JP2018009119A - Flame-retardant grease composition - Google Patents
Flame-retardant grease composition Download PDFInfo
- Publication number
- JP2018009119A JP2018009119A JP2016139957A JP2016139957A JP2018009119A JP 2018009119 A JP2018009119 A JP 2018009119A JP 2016139957 A JP2016139957 A JP 2016139957A JP 2016139957 A JP2016139957 A JP 2016139957A JP 2018009119 A JP2018009119 A JP 2018009119A
- Authority
- JP
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- Prior art keywords
- grease composition
- flame
- mass
- retardant grease
- composition according
- 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
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- 239000004519 grease Substances 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- 239000000344 soap Substances 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 22
- 239000002562 thickening agent Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000003921 oil Substances 0.000 claims abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002199 base oil Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- 239000005077 polysulfide Substances 0.000 claims abstract description 9
- 229920001021 polysulfide Polymers 0.000 claims abstract description 9
- 150000008117 polysulfides Polymers 0.000 claims abstract description 9
- 235000019337 sorbitan trioleate Nutrition 0.000 claims abstract description 9
- 239000004147 Sorbitan trioleate Substances 0.000 claims abstract description 8
- 229960000391 sorbitan trioleate Drugs 0.000 claims abstract description 8
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 claims abstract description 7
- 239000002480 mineral oil Substances 0.000 claims abstract description 7
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 7
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims abstract description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 34
- 239000003112 inhibitor Substances 0.000 claims description 23
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 239000003925 fat Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 235000013877 carbamide Nutrition 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- -1 olefin sulfide Chemical class 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000004202 carbamide Substances 0.000 abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 230000002265 prevention Effects 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 239000000498 cooling water Substances 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000009628 steelmaking Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 125000005609 naphthenate group Chemical group 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 241000047703 Nonion Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical group COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OSYHPZSUMUFXHW-UHFFFAOYSA-N 2,3-ditert-butyl-4-[(2,3-ditert-butyl-4-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=C(O)C=CC(CC=2C(=C(C(O)=CC=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C OSYHPZSUMUFXHW-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/06—Mixtures of thickeners and additives
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/30—Parts of ball or roller bearings
- F16C33/66—Special parts or details in view of lubrication
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16H—GEARING
- F16H57/00—General details of gearing
- F16H57/04—Features relating to lubrication or cooling or heating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
- C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/56—Acids of unknown or incompletely defined constitution
- C10M129/58—Naphthenic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/76—Esters containing free hydroxy or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
- C10M135/04—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
- C10M151/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
Abstract
Description
本発明は製鉄設備等の軸受や歯車に使用可能な難燃性グリース組成物に関する。詳しくは、高温のスケール等が飛散して、グリースに着火し、火災が懸念される一方、冷却水が混入するおそれがある、製鉄設備等の軸受や歯車の箇所に使用可能な難燃性グリース組成物に関する。 The present invention relates to a flame retardant grease composition that can be used for bearings and gears of steelmaking facilities and the like. Specifically, flame retardant grease that can be used for bearings and gears in steelmaking facilities, etc., where high-temperature scales, etc. may scatter and ignite the grease, which may cause a fire, but may contain cooling water. Relates to the composition.
