JP6543120B2 - Grease composition - Google Patents
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- JP6543120B2 JP6543120B2 JP2015138888A JP2015138888A JP6543120B2 JP 6543120 B2 JP6543120 B2 JP 6543120B2 JP 2015138888 A JP2015138888 A JP 2015138888A JP 2015138888 A JP2015138888 A JP 2015138888A JP 6543120 B2 JP6543120 B2 JP 6543120B2
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- grease composition
- grease
- rust
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- perfluoropolyether
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- 239000004519 grease Substances 0.000 title claims description 43
- 239000000203 mixture Substances 0.000 title claims description 26
- 239000010702 perfluoropolyether Substances 0.000 claims description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 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
- 239000002199 base oil Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 7
- 235000010234 sodium benzoate Nutrition 0.000 claims description 7
- 239000004299 sodium benzoate 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
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 29
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 235000013373 food additive Nutrition 0.000 description 7
- 239000002778 food additive Substances 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 239000003795 chemical substances by application 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
- 230000003449 preventive effect Effects 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
- 239000013556 antirust agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052791 calcium Inorganic materials 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 239000000314 lubricant Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 230000003078 antioxidant effect Effects 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
- 238000005536 corrosion prevention Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 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
- 150000004005 nitrosamines Chemical class 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 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
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Lubricants (AREA)
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 which is excellent in heat resistance, rust resistance 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。 A common fluorine grease uses perfluoropolyether as a base oil, a fluorine resin such as polytetrafluoroethylene is used as a thickener, and additives such as a rust inhibitor and an antioxidant as needed. 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 a grease for heat-resistant bearings of automobile electrical equipment and accessories, office equipment, and corrugate machines. Moreover, in recent years, it is also used as a grease for food machinery. The fluorine grease used for such applications is required not only the durability under high temperature environment but also excellent corrosion resistance, environmental compatibility, human safety 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 corrosion inhibitor to be added to fluorine grease, but sodium nitrite is known to react with a secondary amine to form nitrosamine, which is an environmentally harmful substance. Therefore, in recent years, the use of sodium nitrite is limited, and a rust preventive agent to replace sodium nitrite is required. In addition, various compounds have been studied so far as antirust agents 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 having high corrosion resistance can be obtained by using a perfluoropolyether or 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, the addition of a Ca salt or Na salt of an aromatic sulfonic acid or a saturated aliphatic dicarboxylic acid is proposed as a lubricant composition which is excellent in antirust property and also excellent in antirust property after receiving a heat history. (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 having added the aliphatic dibasic acid salt of General formula (1) shown below by 0.1 mass% or more and less than 1.0 mass%, it has the outstanding rust resistance and there is little evaporation loss. A fluorine grease composition has also been proposed (Patent Document 3).
(CH 2 ) n (COO) 2 M m (1)
(Wherein n is an integer of 1 to 19, M is an alkali metal or alkaline earth metal, m is 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 is insufficient in heat resistance, and under severe conditions, is also insufficient in rust prevention. Moreover, since all the raw materials are fluorine-based compounds, the 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。 Further, with regard to dinonyl naphthalene sulfonic acid Ca and petroleum sulfonic acid Na used as aromatic sulfonic acid salts in the example shown in Patent Document 2, the evaporation loss under high temperature environment is large and the heat resistance is insufficient. . Moreover, since these rust inhibitors are liquid rust inhibitors that are not compatible with perfluoropolyether, there is a concern that the rust inhibitors may separate when stored in a long period if added in large amounts. In addition, with regard to sodium sebacate used as a saturated aliphatic dicarboxylate, when it is used in a grease for food machinery, the addition amount is limited.
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 to patent document 3 has little addition amount of a rust preventive agent, depending on evaluation conditions, sufficient rust resistance 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, as a result of intensive investigations by the inventor to achieve both heat resistance, corrosion resistance and safety, the perfluoropolyether and metal salt of aromatic monocarboxylic acid are heat resistance, corrosion resistance and safety. It has been found that the invention is improved, and the present invention has been completed. That is, the object of the present invention is to provide a highly safe fluorine grease composition which is excellent in heat resistance and rust resistance, and in which no environmentally harmful substance is generated.
