群から選ばれた含窒素複素環化合物の誘導体であるのが好ましい。 Y in formula 1 is preferably a derivative of a nitrogen-containing heterocyclic compound selected from the group consisting of pyrrole, pyrrolidine, imidazole, triazole, piperidine, piperazine, morpholine and indole, and particularly consisting of imidazole, triazole and piperidine. Preferably, it is a derivative of a nitrogen-containing heterocyclic compound selected from the group consisting of:
本発明で用いる化１で表されるフッ素含有化合物の具体例としては、以下の化合物を挙げることができる。
基油及び増ちょう剤に、本発明に係る基油拡散防止剤を添加混合して、グリースが得られる。基油としては、ＰＦＰＥ油又はＣＴＦＥ油等の従来公知のフッ素油を採用する。フッ素油の具体例としては、フォンブリン（ソルベイ社製）、クライトックス（ケマーズ社製）、デムナム（ダイキン工業社製）等が挙げられる。増ちょう剤としても、従来公知のものが採用され、たとえば、ポリテトラフルオロエチレン（ＰＴＦＥ）が代表的な増ちょう剤である。 A grease is obtained by adding and mixing the base oil diffusion inhibitor according to the present invention to a base oil and a thickener. As the base oil, a conventionally known fluorine oil such as PFPE oil or CTFE oil is used. Specific examples of fluorine oils include Fomblin (manufactured by Solvay), Krytox (manufactured by Chemours), Demnum (manufactured by Daikin Industries, Ltd.), and the like. As the thickener, a conventionally known thickener is employed, and for example, polytetrafluoroethylene (PTFE) is a typical thickener.
本発明に係る基油拡散防止剤は、市販グリースに添加して、本発明に係るグリースを得てもよい。市販グリースとしては、デムナムグリース（ダイキン工業株式会社製）、バリエルタ（ＮＯＫクリューバー株式会社製）、スミテック（住鉱潤滑剤株式会社製）、モリコート（東レ・ダウコーニング社製）等を挙げることができる。 The base oil diffusion inhibitor according to the present invention may be added to a commercially available grease to obtain the grease according to the present invention. Examples of commercially available greases include Demnum Grease (manufactured by Daikin Industries, Ltd.), Valierta (manufactured by NOK Klüber Co., Ltd.), Sumitec (manufactured by Sumiko Lubricant Co., Ltd.), and Molycoat (manufactured by Toray Dow Corning Co., Ltd.). Can be done.
本発明に係る基油拡散防止剤は、グリースの全構成成分に対して０．１～１０重量％程度添加され、特に０．５～５重量％程度添加されるのが好ましい。この程度の添加量で、満足しうる基油拡散防止効果を得ることができる。 The base oil diffusion inhibitor according to the present invention is added in an amount of about 0.1 to 10% by weight, particularly preferably about 0.5 to 5% by weight, based on the total components of the grease. A satisfactory base oil diffusion prevention effect can be obtained with this amount of addition.
本発明に係る基油拡散防止剤を含有したグリースは、段落００３１に記載の方法で基油の拡散幅を評価した場合、拡散幅が１０ｍｍ以下となるのが好ましく、特に５ｍｍ以下となるのがより好ましい。 When the base oil diffusion width of the grease containing the base oil diffusion inhibitor according to the present invention is evaluated by the method described in paragraph 0031, the diffusion width is preferably 10 mm or less, particularly 5 mm or less. More preferred.
本発明に係る基油拡散防止剤を含有するグリースは、グリースの潤滑特性を損なわせることなく、基油の拡散を良好に防止することができる。したがって、かかるグリースは小型化された機器にも十分に適用しうるものである。 Grease containing the base oil diffusion inhibitor according to the present invention can satisfactorily prevent base oil diffusion without impairing the lubricating properties of the grease. Therefore, such a grease can be sufficiently applied to miniaturized equipment.