製鉄設備、鍛造設備などの塑性加工設備の軸受や歯車の潤滑にはグリースが使用されていている。これらの設備は常に高温や冷却水に曝されている。高温に曝されると、使用済みのグリースが設備の下に垂れ落ちて堆積し、その堆積したグリースにスケールが飛散するとグリースが着火するため、それに起因する火災が問題視されている。また、冷却水が設備にかかると、その設備に使用されているグリースにも冷却水が混入するため、よりグリースが設備外に流出しやすくなる。そもそも、冷却水が混入することで、グリースが設備から容易に流出することは、潤滑性の観点から考えても良くない。したがって、従来の難燃性グリース組成物の特性である耐着火性、自己消火性及び耐荷重性に加え、錆止め性、耐水性にも優れた難燃性グリース組成物が求められている。
特許文献１には、着火温度を高くし、自己消火性及び耐荷重性に優れるグリース組成物が開示されているが、耐水性は考慮されていないため、冷却水がグリースに混入するとグリースが軟化しやすいため流出してしまう恐れがある。
特許文献２には、防錆性、極圧性、耐水性及び耐熱性に優れ、特に難燃性に優れたグリース組成物が開示されている。このグリース組成物は、増ちょう剤にリチウム石けんとカルシウム複合石けんとの混合物を使用し、かつ特定量のカルシウムスルホネートを含有する。
特許文献３には、圧送性に優れ、かつ含水せん断安定性及び防錆性に優れたグリース組成物が開示されているが、難燃性や耐着火性についての記載はない。
特許文献４には、金属フェネートを含有する耐水性グリース組成物が開示されている。この組成物に、ポリグリコールエーテル、脂肪酸ポリエチレングリコールエステル、脂肪酸グリセリンエステル、カルボン酸金属塩、マグネシウムステアレートの一以上を共存させることで、さらに耐水性を向上させている。
製鉄設備の軸受や歯車はその使用環境や使用条件により、そこで使用されるグリース組成物に対し、自己消火性、耐着火性および耐荷重性だけでなく、錆止め性、耐水性も同時に求められており、これらすべての性能を両立したグリースが求められている。
Grease is used to lubricate bearings and gears in plastic processing equipment such as iron making equipment and forging equipment. These facilities are constantly exposed to high temperatures and cooling water. When exposed to high temperatures, used grease hangs down and accumulates under the equipment, and when the scale is scattered on the accumulated grease, the grease is ignited. Further, when the cooling water is applied to the equipment, the cooling water is mixed into the grease used in the equipment, so that the grease is more likely to flow out of the equipment. In the first place, it may not be considered from the viewpoint of lubricity that the grease easily flows out of the facility due to the mixing of the cooling water. Therefore, there is a need for a flame retardant grease composition that is excellent in rust resistance and water resistance in addition to the ignition resistance, self-extinguishing properties, and load resistance that are the characteristics of conventional flame retardant grease compositions.
Patent Document 1 discloses a grease composition that has a high ignition temperature and is excellent in self-extinguishing properties and load resistance. However, since water resistance is not considered, the grease softens when cooling water enters the grease. There is a risk of spilling because it is easy to do.
Patent Document 2 discloses a grease composition that is excellent in rust prevention, extreme pressure, water resistance and heat resistance, and particularly excellent in flame retardancy. This grease composition uses a mixture of lithium soap and calcium composite soap as a thickener and contains a specific amount of calcium sulfonate.
Patent Document 3 discloses a grease composition that is excellent in pumpability and excellent in water-containing shear stability and rust resistance, but does not describe flame retardancy and ignition resistance.
Patent Document 4 discloses a water-resistant grease composition containing a metal phenate. Water resistance is further improved by coexisting one or more of polyglycol ether, fatty acid polyethylene glycol ester, fatty acid glycerin ester, carboxylic acid metal salt, and magnesium stearate in this composition.
Bearings and gears of steelmaking facilities are required to have not only self-extinguishing properties, ignition resistance and load resistance, but also rust prevention properties and water resistance for the grease composition used there depending on the usage environment and conditions. Therefore, there is a need for a grease that satisfies all of these performances.
本発明の目的は、従来の難燃性グリース組成物の耐着火性、自己消火性および耐荷重性を維持しつつ、従来の難燃性グリース組成物よりも錆止め性及び耐水性を向上させた難燃性グリース組成物を提供することである。本発明の他の目的は、前記難燃性グリース組成物を封入した軸受又は歯車を提供することである。 The object of the present invention is to improve rust prevention and water resistance compared to conventional flame retardant grease compositions while maintaining the ignition resistance, self-extinguishing properties and load resistance of conventional flame retardant grease compositions. It is to provide a flame retardant grease composition. Another object of the present invention is to provide a bearing or gear in which the flame retardant grease composition is enclosed.
