JP2017019933A - Grease composition - Google Patents
Grease composition Download PDFInfo
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- JP2017019933A JP2017019933A JP2015138888A JP2015138888A JP2017019933A JP 2017019933 A JP2017019933 A JP 2017019933A JP 2015138888 A JP2015138888 A JP 2015138888A JP 2015138888 A JP2015138888 A JP 2015138888A JP 2017019933 A JP2017019933 A JP 2017019933A
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- grease composition
- grease
- rust
- metal salt
- monocarboxylic acid
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- 239000004519 grease Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 25
- -1 aromatic monocarboxylic acid Chemical class 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical group [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 8
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 8
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 8
- 239000002562 thickening agent Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 4
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011737 fluorine Substances 0.000 abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 42
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 16
- 230000008020 evaporation Effects 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 15
- 230000002265 prevention Effects 0.000 description 15
- 230000003449 preventive effect Effects 0.000 description 15
- 239000002994 raw material Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 8
- 235000013373 food additive Nutrition 0.000 description 7
- 239000002778 food additive Substances 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000002199 base oil Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- NCXUIEDQTCQZRK-UHFFFAOYSA-L disodium;decanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCCCCCC([O-])=O NCXUIEDQTCQZRK-UHFFFAOYSA-L 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 2
- NYHRXCLAJGLCDZ-UHFFFAOYSA-L C(CCCCCCCCC(=O)[O-])(=O)[O-].[Na+].N(=O)O.[Na+] Chemical compound C(CCCCCCCCC(=O)[O-])(=O)[O-].[Na+].N(=O)O.[Na+] NYHRXCLAJGLCDZ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LSXBXNYRHYLVSC-UHFFFAOYSA-L disodium benzoate nitrite Chemical compound N(=O)[O-].[Na+].C(C1=CC=CC=C1)(=O)[O-].[Na+] LSXBXNYRHYLVSC-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000004005 nitrosamines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RAADJDWNEAXLBL-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 RAADJDWNEAXLBL-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
本発明は、耐熱性、防錆性、安全性に優れ、高温環境下で使用するのに好適な、フッ素グリース組成物に関する。 The present invention relates to a fluorine grease composition that is excellent in heat resistance, rust prevention, and safety and is suitable for use in a high temperature environment.
一般的なフッ素グリースは、パーフルオロポリエーテルを基油に用い、増ちょう剤としては、ポリテトラフルオロエチレンなどのフッ素樹脂が使用され、必要に応じて防錆剤、酸化防止剤などの添加剤が処方されている。 General fluorine grease uses perfluoropolyether as the base oil, and as a thickener, fluorine resin such as polytetrafluoroethylene is used, and additives such as rust preventives and antioxidants are used as necessary. Is prescribed.
フッ素グリースは、優れた耐熱性を有していることから、自動車電装・補機、事務機器、コルゲートマシンなどの耐熱軸受用グリースとして主に使用されている。また、近年では食品機械用のグリースとしても使用されている。このような用途に使用されるフッ素グリースには、高温環境下における耐久性だけでなく、優れた防錆性、環境適合性、人体への安全性、コストパフォーマンスも要求される。 Since fluorine grease has excellent heat resistance, it is mainly used as heat-resistant bearing grease for automobile electrical equipment / auxiliary equipment, office equipment, corrugated machines and the like. In recent years, it is also used as a grease for food machinery. Fluorine grease used for such applications is required not only for durability under high temperature environments, but also for excellent rust prevention, environmental compatibility, safety to human bodies, and cost performance.
フッ素グリースに添加する防錆剤としては、亜硝酸ナトリウムが幅広く使用されてきたが、亜硝酸ナトリウムは第二級アミンと反応し、環境負荷物質であるニトロソアミンを生成することが知られている。そのため、近年では亜硝酸ナトリウムの使用が制限され、亜硝酸ナトリウムに代わる防錆剤が求められている。また、亜硝酸ナトリウムに代わる防錆剤としては、これまでに各種の化合物が検討されている。 Sodium nitrite has been widely used as a rust inhibitor to be added to fluorine grease, but sodium nitrite is known to react with secondary amines to produce nitrosamines, which are environmentally hazardous substances. Therefore, in recent years, the use of sodium nitrite has been restricted, and a rust preventive agent replacing sodium nitrite has been demanded. Various compounds have been studied so far as rust preventives to replace sodium nitrite.