実施例１
攪拌装置を備えたガラスフラスコに、化１８の化合物１０．００ｇと、４－アミノ－１－メチルピペリジン２．５２ｇを入れ、６０℃で３時間攪拌しながら反応させた。反応終了後、室温まで冷却した反応液を1 ，３－ビス（トリフルオロメチル）ベンゼンに溶解し、不溶物をろ紙でろ過を行ったのち、溶剤を留去し、化７で表される化合物を含む基油拡散防止剤Ａを得た。
なお、化１８は、ＣＦ3ＯＣＦ2ＣＦ2ＯＣＦ2ＣＦ2ＯＣＦ2ＣＨ2ＯＨ（Ｅｘｆｌｏｕｒ社製）とエピクロロヒドリンを用いて、常法により合成した。
10.00 g of the compound represented by Chemical Formula 18 and 2.52 g of 4-amino-1-methylpiperidine were placed in a glass flask equipped with a stirring device, and reacted with stirring at 60° C. for 3 hours. After the reaction was completed, the reaction solution cooled to room temperature was dissolved in 1,3-bis(trifluoromethyl)benzene, the insoluble materials were filtered through filter paper, the solvent was distilled off, and the compound represented by Chemical Formula 7 was obtained. A base oil diffusion inhibitor A containing the following was obtained.
Compound 18 was synthesized by a conventional method using CF 3 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CH 2 OH (manufactured by Exflour) and epichlorohydrin.
実施例２
攪拌装置を備えたガラスフラスコに、化１８の化合物１０．００ｇとピペラジン１．９０ｇを入れ、１２０℃で６時間反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化８で表される化合物を含む基油拡散防止剤Ｂを得た。
10.00 g of the compound of Chemical Formula 18 and 1.90 g of piperazine were placed in a glass flask equipped with a stirring device, and reacted at 120° C. for 6 hours. After the reaction was completed, the same post-treatment as in Example 1 was performed to obtain a base oil diffusion inhibitor B containing the compound represented by Chemical Formula 8.
実施例３
攪拌装置を備えたガラスフラスコに、化１８の化合物１０．００ｇと３－アミノ１，２，４－トリアゾール０．９２ｇを入れ、１３０℃で６時間反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化９で表される化合物を含む基油拡散防止剤Ｃを得た。
10.00 g of the compound represented by Chemical Formula 18 and 0.92 g of 3-amino 1,2,4-triazole were placed in a glass flask equipped with a stirring device and reacted at 130° C. for 6 hours. After the reaction was completed, the same post-treatment as in Example 1 was performed to obtain a base oil diffusion inhibitor C containing the compound represented by Chemical Formula 9.
実施例４
攪拌装置を備えたガラスフラスコに、化１８の化合物１０．００ｇとコハク酸イミド２．１９ｇを入れ、１３０℃で６時間反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化１０で表される化合物を含む基油拡散防止剤Ｄを得た。
10.00 g of the compound represented by Chemical Formula 18 and 2.19 g of succinimide were placed in a glass flask equipped with a stirring device, and reacted at 130° C. for 6 hours. After the reaction was completed, the same post-treatment as in Example 1 was performed to obtain a base oil diffusion inhibitor D containing the compound represented by Chemical Formula 10.
実施例５
攪拌装置を備えたガラスフラスコに、化１８の化合物１０．００ｇと３－アミノピロリジン１．９０ｇを入れ、６０℃で３時間反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化１１で表される化合物を含む基油拡散防止剤Ｅを得た。
10.00 g of the compound represented by Chemical Formula 18 and 1.90 g of 3-aminopyrrolidine were placed in a glass flask equipped with a stirring device, and reacted at 60° C. for 3 hours. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain a base oil diffusion inhibitor E containing the compound represented by Chemical Formula 11.