〔１〕増ちょう剤として、金属石けん系およびウレア系からなる群から選ばれる少なくとも１種と、
基油として、４０℃における動粘度が３００〜１０００ｍｍ2／ｓの鉱物油と、
耐荷重添加剤として、硫化油脂、硫化オレフィンおよびポリスルフィドから選ばれる少なくとも１種と、
さび止め剤として、ナフテン酸亜鉛及びソルビタントリオレートから選ばれる少なくとも１種と、
界面活性剤として、塩基性カルシウムフェネートとポリエチレングリコールモノオレートの２種とを含み、
グリース燃焼性試験において、９００℃で着火しない難燃性グリース組成物。
〔２〕さらに、耐荷重添加剤として硫化油脂を含有する前記〔１〕記載の難燃性グリース組成物。
〔３〕耐荷重添加剤として、硫化油脂、硫化オレフィン、ポリスルフィドの３種を含有する前記〔２〕記載の難燃性グリース組成物。
〔４〕組成物の全質量を基準として、耐荷重添加剤を０．５〜２０質量％含む前記〔１〕〜〔３〕のいずれか１項記載の難燃性グリース組成物。
〔５〕錆び止め剤が、ソルビタントリオレートである前記〔１〕〜〔４〕のいずれか１項記載の難燃性グリース組成物。
〔６〕組成物の全質量を基準として、錆び止め剤を０．５〜５.０質量％含む前記〔１〕〜〔５〕のいずれか１項記載の難燃性グリース組成物。
〔７〕組成物の全質量を基準として、界面活性剤を０．３〜２．７質量％含む前記〔１〕〜〔６〕のいずれか１項記載の難燃性グリース組成物。
〔８〕耐荷重添加剤が硫化オレフィンである前記〔１〕及び〔４〕〜〔７〕のいずれか１項記載の難燃性グリース組成物。
〔９〕硫化オレフィンの含有量が、組成物の全質量を基準として、１〜２０質量％である前記〔８〕記載の難燃性グリース組成物。
〔１０〕増ちょう剤がリチウム石けんである前記〔１〕〜〔９〕のいずれか１項記載の難燃性グリース組成物。
〔１１〕前記〔１〕〜〔１０〕のいずれか１項記載の難燃性グリース組成物を封入してなる軸受又は歯車。
〔１２〕製鉄設備用である前記〔１１〕記載の軸受又は歯車。
[1] As a thickener, at least one selected from the group consisting of metal soaps and ureas,
As a base oil, a mineral oil having a kinematic viscosity at 40 ° C. of 300 to 1000 mm 2 / s,
As a load bearing additive, at least one selected from sulfurized fats and oils, sulfurized olefins and polysulfides,
As a rust inhibitor, at least one selected from zinc naphthenate and sorbitan trioleate,
As a surfactant, two kinds of basic calcium phenate and polyethylene glycol monooleate are included,
A flame retardant grease composition that does not ignite at 900 ° C. in a grease flammability test.
[2] The flame retardant grease composition according to [1], further containing sulfurized fats and oils as a load-bearing additive.
[3] The flame retardant grease composition according to the above [2], which contains three kinds of sulfurized oil, sulfurized olefin, and polysulfide as load-bearing additives.
[4] The flame retardant grease composition according to any one of [1] to [3], including 0.5 to 20% by mass of a load-bearing additive based on the total mass of the composition.
[5] The flame retardant grease composition according to any one of [1] to [4], wherein the rust inhibitor is sorbitan trioleate.
[6] The flame retardant grease composition according to any one of the above [1] to [5], which contains 0.5 to 5.0% by mass of a rust inhibitor based on the total mass of the composition.
[7] The flame retardant grease composition according to any one of [1] to [6], which contains 0.3 to 2.7% by mass of a surfactant based on the total mass of the composition.
[8] The flame retardant grease composition according to any one of [1] and [4] to [7], wherein the load bearing additive is a sulfurized olefin.