上記課題を解決するために請求項１に記載の本発明は、基油がパーフルオロポリエーテルであって、安息香酸ナトリウムが、グリース組成物の全質量に対して、０．１〜４０．０質量％添加されていることを特徴とする。 In order to solve the above problems, according to the present invention as set forth in claim 1 , the base oil is a perfluoropolyether and sodium benzoate is 0.1-40.0 with respect to the total mass of the grease composition. It is characterized in that it is added by mass%.
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、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さらに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 2 is the grease composition according to claim 1, which is further selected from polytetrafluoroethylene, carbon black, silica and melamine cyanurate as a thickener. It is characterized in that it further contains at least one of
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、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 problems, the present invention according to claim 3 is the grease composition according to claim 1 or 2 , wherein the kinematic viscosity of the perfluoropolyether at 40 ° C is 10 to 1000 mm 2 / s. It is characterized by
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、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 4 is characterized in that the grease composition according to any one of claims 1 to 3 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。 The grease composition according to the present invention has higher safety than conventional grease compositions using sodium nitrite or sodium sebacate as a rust inhibitor, and further sacrifices both heat resistance and rust resistance. In addition, there is an effect of suppressing the occurrence of rust in an environment mixed with salt water and showing 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 the preferred embodiments.
[Base oil]
The base oil used in the grease composition according to the present invention may be any perfluoropolyether used as a lubricating oil. 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 of less than 10 mm 2 / s at 40 ° C. have a short molecular weight, so the amount of evaporation in a high temperature environment is large and they are not suitable for use at high temperatures. Further, those having a kinematic viscosity at 40 ° C. exceeding 1000 mm 2 / s have high pour points and are not suitable for use in a low temperature environment. Of course, in consideration of such an environment of use, it is possible to use one having a kinematic viscosity at 40 ° C. which is not 10 to 1000 mm 2 / sec. Further, the ratio of the base oil to the total amount of grease is preferably 50 to 90% by 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]
The metal salt of an aromatic monocarboxylic acid used in the grease composition according to the present invention is that the aromatic monocarboxylic acid is, for example, benzoic acid, naphthoic acid, phenylacetic acid, toluic acid, and derivatives of these acids preferable. The metal salts include metal salts of alkali metals such as lithium, sodium, potassium, calcium and magnesium, and alkaline earth metals. As a specific example, sodium benzoate, potassium benzoate, calcium benzoate and the like are preferable. Moreover, it is preferable that the ratio of the aromatic monocarboxylic-acid metal salt with respect to the whole quantity of grease is 0.1-40.0 mass% normally. More preferably, it is 2.0-25.0 mass%. In addition, metal salts of aromatic monocarboxylic acids have an effect as a rust inhibitor, 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 thickening agent used in the grease composition according to the present invention can be used as long as it can be dispersed in perfluoropolyether and made into a semisolid grease. For example, metal soaps, urea compounds, sodium terephthalate, polytetrafluoroethylene, carbon black, melamine cyanurate, silica and the like can be mentioned. When heat resistance is considered, polytetrafluoroethylene, carbon black, silica, and melamine cyanurate are preferable. Further, the proportion of the thickener to the total amount of grease is preferably less than 50% by mass. If it exceeds 50% by mass, it becomes too hard and it is difficult to use as a grease. In addition, since a perfluoropolyether can be made grease-like even if it is only an 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 to 8, the heat resistance was evaluated using various rustproofing agents described below.
［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
[Antirust agent]
The following were used as rust inhibitors.
Sodium benzoate: manufactured by Fushimi Pharmaceutical Co., Ltd. Sodium benzoate Sodium nitrite: Pure Chemical Co., Ltd. Reagent special grade Sodium nitrite Sodium sebacate: BASF IRGACOR DSS G
Calcium aromatic sulfonate: KING NA-SUL 729
PFPE derivative A: Solvay FOMBLIN DA305
PFPE derivative B: Solvay FOMBLIN DA306 VAC
PFPE derivative C: Solvay FOMBLIN DA308
PFPE Derivative D: Clyxtox 157 FS-L manufactured by Dupont
PFPE Derivative E: Clyxtox 157 FS-H manufactured by Dupont
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
The evaporation loss test was implemented about said various rust preventive agents.