例えば、分子末端に官能基を有するパーフルオロポリエーテル若しくはフルオロポリエーテル誘導体を使用することにより、高い腐食耐性を付与させたフッ素グリースが得られることが報告されている（特許文献１）。 For example, it has been reported that a fluorine grease imparted with high corrosion resistance can be obtained by using a perfluoropolyether or a fluoropolyether derivative having a functional group at the molecular end (Patent Document 1).
また、芳香族スルホン酸または飽和脂肪族ジカルボン酸のＣａ塩またはＮａ塩を添加することで、防錆性に優れ、熱履歴を受けた後の防錆性も良好な潤滑剤組成物も提案されている（特許文献２）。 Also, by adding Ca salt or Na salt of aromatic sulfonic acid or saturated aliphatic dicarboxylic acid, a lubricant composition having excellent rust prevention property and good rust prevention property after receiving a heat history has also been proposed. (Patent Document 2).
さらに、以下に示す一般式（１）の脂肪族二塩基酸塩を０．１質量％以上、１．０質量％未満で添加することで、優れた防錆性を有し、蒸発減量が少ないフッ素グリース組成物も提案されている（特許文献３）。
（ＣＨ２）ｎ（ＣＯＯ）２Ｍｍ・・・（１）
（式中、ｎは１〜１９の整数、Ｍはアルカリ金属又はアルカリ土類金属を示し、ｍはＭがアルカリ金属のときは２、アルカリ土類金属のときは１を示す。）
Furthermore, by adding the aliphatic dibasic acid salt of the general formula (1) shown below in an amount of 0.1% by mass or more and less than 1.0% by mass, it has excellent rust preventive properties and low evaporation loss. A fluorine grease composition has also been proposed (Patent Document 3).
(CH 2 ) n (COO) 2 M m (1)
(In the formula, n represents an integer of 1 to 19, M represents an alkali metal or alkaline earth metal, m represents 2 when M is an alkali metal, and 1 when M is an alkaline earth metal.)
しかしながら、特許文献１の潤滑グリースは、耐熱性が不十分であり、厳しい条件下では、防錆性も不足する。また、全ての原料がフッ素系の化合物であるため、コストは高価である。 However, the lubricating grease of Patent Document 1 has insufficient heat resistance, and under harsh conditions, it also lacks rust prevention. Moreover, since all the raw materials are fluorine-type compounds, cost is expensive.
また、特許文献２に示す実施例において芳香族スルホン酸塩として使用されているジノニルナフタレンスルホン酸Ｃａと石油スルホン酸Ｎａに関しては、高温環境下における蒸発減量が多く、耐熱性が不十分である。また、これらの防錆剤はパーフルオロポリエーテルとは相溶性のない液体の防錆剤であるため、多量に添加すると長期間保管した場合、防錆剤が分離する懸念もある。さらに、飽和脂肪族ジカルボン酸塩として使用されているセバシン酸ナトリウムに関しては、食品機械用のグリースに使用する場合は添加量に制約が生じる。 In addition, dinonyl naphthalene sulfonate Ca and petroleum sulfonate Na used as aromatic sulfonates in the examples shown in Patent Document 2 have a large evaporation loss in a high temperature environment and have insufficient heat resistance. . Moreover, since these rust preventive agents are liquid rust preventive agents that are not compatible with perfluoropolyether, there is a concern that the rust preventive agent will be separated when stored for a long period of time when added in a large amount. Further, regarding sodium sebacate used as a saturated aliphatic dicarboxylate, there is a restriction on the amount of addition when used in grease for food machinery.
また、特許文献３に示すグリース組成物は、防錆剤の添加量が少ないため、評価条件によっては、十分な防錆性を発揮しないことがある。 Moreover, since the grease composition shown in patent document 3 has little addition amount of a rust preventive agent, depending on evaluation conditions, sufficient rust prevention property may not be exhibited.