[9] The flame retardant grease composition according to [8], wherein the content of sulfurized olefin is 1 to 20% by mass based on the total mass of the composition.
[10] The flame retardant grease composition according to any one of [1] to [9], wherein the thickener is lithium soap.
[11] A bearing or gear formed by enclosing the flame retardant grease composition according to any one of [1] to [10].
[12] The bearing or gear according to the above [11], which is used for iron making equipment.
本発明の難燃性グリース組成物は、従来のグリース組成物よりも錆止め性及び耐水性に優れ、かつ耐着火性、自己消火性及び耐荷重性も満足いくレベルであり、冷却水が混入しても流出し難く、製鉄設備等の火災の危険性をさらに低減できる。 The flame retardant grease composition of the present invention is superior to conventional grease compositions in terms of rust prevention and water resistance, and has satisfactory levels of ignition resistance, self-extinguishing properties and load resistance, and is mixed with cooling water. However, it is difficult to spill out, and the risk of fire in steelmaking facilities can be further reduced.
〔増ちょう剤〕
本発明で使用する増ちょう剤は、金属石けん系増ちょう剤及びウレア系増ちょう剤からなる群から選ばれる少なくとも１種である。
金属石けん系増ちょう剤としては、アルカリ金属石けん（例えば、リチウム石けん、ナトリウム石けん）、アルカリ土類金属石けん（例えば、カルシウム石けん）、複合アルカリ金属石けん（例えば、複合リチウム石けん）、複合アルカリ土類金属石けん（例えば、複合カルシウム石けん）、これらの１種または２種以上の組み合わせが挙げられる。
ウレア系増ちょう剤としては、芳香族ウレア化合物、脂肪族ウレア化合物、脂環式ウレア化合物、これらの１種または２種以上の組み合わせが挙げられる。
金属石けん系増ちょう剤が好ましく、特にリチウム石けんが好ましい。脂肪酸としてヒマシ硬化脂肪酸やヒマシ硬化油が使用される。とりわけ、増ちょう剤が、脂肪酸がヒマシ硬化脂肪酸であるリチウム石けんのみであるのが好ましい。
本発明の組成物中の増ちょう剤の含有量は、所望のちょう度が得られれば良く、例えば、グリース組成物全体に対して好ましくは１〜３０質量％、さらに好ましくは１〜１５％である。
[Thickener]
The thickener used in the present invention is at least one selected from the group consisting of a metal soap thickener and a urea thickener.
Examples of the metal soap thickener include alkali metal soap (for example, lithium soap and sodium soap), alkaline earth metal soap (for example, calcium soap), composite alkali metal soap (for example, composite lithium soap), and composite alkaline earth. Metal soap (for example, complex calcium soap), these 1 type, or 2 or more types of combinations are mentioned.
Examples of urea thickeners include aromatic urea compounds, aliphatic urea compounds, alicyclic urea compounds, and combinations of one or more of these.
Metal soap thickeners are preferred, and lithium soap is particularly preferred. As the fatty acid, castor-cured fatty acid or castor-cured oil is used. In particular, it is preferable that the thickener is only lithium soap whose fatty acid is castor-hardened fatty acid.
The content of the thickener in the composition of the present invention is only required to be a desired consistency. For example, it is preferably 1 to 30% by mass, more preferably 1 to 15% with respect to the entire grease composition. is there.