実施例６
攪拌装置を備えたガラスフラスコに、化１９の化合物５．００g と３－アミノ－１，２，４－トリアゾール０．３９ｇを入れ、１３０℃で６時間反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化１２で表される化合物を含む基油拡散防止剤Ｆを得た。
なお、化１９は、ＣＦ3ＣＦ2ＣＦ2ＯＣＦ（ＣＦ3）ＣＦ2ＯＣＦ（ＣＦ3）ＣＨ2ＯＨ（ユニマテック社製）とエピクロロヒドリンを用いて、常法により合成した。
Into a glass flask equipped with a stirring device were placed 5.00 g of the compound represented by Chemical Formula 19 and 0.39 g of 3-amino-1,2,4-triazole, and the mixture was reacted at 130° C. for 6 hours. After the reaction was completed, the same post-treatment as in Example 1 was performed to obtain a base oil diffusion inhibitor F containing the compound represented by Chemical Formula 12.
Compound 19 was synthesized by a conventional method using CF 3 CF 2 CF 2 OCF (CF 3 )CF 2 OCF (CF 3 )CH 2 OH (manufactured by Unimatec) and epichlorohydrin.
実施例７
攪拌装置を備えたガラスフラスコに、化１９の化合物１０．００g とイミダゾール１．２６ｇを入れ、１１０℃で６時間反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化１３で表される化合物を含む基油拡散防止剤Ｇを得た。
10.00 g of the compound represented by Chemical Formula 19 and 1.26 g of imidazole were placed in a glass flask equipped with a stirring device and reacted at 110° C. for 6 hours. After the reaction was completed, the same post-treatment as in Example 1 was performed to obtain a base oil diffusion inhibitor G containing the compound represented by Chemical Formula 13.
実施例８
攪拌装置を備えたガラスフラスコに、化１９の化合物５．００g と３－アミノピロリジン０．８０ｇを入れ、６０℃で３時間反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化１４で表される化合物を含む基油拡散防止剤Ｈを得た。
Into a glass flask equipped with a stirrer were placed 5.00 g of the compound represented by Chemical Formula 19 and 0.80 g of 3-aminopyrrolidine, and the mixture was reacted at 60° C. for 3 hours. After the reaction was completed, the same post-treatment as in Example 1 was performed to obtain a base oil diffusion inhibitor H containing the compound represented by Chemical Formula 14.
実施例９
攪拌装置を備えたガラスフラスコに、化２０の化合物３．５４g と３－アミノピロリジン０．８０ｇ及びメタノール１０ｇを入れ、４０℃で６時間反応させた。反応終了後、室温まで冷却した反応液を精製水及び飽和食塩水で洗浄し、次いで硫酸ナトリウムで乾燥し、溶剤を溜去することにより、化１５で表される化合物を含む基油拡散防止剤Ｉを得た。
なお、化２０の化合物は、Ｅｘｆｌｏｕｒ社から購入したものをそのまま使用した。
Into a glass flask equipped with a stirring device, 3.54 g of the compound of formula 20, 0.80 g of 3-aminopyrrolidine, and 10 g of methanol were placed, and the mixture was reacted at 40° C. for 6 hours. After the reaction is completed, the reaction solution cooled to room temperature is washed with purified water and saturated brine, then dried over sodium sulfate, and the solvent is distilled off to obtain a base oil diffusion inhibitor containing the compound represented by Chemical Formula 15. I got I.
The compound represented by Chemical Formula 20 was purchased from Exflour and used as it was.
実施例１０
攪拌装置を備えたガラスフラスコに、化２０の化合物１０．００g とＮ－（２－アミノエチル) ピペラジン２．２５ｇ及びメタノール３０ｇを入れ、４０℃で６時間反応させた。反応終了後、室温まで冷却した反応液を精製水及び飽和食塩水で洗浄し、次いで硫酸ナトリウムで乾燥し、溶剤を溜去することにより、化１６で表される化合物を含む基油拡散防止剤Ｊを得た。
Into a glass flask equipped with a stirring device were placed 10.00 g of the compound of formula 20, 2.25 g of N-(2-aminoethyl)piperazine, and 30 g of methanol, and the mixture was reacted at 40° C. for 6 hours. After completion of the reaction, the reaction solution cooled to room temperature is washed with purified water and saturated brine, then dried over sodium sulfate, and the solvent is distilled off to obtain a base oil diffusion inhibitor containing the compound represented by Chemical Formula 16. I got J.