そこで、本発明者は、耐熱性、防錆性、安全性を両立させるために、鋭意検討した結果、パーフルオロポリエーテルおよび芳香族モノカルボン酸金属塩が耐熱性、防錆性、安全性を向上させることを見出し、本発明を完成するに至った。すなわち、本発明は、耐熱性、防錆性に優れ、環境負荷物質の発生しない、安全性の高いフッ素グリース組成物を提供することを目的とする。 Therefore, the present inventor has made extensive studies in order to achieve both heat resistance, rust prevention and safety, and as a result, perfluoropolyether and aromatic monocarboxylic acid metal salt have heat resistance, rust prevention and safety. The inventors have found that the present invention has been improved and have completed the present invention. That is, an object of the present invention is to provide a highly safe fluorine grease composition that is excellent in heat resistance and rust prevention properties and does not generate an environmental load substance.
上記課題を解決するために請求項１に記載の本発明は、パーフルオロポリエーテルおよび芳香族モノカルボン酸金属塩を含有していることを特徴とするグリース組成物を提供する。 In order to solve the above problems, the present invention according to claim 1 provides a grease composition characterized by containing a perfluoropolyether and an aromatic monocarboxylic acid metal salt.
上記課題を解決するために請求項２に記載の本発明は、請求項１に記載のグリース組成物において、芳香族モノカルボン酸金属塩が安息香酸ナトリウムであり、グリース組成物の全質量に対して、０．１〜４０．０質量％含有していることを特徴とする。 In order to solve the above problems, the present invention according to claim 2 is the grease composition according to claim 1, wherein the aromatic monocarboxylic acid metal salt is sodium benzoate, and the total weight of the grease composition is And 0.1 to 40.0% by mass.
上記課題を解決するために請求項３に記載の本発明は、請求項１又は２に記載のグリース組成物において、更に、増ちょう剤として、ポリテトラフルオロエチレン、カーボンブラック、シリカ、メラミンシアヌレートから選ばれる少なくとも一種を含有していることを特徴とする。 In order to solve the above-mentioned problems, the present invention according to claim 3 is the grease composition according to claim 1 or 2, further comprising polytetrafluoroethylene, carbon black, silica, melamine cyanurate as a thickener. It contains at least one selected from
上記課題を解決するために請求項４に記載の本発明は、請求項１〜３のいずれか１項に記載のグリース組成物において、パーフルオロポリエーテルの４０℃での動粘度が１０〜１０００ｍｍ２／秒であることを特徴とする。 In order to solve the above-mentioned problem, the present invention according to claim 4 is the grease composition according to any one of claims 1 to 3, wherein the kinematic viscosity of the perfluoropolyether at 40 ° C. is 10 to 1000 mm. 2 / sec.
上記課題を解決するために請求項５に記載の本発明は、請求項１〜４のいずれか１項に記載のグリース組成物において、グリース組成物が転がり軸受用であることを特徴とする。 In order to solve the above problems, the present invention according to claim 5 is characterized in that in the grease composition according to any one of claims 1 to 4, the grease composition is for a rolling bearing.
本発明に係るグリース組成物によれば、防錆剤として亜硝酸ナトリウムやセバシン酸ナトリウムを使用した従来のグリース組成物よりも安全性が高く、しかも、耐熱性及び防錆性のいずれをも犠牲にすることなく両立することができ、さらに、塩水が混入する環境下でも錆の発生を抑制すると共に高温環境下でも優れた耐久性を示すという効果がある。 According to the grease composition of the present invention, it is safer than conventional grease compositions using sodium nitrite or sodium sebacate as a rust inhibitor, and sacrifices both heat resistance and rust resistance. In addition, there is an effect of suppressing the generation of rust even in an environment where salt water is mixed and exhibiting excellent durability even in a high temperature environment.
本発明に係るグリース組成物について以下好ましい実施形態に基づいて詳細に説明する。
［基油］
本発明に係るグリース組成物に使用する基油は、潤滑油として使用されるパーフルオロポリエーテルであれば、全て使用可能である。そして、好ましくは４０℃における動粘度が１０〜１０００ｍｍ２／秒であり、更に好ましくは４０℃における動粘度が１００〜６００ｍｍ２／秒である。４０℃における動粘度が１０ｍｍ２／秒未満のものは、分子量が短いため、高温環境下における蒸発量が多くなり、高温での使用に適さない。また、４０℃における動粘度が１０００ｍｍ２／秒を超えるものは、流動点が高くなり低温環境下での使用に適さない。もちろん、そのような使用環境を考慮した上で４０℃における動粘度が１０〜１０００ｍｍ２／秒でないものを用いることは可能である。また、グリース全体量に対する基油の割合は、５０〜９０質量％であることが好ましい。
The grease composition according to the present invention will be described in detail below based on preferred embodiments.