〔基油〕
本発明で使用する基油は、４０℃における動粘度が３００〜１０００ｍｍ2／ｓ、好ましくは４２０〜１０００ｍｍ2／ｓ、さらに好ましくは４８０〜１０００ｍｍ2／ｓの鉱物油である。４０℃における動粘度が３００ｍｍ2／ｓ以上の鉱物油は、後述する軟膏缶燃焼試験で燃焼時間が５分未満であり、自己消火性に優れる。鉱物油としては、例えば、減圧蒸留残渣油やポリスチレン換算で１０００から３０００の分子量を示す鉱物油を使用することができる。４０℃における動粘度が３００ｍｍ2／ｓ以上であっても、エステル系やフェニルエーテル系といった合成油の場合、コストが多くかかり、製鉄設備用としては適さない。本発明の組成物中の基油の含有量は、好ましくは５０〜９７質量％、さらに好ましくは８０〜９５％である。
[Base oil]
The base oil used in the present invention, kinematic viscosity at 40 ℃ is 300 to 1000 mm 2 / s, preferably 420~1000mm 2 / s, still mineral oil preferably 480~1000mm 2 / s. Mineral oil having a kinematic viscosity at 40 ° C. of 300 mm 2 / s or more has a combustion time of less than 5 minutes in an ointment can combustion test described later, and is excellent in self-extinguishing properties. As the mineral oil, for example, a vacuum distillation residue oil or a mineral oil having a molecular weight of 1000 to 3000 in terms of polystyrene can be used. Even if the kinematic viscosity at 40 ° C. is 300 mm 2 / s or more, in the case of synthetic oils such as ester-based and phenyl ether-based ones, the cost is high and it is not suitable for use in steelmaking facilities. The content of the base oil in the composition of the present invention is preferably 50 to 97% by mass, more preferably 80 to 95%.
〔耐荷重添加剤〕
本発明で使用する耐荷重添加剤は、硫化オレフィン及びポリスルフィドからなる群から選ばれ、単独でも２種を組み合わせて使用することもできる。前記耐荷重添加剤に、さらに硫化油脂を添加することができる。好ましくは２種を使用すること、さらに好ましくは３種すべてを使用することである。
本発明の組成物中の耐荷重添加剤の含有量は好ましくは０．５〜２０質量％、さらに好ましくは１〜１０質量％である。このような範囲で耐荷重添加剤を含むことにより、耐着火性である着火温度を低下させることなく、耐荷重性も両立させることができる。前記添加量の範囲に満たない場合、耐荷重性が不足する。
本発明の組成物中に耐荷重添加剤として硫化オレフィンのみを含有する場合、その含有量は、好ましくは０．８〜２０質量％、より好ましくは１〜２０質量％、さらに好ましくは１〜１０質量％である。このような範囲で硫化オレフィンを含むことにより、着火温度を低下させることなく、耐荷重性も両立させることができる。
(Load bearing additive)
The load bearing additive used in the present invention is selected from the group consisting of sulfurized olefins and polysulfides, and can be used alone or in combination of two. Sulfurized fats and oils can be further added to the load bearing additive. Preferably, two types are used, and more preferably all three types are used.
The content of the load bearing additive in the composition of the present invention is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass. By including the load resistance additive in such a range, it is possible to achieve both load resistance without lowering the ignition temperature which is ignition resistance. When it is less than the range of the addition amount, load resistance is insufficient.
When the composition of the present invention contains only a sulfurized olefin as a load-bearing additive, the content is preferably 0.8 to 20% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 10%. % By mass. By including the sulfurized olefin within such a range, it is possible to achieve both load resistance without lowering the ignition temperature.