(1) Evaporative loss test [Test conditions]
0.30 ± 0.01 g of various raw materials were weighed in a 10 mL beaker, and stationary heating was performed in a constant temperature bath at 200 ° C. for 3 hours, and weight loss was measured after taking out. The test results were evaporation weight loss, and the following five evaluations were made.
Evaluation A: Evaporative weight loss less than 2% Evaluation B: Evaporative weight loss 2% to less than 5% Evaluation C: Evaporative weight loss 5% to less than 10% Evaluation D: Evaporative weight loss 10% to less than 20% Evaluation E: Evaporative weight 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 state of listing on the US Food Additives List (EAFUS) and the state of listing on 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 Additives List (EAFUS)
The raw materials listed in this list are highly safe raw materials recognized as food additives in the United States, and were judged to be applicable to greases for food machinery. In this case, the various raw materials to be used use what satisfy | fills the criteria as a food additive.
（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
About the rustproofing agent which is not listed in the above-mentioned US food additive list (EAFUS), the loading situation to HX-1 specified by NSF was confirmed. The raw materials listed in HX-1 are raw materials and components that can be used as lubricants that can be used in places where food may be accidentally touched, and those that are not listed can not be used in food machinery grease It was judged that the raw material was low in safety.
以上の結果を表１に示す。 The above 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 small evaporation loss of 1.4%, which is an evaluation A, and it can be seen that the heat resistance is excellent. 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 small evaporation loss of 0.8 and is an evaluation A, and although it is included in the list of US food additives, it reacts with a secondary amine and is an environmentally hazardous substance. Its use has been limited in recent years as it produces certain nitrosamines. The sodium sebacate of Comparative Example 2 has an evaporation loss of 2.3 and a rating of B, and both heat resistance and safety are slightly inferior. Others have a large amount of evaporation loss and the heat resistance is significantly 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 corrosion resistance 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 Clitex GPL105
Dynamic 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 to 12 μm Primary particle size 0.2 μm 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
[Antirust agent]
Sodium benzoate: manufactured by Fushimi Pharmaceutical Co., Ltd. Sodium benzoate Sodium nitrite: Pure Chemical Co., Ltd. Reagent special grade Sodium nitrite Sodium sebacate: BASF IRGACOR DSS G
Calcium aromatic sulfonate: KING NA-SUL 729
PFPE derivative A: Solvay FOMBLIN DA305
PFPE derivative B: Solvay FOMBLIN DA306 VAC
PFPE derivative C: Solvay FOMBLIN DA308
PFPE Derivative D: Clyxtox 157 FS-L manufactured by Dupont
PFPE Derivative E: Clyxtox 157 FS-H manufactured by Dupont
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。 The grease was prepared by thoroughly mixing the base oil, the thickener, and various ingredients of the rust preventive agent, and passing through a three-roll mill to obtain a grease composition.
（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 The tapered roller bearing which applied grease and was made to run in contact was immersed in 1 mass% salt water for 10 seconds, and was left to stand in a high humidity environment. After the test, the bearing was taken out and the outer ring rolling surface was observed visually. In the evaluation, the outer ring rolling surface was divided into 32 sections, and the rate of occurrence of rust was calculated based on how many sections the rust was generated.
Bearings: 4T-30204
Grease loading quantity: 4.0 g
Familiar operating condition: 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 formulation of each grease and the test results of bearing corrosion 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。 In Examples 2 to 5 in which sodium benzoate is used as a rust inhibitor, the rusting rate in bearing rusting is as low as 0 to 3%, and it can be seen that the corrosion resistance is excellent. Further, in Comparative Example 9 in which the rust inhibitor is not added, the rusting rate is 100%, and in Comparative Examples 13 to 17 in which the PFPE derivative is added, the rusting rate is 56% in Comparative Example 15; The rust resistance was significantly inferior at 75 to 100%. Furthermore, the rusting rate was 16 to 31% for Comparative Examples 10 to 12, and the rust resistance was inferior 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, the safety is higher than that of the conventional grease composition using sodium nitrite or sodium sebacate as the rust inhibitor, and moreover, the heat resistance and the rust resistance It can be seen that both can be compatible, and furthermore, the occurrence of rust can be suppressed, and excellent durability can be exhibited even in a high temperature environment.
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