[Base oil]
As the base oil used in the grease composition according to the present invention, any perfluoropolyether used as a lubricating oil can be used. And preferably, the kinematic viscosity at 40 ° C. is 10 to 1000 mm 2 / sec, and more preferably the kinematic viscosity at 40 ° C. is 100 to 600 mm 2 / sec. Those having a kinematic viscosity at 40 ° C. of less than 10 mm 2 / sec have a short molecular weight, and therefore the amount of evaporation in a high-temperature environment increases and is not suitable for use at high temperatures. Moreover, when the kinematic viscosity at 40 ° C. exceeds 1000 mm 2 / sec, the pour point becomes high and it is not suitable for use in a low temperature environment. Of course, it is possible to use a material whose kinematic viscosity at 40 ° C. is not 10 to 1000 mm 2 / second in consideration of such a use environment. Moreover, it is preferable that the ratio of the base oil with respect to the grease whole quantity is 50-90 mass%.
［芳香族モノカルボン酸金属塩］
本発明に係るグリース組成物に使用する芳香族モノカルボン酸金属塩は、芳香族モノカルボン酸が、例えば、安息香酸、ナフトエ酸、フェニル酢酸、トルイル酸、およびこれらの酸の誘導体であることが好ましい。また、金属塩としては、リチウム、ナトリウム、カリウム、カルシウム、マグネシウムなどのアルカリ金属やアルカリ土類金属の金属塩が挙げられる。具体例としては、安息香酸ナトリウム、安息香酸カリウム、安息香酸カルシウムなどが好ましい。また、グリース全体量に対する芳香族モノカルボン酸金属塩の割合は、通常は０．１〜４０．０質量％であることが好ましい。更に好ましくは、２．０〜２５．０質量％である。また、芳香族モノカルボン酸金属塩は防錆剤としての効果があるが、増ちょう剤として用いることもできる。
[Aromatic monocarboxylic acid metal salt]
In the aromatic monocarboxylic acid metal salt used in the grease composition according to the present invention, the aromatic monocarboxylic acid is, for example, benzoic acid, naphthoic acid, phenylacetic acid, toluic acid, and derivatives of these acids. preferable. Examples of the metal salt include metal salts of alkali metals and alkaline earth metals such as lithium, sodium, potassium, calcium, and magnesium. Specific examples include sodium benzoate, potassium benzoate, and calcium benzoate. The ratio of the aromatic monocarboxylic acid metal salt to the total amount of grease is usually preferably 0.1 to 40.0% by mass. More preferably, it is 2.0-25.0 mass%. In addition, the aromatic monocarboxylic acid metal salt has an effect as a rust preventive, but can also be used as a thickener.
［増ちょう剤］
本発明に係るグリース組成物に使用する増ちょう剤は、パーフルオロポリエーテルに分散し、半固体のグリース状にできるものであれば、全て使用できる。例えば、金属石けん、ウレア化合物、ナトリウムテレフタレート、ポリテトラフルオロエチレン、カーボンブラック、メラミンシアヌレート、シリカなどが挙げられる。耐熱性を考慮した場合には、ポリテトラフルオロエチレン、カーボンブラック、シリカ、メラミンシアヌレートが好ましい。また、グリース全体量に対する増ちょう剤の割合は、５０質量％未満であることが好ましい。５０質量％を超えると硬くなりすぎてしまい、グリースとしては使用しにくい。尚、芳香族モノカルボン酸金属塩だけでも、パーフルオロポリエーテルをグリース状にすることができるため、増ちょう剤を使用しなくても良い場合もある。
[Thickener]
Any thickener used in the grease composition according to the present invention can be used as long as it can be dispersed in perfluoropolyether to form a semi-solid grease. For example, metal soap, urea compound, sodium terephthalate, polytetrafluoroethylene, carbon black, melamine cyanurate, silica and the like can be mentioned. In consideration of heat resistance, polytetrafluoroethylene, carbon black, silica, and melamine cyanurate are preferable. Moreover, it is preferable that the ratio of the thickener with respect to the whole amount of grease is less than 50 mass%. If it exceeds 50% by mass, it becomes too hard and is difficult to use as a grease. In addition, since the perfluoropolyether can be made into a grease state with only the aromatic monocarboxylic acid metal salt, it may not be necessary to use a thickener.