本発明で使用する硫化オレフィンは下記一般式で示され、
Ｒ1Ｓ−（Ｓx−Ｒ2−Ｓy）n−Ｒ1
（式中ｘは０または１から２の整数、ｙは１〜３の整数、ｎは１〜１０の整数を表し、Ｒ1およびＲ2はそれぞれ炭素原子数４〜１０の一価または二価のアルキル基またはアルケニル基を表す。）
本発明の組成物が、耐荷重添加剤として前記３種を含有する場合、硫化オレフィンの含有量が０．３〜１０質量％であり、硫化油脂の含有量が０．１〜５．０質量％であり、ポリスルフィドの含有量が０．１〜５．０質量％であるのが好ましい。
硫化オレフィンは、公知の方法により合成しても市販品を用いても良い。市販品として、ＡＮＧＬＡＭＯＬ３３（日本ルブリゾール（株））、ＮＡ−ＬＵＢＥ ＥＰ−５１２０（ＫＩＮＧ ＩＮＤ ＵＳＴＲＩＥＳ社）、ＮＡ−ＬＵＢＥ ＥＰ−５１３０ＬＣ（ＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ社）、ＮＡ−ＬＵＢＥ ＥＰ−５４１５（ＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ社）等があげられる。
本発明で使用する硫化油脂は公知の方法により合成しても市販品を用いても良い。市販の硫化油脂としては、ＤＡＩＬＵＢＥ ＦＳ−１５０（ＤＩＣ（株））、ＤＡＩＬＵＢＥ Ｓ−２９０（ＤＩＣ（株））、ＤＡＩＬＵＢＥ Ｓ−３１０ＫＤ（ＤＩＣ（株））、ＤＡＩＬＵＢＥ ＧＳ−１1０（ＤＩＣ（株））等があげられる。
本発明で使用するポリスルフィドは公知の方法により合成しても市販品を用いても良い。市販のポリスルフィドとしては、ＤＡＩＬＵＢＥ ＧＳ-４６０（ＤＩＣ（株））、ＴＰＳ−２０（アルケマ（株））等があげられる。
The sulfurized olefin used in the present invention is represented by the following general formula:
R 1 S- (S x -R 2 -S y) n -R 1
(Wherein x is 0 or an integer of 1 to 2, y is an integer of 1 to 3, n is an integer of 1 to 10, and R 1 and R 2 are each monovalent or divalent having 4 to 10 carbon atoms. Represents an alkyl group or an alkenyl group.)
When the composition of the present invention contains the above three kinds as load-bearing additives, the content of sulfurized olefin is 0.3 to 10% by mass, and the content of sulfurized fat and oil is 0.1 to 5.0% by mass. %, And the polysulfide content is preferably 0.1 to 5.0% by mass.
The sulfurized olefin may be synthesized by a known method or a commercially available product may be used. As commercial products, ANGLAMOL33 (Nippon Lubrizol Co., Ltd.), NA-LUBE EP-5120 (KING INDUSTRIES), NA-LUBE EP-5130LC (KING INDUSTRIES), NA-LUBE EP-5415 (KING INDUSTRIES), etc. Can be given.
The sulfurized fat used in the present invention may be synthesized by a known method or a commercially available product. Commercially available sulfurized fats and oils include DAILUBE FS-150 (DIC Corporation), DAILUBE S-290 (DIC Corporation), DAILUBE S-310KD (DIC Corporation), DAILUBE GS-11 (DIC Corporation). Etc.
The polysulfide used in the present invention may be synthesized by a known method or a commercially available product. Examples of commercially available polysulfides include DAILUBE GS-460 (DIC Corporation), TPS-20 (Arkema Corporation), and the like.
〔錆止め剤〕
本発明のグリース組成物は、錆止め剤を含むことにより、水がかかる場合でも発錆しないグリース組成物を提供することができる。本発明で用いる錆止め剤は、ナフテン酸Ｚｎおよびソルビタントリオレートからなる群から選ばれる少なくとも１種である。ソルビタントリオレートが好ましい。両者を併用するのもまた好ましい。本発明者らが得た知見によると、これら以外の錆止め剤は、錆止め性向上には寄与するものの、着火温度の低下や燃焼時間の延長を起こし、自己消火性を低下させることがあるため、含まないのが好ましい。
本発明の組成物中の錆止め剤の含有量は、前記２種を併用する場合、好ましくは０．３〜５．０質量％、より好ましくは０．５〜３．０質量％、さらに好ましくは１．０〜２．０質量％である。
本発明の錆止め剤がナフテン酸Ｚｎの場合、本発明の組成物中の錆止め剤の含有量は、好ましくは０．３〜５．０質量％、より好ましくは０．５〜３．０質量％、さらに好ましくは１．０〜２．０質量％である。
本発明の錆止め剤がソルビタントリオレートの場合、本発明の組成物中の錆止め剤の含有量は、好ましくは０．３〜５．０質量％、より好ましくは０．４〜４．０質量％、さらに好ましくは０．５〜３．０質量％である。
(Rust inhibitor)
By including a rust inhibitor, the grease composition of the present invention can provide a grease composition that does not rust even when water is applied. The rust inhibitor used in the present invention is at least one selected from the group consisting of Zn naphthenate and sorbitan trioleate. Sorbitan trioleate is preferred. It is also preferable to use both in combination. According to the knowledge obtained by the present inventors, rust inhibitors other than these contribute to the improvement of rust prevention properties, but they cause a decrease in ignition temperature and an increase in combustion time, which may reduce self-extinguishing properties, It is preferably not included.