実施例１１
攪拌装置を備えたガラスフラスコに、化２１の化合物２．２２g と３－アミノピロリジン０．８０ｇ及びメタノール１０ｇを入れ、４０℃で６時間反応させた。反応終了後、室温まで冷却した反応液を精製水及び飽和食塩水で洗浄し、次いで硫酸ナトリウムで乾燥し、溶剤を溜去することにより、化１７で表される化合物を含む基油拡散防止剤Ｋを得た。
なお、化２１は、ＡＮＬＥＳ社から購入したＣＦ3ＯＣＦ2ＯＣＦ2ＯＣＦ2ＯＣＦ2ＣＯ2Ｈとメタノールから、常法により合成した。
［化２１］
ＣＦ3ＯＣＦ2ＯＣＦ2ＯＣＦ2ＯＣＦ2ＣＯ2ＣＨ3
Into a glass flask equipped with a stirrer, 2.22 g of the compound of formula 21, 0.80 g of 3-aminopyrrolidine, and 10 g of methanol were placed and reacted at 40° C. for 6 hours. After the reaction is completed, the reaction solution cooled to room temperature is washed with purified water and saturated brine, then dried over sodium sulfate, and the solvent is distilled off to obtain a base oil diffusion inhibitor containing the compound represented by Chemical Formula 17. I got K.
In addition, Chemical Formula 21 was synthesized by a conventional method from CF 3 OCF 2 OCF 2 OCF 2 OCF 2 CO 2 H purchased from ANLES and methanol.
[chemical formula 21]
CF 3 OCF 2 OCF 2 OCF 2 OCF 2 CO 2 CH 3
比較例１
攪拌装置を備えたガラスフラスコに、化１８の化合物１０．００g とトリエチレンテトラミン１．６１ｇ及び１，３－ビス（トリフルオロメチル) ベンゼン１０ｇを入れ６０℃で４時間攪拌しながら反応させた。反応終了後、室温まで冷却した反応液を精製水及び飽和食塩水で洗浄し、次いで硫酸ナトリウムで乾燥し、溶剤を留去することにより、化２２で表される化合物を含む基油拡散防止剤Ｌを得た。
Into a glass flask equipped with a stirring device, 10.00 g of the compound of formula 18, 1.61 g of triethylenetetramine, and 10 g of 1,3-bis(trifluoromethyl)benzene were placed and reacted with stirring at 60° C. for 4 hours. After completion of the reaction, the reaction solution cooled to room temperature is washed with purified water and saturated brine, then dried over sodium sulfate, and the solvent is distilled off to obtain a base oil diffusion inhibitor containing the compound represented by Chemical Formula 22. I got L.
比較例２
攪拌装置を備えたガラスフラスコに、化２３の化合物１０．８７ｇと３－アミノ－１，２，４－トリアゾール１．０９ｇを入れ、１２０℃で4 時間攪拌しながら反応させた。反応終了後、実施例１と同様の後処理を行うことにより、化２４で表される化合物を含む基油拡散防止剤Ｍを得た。
10.87 g of the compound represented by Chemical Formula 23 and 1.09 g of 3-amino-1,2,4-triazole were placed in a glass flask equipped with a stirring device, and reacted with stirring at 120° C. for 4 hours. After the reaction was completed, the same post-treatment as in Example 1 was carried out to obtain a base oil diffusion inhibitor M containing the compound represented by Chemical Formula 24.