次に、本発明に係るグリース組成物について、具体的な実施例を示しながら説明する。実施例１及び比較例１〜８では、下記の各種防錆剤を用いて耐熱性を評価した。 Next, the grease composition according to the present invention will be described with reference to specific examples. In Example 1 and Comparative Examples 1-8, heat resistance was evaluated using the following various rust preventives.
［防錆剤］
防錆剤として以下のものを使用した。
安息香酸ナトリウム：（株）伏見製薬所製 安息香酸ナトリウム
亜硝酸ナトリウム：純正化学（株） 試薬特級 亜硝酸ナトリウム
セバシン酸ナトリウム：ＢＡＳＦ社製 ＩＲＧＡＣＯＲ ＤＳＳ Ｇ
芳香族スルホン酸カルシウム：ＫＩＮＧ社製 ＮＡ−ＳＵＬ ７２９
ＰＦＰＥ誘導体Ａ：Ｓｏｌｖａｙ社製 ＦＯＭＢＬＩＮ ＤＡ３０５
ＰＦＰＥ誘導体Ｂ：Ｓｏｌｖａｙ社製 ＦＯＭＢＬＩＮ ＤＡ３０６ ＶＡＣ
ＰＦＰＥ誘導体Ｃ：Ｓｏｌｖａｙ社製 ＦＯＭＢＬＩＮ ＤＡ３０８
ＰＦＰＥ誘導体Ｄ：Ｄｕｐｏｎｔ社製 クライトックス１５７ＦＳ−Ｌ
ＰＦＰＥ誘導体Ｅ：Ｄｕｐｏｎｔ社製 クライトックス１５７ＦＳ−Ｈ
[Rust preventive]
The following were used as rust inhibitors.
Sodium benzoate: manufactured by Fushimi Pharmaceutical Co., Ltd. Sodium benzoate Sodium nitrite: Pure Chemicals Co., Ltd. Reagent special grade Sodium nitrite Sodium sebacate: BASF Corporation IRGACOR DSS G
Aromatic calcium sulfonate: NA-SUL 729 manufactured by KING
PFPE derivative A: FOMBLIN DA305 manufactured by Solvay
PFPE derivative B: FOMBLIN DA306 VAC manufactured by Solvay
PFPE derivative C: FOMBLIN DA308 manufactured by Solvay
PFPE derivative D: Krytox 157FS-L manufactured by Dupont
PFPE derivative E: Dupont Krytox 157FS-H
上記の各種防錆剤について、蒸発損失試験を実施した。
（１）蒸発損失試験
［試験条件］
１０ｍＬのビーカーに各種原料を０．３０±０．０１ｇを計量し、２００℃の恒温槽で３時間の静置加熱し、取り出し後に重量減を測定した。試験結果は蒸発減量で、以下の５段階の評価とした。
評価Ａ：蒸発減量２％未満
評価Ｂ：蒸発減量２％以上〜５％未満
評価Ｃ：蒸発減量５％以上〜１０％未満
評価Ｄ：蒸発減量１０％以上〜２０％未満
評価Ｅ：蒸発減量２０％以上
An evaporation loss test was performed on the various rust inhibitors described above.
(1) Evaporation loss test [Test conditions]
In a 10 mL beaker, 0.30 ± 0.01 g of various raw materials were weighed, left to stand in a thermostatic bath at 200 ° C. for 3 hours, and weight loss was measured after removal. The test result was evaporation loss, and was evaluated in the following five stages.