比較例３
攪拌装置を備えたガラスフラスコに化２５の化合物５．００ｇとＮ，Ｎ－ジエチル－１，３－ジアミノプロパン１．７３ｇ及び１，３－ビス（トリフルオロメチル) ベンゼン１０ｇを入れ、６０℃で4 時間攪拌しながら反応させた。反応終了後、比較例１と同様の後処理を行うことにより、化２６で表される化合物を含む基油拡散防止剤Ｎを得た。
5.00 g of the compound of chemical formula 25, 1.73 g of N,N-diethyl-1,3-diaminopropane, and 10 g of 1,3-bis(trifluoromethyl)benzene were placed in a glass flask equipped with a stirring device, and the mixture was heated at 60°C. The reaction was allowed to proceed for 4 hours with stirring. After the reaction was completed, the same post-treatment as in Comparative Example 1 was performed to obtain a base oil diffusion inhibitor N containing the compound represented by Chemical Formula 26.
比較例４
化１８の化合物を、基油拡散防止剤Ｏとした。
Comparative example 4
The compound of Chemical Formula 18 was used as base oil diffusion inhibitor O.
比較例５
化１９の化合物を、基油拡散防止剤Ｐとした。
Comparative example 5
The compound of Chemical Formula 19 was used as a base oil diffusion inhibitor P.
比較例６
化２０の化合物を、基油拡散防止剤Ｑとした。
Comparative example 6
The compound of Chemical Formula 20 was used as base oil diffusion inhibitor Q.
比較例７
化２１の化合物を、基油拡散防止剤Ｒとした。
Comparative example 7
The compound of Chemical Formula 21 was used as a base oil diffusion inhibitor R.
［基油拡散防止性能の評価（その１）］
実施例１～１１で得られた基油拡散防止剤Ａ～Ｋ及び比較例１～５で得られた基油拡散防止剤Ｌ～Ｒの各々を、モリコート ＨＰ－３００グリース（東レ・ダウコーニング社製；フッ素油を基油とするグリース）に３重量％添加し、均一に攪拌して１８種類のグリースを得た。得られた１８種類の各グリースを、図１に示す如く、直径６ｍｍ、高さ１ｍｍの円筒状になるようにポリエステルフィルム（ソマール社製；グレード「ソマブラックフィルムＲ」タイプ「１００ＭＤ」）に塗布した。なお、モリコート ＨＰ－３００グリースに、基油拡散防止剤を添加することなく、そのまま塗布したものを比較例８とした。
グリースを塗布した後、８０℃の恒温器に入れ促進試験を行い、２４時間後の基油の拡散状態を評価した。この評価は、図１に示すように、基油が滲み出し拡散した直径Ａｍｍを測定し、Ａｍｍ－６ｍｍ＝拡散幅（ｍｍ）を計算した。この結果を、表１に示した。拡散幅（ｍｍ）の値が小さいほど、基油拡散防止性能に優れる。
[Evaluation of base oil diffusion prevention performance (Part 1)]
Each of the base oil diffusion inhibitors A to K obtained in Examples 1 to 11 and the base oil diffusion inhibitors L to R obtained in Comparative Examples 1 to 5 was mixed with Molykote HP-300 Grease (Toray/Dow Corning Co., Ltd.). 3% by weight was added to a grease containing fluorine oil as a base oil) and stirred uniformly to obtain 18 types of grease. Each of the 18 types of grease obtained was applied to a polyester film (manufactured by Somar Corporation; grade "Soma Black Film R" type "100MD") in a cylindrical shape with a diameter of 6 mm and a height of 1 mm, as shown in Figure 1. did. Comparative Example 8 was prepared by applying Molykote HP-300 grease as it was without adding a base oil diffusion inhibitor.
After applying the grease, it was placed in a thermostat at 80° C. to perform an acceleration test, and the state of base oil diffusion after 24 hours was evaluated. For this evaluation, as shown in FIG. 1, the diameter Amm in which the base oil exuded and spread was measured, and Amm-6mm=diffusion width (mm) was calculated. The results are shown in Table 1. The smaller the value of the diffusion width (mm), the better the base oil diffusion prevention performance.