Evaluation A: Evaporation loss less than 2% Evaluation B: Evaporation loss from 2% to less than 5% Evaluation C: Evaporation loss from 5% to less than 10% Evaluation D: Evaporation loss from 10% to less than 20% Evaluation E: Evaporation loss 20 %that's all
また、各種原料の安全性は、米国の食品添加物リスト（ＥＡＦＵＳ）への収載状況とＮＳＦが規定しているＨＸ−１への収載状況で判断した。 In addition, the safety of various raw materials was judged based on the status of inclusion in the US food additive list (EAFUS) and the status of inclusion in HX-1 defined by NSF.
（２）米国食品添加物リスト（ＥＡＦＵＳ）
このリストに収載されている原料は、米国の食品添加物として認められた安全性の高い原料であり、食品機械用グリースにも適用できると判断した。この場合、使用する各種原料は食品添加物としての基準を満たすものを用いる。
(2) US Food Additive List (EAFUS)
The raw materials on this list are highly safe raw materials that are recognized as food additives in the United States, and are judged to be applicable to grease for food machinery. In this case, the various raw materials used satisfy the standards for food additives.
（３）ＮＳＦ ＨＸ−１
上記の米国食品添加物リスト（ＥＡＦＵＳ）に収載のない防錆剤については、ＮＳＦが規定しているＨＸ−１への収載状況を確認した。ＨＸ−１に収載されている原料は、偶発的に食品に触れる可能性がある箇所で使用できる潤滑剤に使用できる原料・成分であり、収載のないものは、食品機械用グリースには使用できない、安全性の低い原料であると判断した。
(3) NSF HX-1
For rust inhibitors not listed on the above US Food Additives List (EAFUS), the status of listing in HX-1 defined by NSF was confirmed. The raw materials listed in HX-1 are raw materials / components that can be used for lubricants that can be used in places where food may accidentally come into contact with food. Those that are not listed cannot be used as grease for food machinery. Therefore, it was judged that the raw material was low in safety.
以上の結果を表１に示す。 The results are shown in Table 1.
表１に示すように、実施例１の安息香酸ナトリウムは蒸発減量が１．４％と少なく、評価Aであり、耐熱性に優れていることが分かる。また、米国食品添加物リストにも収載されており、安全性の高い防錆剤である。比較例１の亜硝酸ナトリウムに関しては、蒸発減量が０．８と少なく、評価Aであり、米国食品添加物リストにも収載されてはいるが、第二級アミンと反応し、環境負荷物質であるニトロソアミンを生成することから、近年では使用が制限されている。比較例２のセバシン酸ナトリウムに関しては、蒸発減量が２．３で評価Ｂであり、耐熱性と安全性ともに、わずかに劣る。その他のものは、蒸発減量が多く、耐熱性が大幅に劣る。 As shown in Table 1, the sodium benzoate of Example 1 has a low evaporation loss of 1.4%, which is an evaluation A, and is excellent in heat resistance. It is also listed on the US Food Additives List and is a highly safe rust inhibitor. The sodium nitrite of Comparative Example 1 has a low evaporation loss of 0.8 and is rated A. Although it is listed in the US food additive list, it reacts with secondary amines and is an environmentally hazardous substance. Since it produces certain nitrosamines, its use has been limited in recent years. Regarding the sodium sebacate of Comparative Example 2, the evaporation loss is 2.3, which is an evaluation B, and both heat resistance and safety are slightly inferior. Others have a large amount of evaporation loss, and heat resistance is greatly inferior.
次に、実施例２〜５、比較例９〜１７では、下記の各種原料を用いてグリースを調製し、防錆性の評価を行った。 Next, in Examples 2 to 5 and Comparative Examples 9 to 17, greases were prepared using the following various raw materials, and the antirust property was evaluated.
［基油］
パーフルオロポリエーテル（ＰＦＰＥ）
ＤｕＰｏｎｔ社製 クライトックスＧＰＬ１０５
動粘度（４０℃）１６０ｍｍ２／秒
[Base oil]
Perfluoropolyether (PFPE)
DuPont Krytox GPL105
Kinematic viscosity (40 ° C.) 160 mm 2 / sec
［増ちょう剤］
ポリテトラフルオロエチレン（ＰＴＦＥ）
ＤｕＰｏｎｔ社製 ドライフィルムＧＴ
平均粒径４〜１２μｍ 一次粒径０．２μｍ以下
[Thickener]
Polytetrafluoroethylene (PTFE)
DuPont dry film GT
Average particle size 4-12μm Primary particle size 0.2μm or less
［防錆剤］
安息香酸ナトリウム：（株）伏見製薬所製 安息香酸ナトリウム
亜硝酸ナトリウム：純正化学（株） 試薬特級 亜硝酸ナトリウム
セバシン酸ナトリウム：ＢＡＳＦ社製 ＩＲＧＡＣＯＲ ＤＳＳ Ｇ
芳香族スルホン酸カルシウム：ＫＩＮＧ社製 ＮＡ−ＳＵＬ ７２９
ＰＦＰＥ誘導体Ａ：Ｓｏｌｖａｙ社製 ＦＯＭＢＬＩＮ ＤＡ３０５
ＰＦＰＥ誘導体Ｂ：Ｓｏｌｖａｙ社製 ＦＯＭＢＬＩＮ ＤＡ３０６ ＶＡＣ
ＰＦＰＥ誘導体Ｃ：Ｓｏｌｖａｙ社製 ＦＯＭＢＬＩＮ ＤＡ３０８
ＰＦＰＥ誘導体Ｄ：Ｄｕｐｏｎｔ社製 クライトックス１５７ＦＳ−Ｌ
ＰＦＰＥ誘導体Ｅ：Ｄｕｐｏｎｔ社製 クライトックス１５７ＦＳ−Ｈ
[Rust preventive]
Sodium benzoate: manufactured by Fushimi Pharmaceutical Co., Ltd. Sodium benzoate Sodium nitrite: Pure Chemicals Co., Ltd. Reagent special grade Sodium nitrite Sodium sebacate: BASF Corporation IRGACOR DSS G
Aromatic calcium sulfonate: NA-SUL 729 manufactured by KING
PFPE derivative A: FOMBLIN DA305 manufactured by Solvay
PFPE derivative B: FOMBLIN DA306 VAC manufactured by Solvay
PFPE derivative C: FOMBLIN DA308 manufactured by Solvay
PFPE derivative D: Krytox 157FS-L manufactured by Dupont
PFPE derivative E: Dupont Krytox 157FS-H
グリースの調製方法は、基油、増ちょう剤、防錆剤の各種原料を十分に混合した後に、３本ロールミルを通して、グリース組成物を得た。 As a method for preparing grease, after thoroughly mixing various raw materials of base oil, thickener and rust preventive agent, a grease composition was obtained through a three-roll mill.
（４）軸受防錆
グリースを塗布してなじみ運転させた円錐ころ軸受を、１質量％の塩水に１０秒間浸漬させ、高湿環境下で静置させた。試験後に軸受を取り出し、外輪転走面を目視で観察した。評価は外輪転走面を３２区画に分割し、そのうち何区画に錆が発生しているかで、錆発生率を算出した。
軸受 ： ４Ｔ−３０２０４
グリース封入量： ４．０ｇ
なじみ運転条件： Ｆa＝１０ｋｇｆ １７５０ｒｐｍ ６０秒
試験温度 ： ４０℃
試験湿度 ： １００％ＲＨ
試験時間 ： ４８ｈ
(4) Bearing rust prevention A tapered roller bearing applied with grease and allowed to run is immersed in 1% by mass of salt water for 10 seconds and allowed to stand in a high humidity environment. The bearing was taken out after the test, and the outer ring rolling surface was visually observed. In the evaluation, the outer ring raceway surface was divided into 32 sections, and the rust generation rate was calculated according to how many sections of the outer ring were rusted.
Bearing: 4T-30204
Grease filling amount: 4.0 g
Familiar operating conditions: Fa = 10 kgf 1750 rpm 60 seconds Test temperature: 40 ° C.
Test humidity: 100% RH
Test time: 48h
各グリースの配合と軸受防錆の試験結果を表２〜４に示す。 Tables 2 to 4 show the composition of each grease and the test results of bearing rust prevention.