［表１］
━━━━━━━━━━━━━━━━
拡散幅（ｍｍ）
━━━━━━━━━━━━━━━━
実施例１ ２ｍｍ
実施例２ ０ｍｍ
実施例３ ０ｍｍ
実施例４ ０ｍｍ
実施例５ ０ｍｍ
実施例６ ６ｍｍ
実施例７ ８ｍｍ
実施例８ ６ｍｍ
実施例９ ２ｍｍ
実施例１０ ２ｍｍ
実施例１１ ２ｍｍ
比較例１ ３４ｍｍ
比較例２ ２８ｍｍ
比較例３ ３３ｍｍ
比較例４ ２７ｍｍ
比較例５ ２２ｍｍ
比較例６ ２５ｍｍ
比較例７ ３０ｍｍ
比較例８ ３６ｍｍ
━━━━━━━━━━━━━━━━
[Table 1]
━━━━━━━━━━━━━━━━
Diffusion width (mm)
━━━━━━━━━━━━━━━━
Example 1 2mm
Example 2 0mm
Example 3 0mm
Example 4 0mm
Example 5 0mm
Example 6 6mm
Example 7 8mm
Example 8 6mm
Example 9 2mm
Example 10 2mm
Example 11 2mm
Comparative example 1 34mm
Comparative example 2 28mm
Comparative example 3 33mm
Comparative example 4 27mm
Comparative example 5 22mm
Comparative example 6 25mm
Comparative example 7 30mm
Comparative example 8 36mm
━━━━━━━━━━━━━━━━
表１から明らかなように、実施例に係る基油拡散防止剤を添加したグリースは、基油の拡散幅が８ｍｍ以下となっており、基油の拡散が顕著に防止されていることが分かる。 As is clear from Table 1, the base oil diffusion width of the grease to which the base oil diffusion inhibitor according to the example was added was 8 mm or less, indicating that base oil diffusion was significantly prevented. .
［基油拡散防止性能の評価（その２）］
実施例４及び５で得られた基油拡散防止剤Ｄ及びＥの各々を、モリコート ＨＰ－３００グリースに１重量％添加し、均一に攪拌して２種類のグリースを得た。得られた２種類の各グリースにつき、基油拡散防止性能の評価（その１）と同一の方法で基油の拡散状態を評価した。その結果、実施例４の基油拡散防止剤Ｄを添加したグリースは拡散幅が２ｍｍであり、実施例５の基油拡散防止剤Ｅを添加したグリースは拡散幅が２ｍｍであり、いずれも基油の拡散が顕著に防止されていることが分かる。
[Evaluation of base oil diffusion prevention performance (part 2)]
Each of the base oil diffusion inhibitors D and E obtained in Examples 4 and 5 was added in an amount of 1% by weight to Molykote HP-300 grease and stirred uniformly to obtain two types of grease. For each of the two types of grease obtained, the base oil diffusion state was evaluated using the same method as in the evaluation of base oil diffusion prevention performance (part 1). As a result, the grease to which base oil diffusion inhibitor D of Example 4 was added had a diffusion width of 2 mm, and the grease to which base oil diffusion inhibitor E of Example 5 was added had a diffusion width of 2 mm. It can be seen that oil diffusion is significantly prevented.