防錆剤として、安息香酸ナトリウムを用いた実施例２〜５は、軸受防錆における発錆率が０〜３％と低く、防錆性に優れていることが分かる。また、防錆剤が添加されていない比較例９は発錆率が１００％であり、ＰＦＰＥ誘導体を添加した比較例１３〜１７では、比較例１５が、発錆率が５６％、それ以外は７５〜１００％と防錆性が大幅に劣っていた。更に、比較例１０〜１２に関しては発錆率が１６〜３１％であり、実施例２〜５に比べて防錆性が劣る結果となった。 It can be seen that Examples 2 to 5 using sodium benzoate as a rust inhibitor have a low rusting rate of 0 to 3% in bearing rust prevention and are excellent in rust prevention. Moreover, the comparative example 9 to which the rust preventive agent is not added has a rusting rate of 100%. In comparative examples 13 to 17 to which the PFPE derivative is added, the comparative example 15 has a rusting rate of 56%. 75-100% and rust prevention property were significantly inferior. Furthermore, in Comparative Examples 10 to 12, the rusting rate was 16 to 31%, and the results were inferior in rust prevention compared to Examples 2 to 5.
以上のように、本発明に係るグリース組成物によれば、防錆剤として亜硝酸ナトリウムやセバシン酸ナトリウムを使用した従来のグリース組成物よりも安全性が高く、しかも、耐熱性及び防錆性のいずれも両立することができ、さらに、錆の発生を抑制し、高温環境下でも優れた耐久性を示すことがわかる。 As described above, according to the grease composition according to the present invention, safety is higher than conventional grease compositions using sodium nitrite or sodium sebacate as a rust preventive agent, and heat resistance and rust resistance are improved. It can be seen that both of them can be compatible, and further, the generation of rust is suppressed and excellent durability is exhibited even in a high temperature environment.
Claims (5)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107557125A (en) * | 2017-09-26 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of PFPE type conductive grease and preparation method thereof |
| WO2018181431A1 (en) * | 2017-03-31 | 2018-10-04 | 出光興産株式会社 | Grease composition and method for producing grease composition |
| JP2020055952A (en) * | 2018-10-02 | 2020-04-09 | 出光興産株式会社 | Grease composition and method for manufacturing grease composition |
| JP7360127B2 (en) | 2020-03-30 | 2023-10-12 | 株式会社ニッペコ | Grease for bearings |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02158692A (en) * | 1988-10-26 | 1990-06-19 | Imperial Chem Ind Plc <Ici> | Grease composition |
| JPH07268370A (en) * | 1993-12-01 | 1995-10-17 | Ausimont Spa | Hydrogenated mineral or synthetic grease having improved characteristic |
| JP2003262228A (en) * | 2002-03-07 | 2003-09-19 | Nsk Ltd | Rolling device |
| JP2008266656A (en) * | 2008-07-04 | 2008-11-06 | Tonengeneral Sekiyu Kk | Lubricating oil composition |
-
2015
- 2015-07-10 JP JP2015138888A patent/JP6543120B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02158692A (en) * | 1988-10-26 | 1990-06-19 | Imperial Chem Ind Plc <Ici> | Grease composition |
| JPH07268370A (en) * | 1993-12-01 | 1995-10-17 | Ausimont Spa | Hydrogenated mineral or synthetic grease having improved characteristic |
| JP2003262228A (en) * | 2002-03-07 | 2003-09-19 | Nsk Ltd | Rolling device |
| JP2008266656A (en) * | 2008-07-04 | 2008-11-06 | Tonengeneral Sekiyu Kk | Lubricating oil composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181431A1 (en) * | 2017-03-31 | 2018-10-04 | 出光興産株式会社 | Grease composition and method for producing grease composition |
| CN107557125A (en) * | 2017-09-26 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of PFPE type conductive grease and preparation method thereof |
| CN107557125B (en) * | 2017-09-26 | 2020-07-21 | 中国石油化工股份有限公司 | Perfluoropolyether conductive lubricating grease and preparation method thereof |
| JP2020055952A (en) * | 2018-10-02 | 2020-04-09 | 出光興産株式会社 | Grease composition and method for manufacturing grease composition |
| JP7078508B2 (en) | 2018-10-02 | 2022-05-31 | 出光興産株式会社 | Grease composition and method for manufacturing grease composition |
| JP7360127B2 (en) | 2020-03-30 | 2023-10-12 | 株式会社ニッペコ | Grease for bearings |
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