［基油拡散防止性能の評価（その３）］
実施例２～５で得られた基油拡散防止剤Ｂ～Ｅの各々を、バリエルタ ＩＥＬ／Ｖグリース（ユニマテック社製；フッ素油を基油とするグリース）に３重量％添加し、均一に攪拌して４種類のグリースを得た。得られた４種類の各グリースにつき、基油拡散防止性能の評価（その１）と同一の方法で基油の拡散状態を評価した。なお、バリエルタ ＩＥＬ／Ｖグリースに、基油拡散防止剤を添加することなく、そのまま塗布したものを比較例９とした。その結果、実施例２の基油拡散防止剤Ｂを添加したグリースは拡散幅が２ｍｍであり、実施例３の基油拡散防止剤Ｃを添加したグリースは拡散幅が０ｍｍであり、実施例４の基油拡散防止剤Ｄを添加したグリースは拡散幅が０ｍｍであり、実施例５の基油拡散防止剤Ｅを添加したグリースは拡散幅が０ｍｍであった。なお、比較例９のグリースの拡散幅は３８ｍｍであった。したがって、実施例２～５で得られた基油拡散防止剤Ｂ～Ｅを添加すると、いずれも基油の拡散が顕著に防止されていることが分かる。
[Evaluation of base oil diffusion prevention performance (part 3)]
3% by weight of each of the base oil diffusion inhibitors B to E obtained in Examples 2 to 5 was added to Varierta IEL/V Grease (manufactured by Unimatec; grease with fluorine oil as the base oil) and stirred uniformly. Four types of grease were obtained. For each of the four types of grease obtained, the base oil diffusion state was evaluated using the same method as in the evaluation of base oil diffusion prevention performance (part 1). Comparative Example 9 was prepared by applying Varielta IEL/V grease as it was without adding a base oil diffusion inhibitor. As a result, the grease containing the base oil diffusion inhibitor B of Example 2 had a diffusion width of 2 mm, the grease containing the base oil diffusion inhibitor C of Example 3 had a diffusion width of 0 mm, and the grease of Example 4 had a diffusion width of 2 mm. The grease to which the base oil diffusion inhibitor D of Example 5 was added had a diffusion width of 0 mm, and the grease to which the base oil diffusion inhibitor E of Example 5 was added had a diffusion width of 0 mm. Note that the spread width of the grease in Comparative Example 9 was 38 mm. Therefore, it can be seen that when the base oil diffusion inhibitors B to E obtained in Examples 2 to 5 were added, base oil diffusion was significantly prevented in all cases.
Claims (6)
［化１］
Ｒ1（ＯＣＦＲ2ＣＦ2）n1（ＯＣＦＲ3）n2－Ｚ－Ｙ
（式中、Ｒ1は炭素数１～５のパーフルオロアルキル基であり、Ｒ2及びＲ3はフッ素原子又はトリフルオロメチル基であり、ｎ１は０～４の整数であり、ｎ２は１以上の整数であり、ｎ１＋ｎ２は１～１０の整数である。ＺはＣ（Ｏ）又はＣＨ2ＯＣＨ2ＣＨ（ＯＨ）ＣＨ2であり、Ｙは含窒素複素環を含む基である。なお、（ＯＣＦＲ2ＣＦ2）と（ＯＣＦＲ3）の出現順序は無作為である。） A base oil diffusion inhibitor comprising a fluorine-containing compound represented by formula 1, which is a base oil diffusion inhibitor made of fluorine oil.
[Chemical formula 1]
R 1 (OCFR 2 CF 2 ) n1 (OCFR 3 ) n2 -Z-Y
(In the formula, R 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, R 2 and R 3 are a fluorine atom or a trifluoromethyl group, n1 is an integer of 0 to 4, and n2 is 1 or more. n1+n2 is an integer of 1 to 10. Z is C(O) or CH 2 OCH 2 CH(OH)CH 2 , and Y is a group containing a nitrogen-containing heterocycle. The order of appearance of OCFR 2 CF 2 ) and (OCFR 3 ) is random.)
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| JP2010254736A (en) | 2009-04-21 | 2010-11-11 | Unimatec Co Ltd | Method for producing fluorine-containing polyether carboxylic acid amide |
| JP2010254737A (en) | 2009-04-21 | 2010-11-11 | Nok Kluber Kk | Fluorine-based lubricant composition |
| JP2010254738A5 (en) | 2009-04-21 | 2012-05-24 | ||
| WO2018139174A1 (en) | 2017-01-26 | 2018-08-02 | 昭和電工株式会社 | Fluoroether compound, lubricant for magnetic recording medium, and magnetic recording medium |
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| JP2010254737A (en) | 2009-04-21 | 2010-11-11 | Nok Kluber Kk | Fluorine-based lubricant composition |
| JP2010254738A5 (en) | 2009-04-21 | 2012-05-24 | ||
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