The content of the rust inhibitor in the composition of the present invention is preferably 0.3 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, and still more preferably when the two types are used in combination. It is 1.0-2.0 mass%.
When the rust inhibitor of the present invention is Zn naphthenate, the content of the rust inhibitor in the composition of the present invention is preferably 0.3 to 5.0 mass%, more preferably 0.5 to 3.0 mass%. More preferably, it is 1.0-2.0 mass%.
When the rust inhibitor of the present invention is sorbitan trioleate, the content of the rust inhibitor in the composition of the present invention is preferably 0.3 to 5.0 mass%, more preferably 0.4 to 4.0 mass%. More preferably, it is 0.5 to 3.0% by mass.
錆止め剤の含有量を前記範囲にすることで、耐着火性および自己消火性を低下させず、錆止め性を向上させることができる。含有量を０．３質量％以上にすることにより、満足のいく錆止めが得られる。含有量が５．０質量％を超えても錆止め性を向上させることはできるが、含有量を３．０質量％以下にすることにより、耐着火性および自己消火性を維持しながら錆止め性を向上させることができる。
錆止め剤としては市販品を使用することができる。市販のナフテン酸Ｚｎとしては、ＤＡＩＬＵＢＥ Ｚ−５００（ＤＩＣ（株））、ＤＡＩＬＵＢＥ Ｚ−３００（ＤＩＣ（株））Ｚｎ−ＮＡＰＨＴＨＥＮＡＴＥ １０％（ＤＩＣ（株））等が挙げられる。市販のソルビタンモノオレートとしては、ノニオン ＯＰ−８０Ｒ（日油（株））、エマゾール Ｏ−１０Ｖ（花王（株））、レオドール ＡＯ−１０Ｖ（花王（株））、レオドール ＳＰ−Ｏ１０Ｖ（花王（株））等が挙げられる。市販のソルビタントリオレートとしては、ノニオン ＯＰ−８５Ｒ（日油（株））、エマゾール Ｏ−３０Ｖ（花王（株））、レオドール ＳＰ−Ｏ３０Ｖ（花王（株））、リケマールＯＲ−８５（理研ビタミン（株））等が挙げられる。
By making content of a rust inhibitor into the said range, ignitability and self-extinguishing property are not reduced, but rust prevention property can be improved. Satisfactory rust prevention can be obtained by setting the content to 0.3% by mass or more. Even if the content exceeds 5.0% by mass, the rust-preventing property can be improved, but by making the content 3.0% by mass or less, the rust-preventing property is maintained while maintaining the ignition resistance and the self-extinguishing property. Can be improved.
A commercially available product can be used as the rust inhibitor. Examples of commercially available Zn naphthenate include DAILUBE Z-500 (DIC Corporation), DAILUBE Z-300 (DIC Corporation), Zn-NAPHTHENATE 10% (DIC Corporation), and the like. Commercially available sorbitan monooleates include Nonion OP-80R (NOF Corporation), Emazole O-10V (Kao Corporation), Rheodor AO-10V (Kao Corporation), Rheodor SP-O10V (Kao Corporation) )) And the like. Commercially available sorbitan trioleates include Nonion OP-85R (NOF Corporation), Emazole O-30V (Kao Corporation), Rheodor SP-O30V (Kao Corporation), Riquemar OR-85 (RIKEN Vitamin ( Etc.).
〔界面活性剤〕
本発明で使用する界面活性剤は塩基性Ｃａフェネートとポリエチレングリコールモノオレートの２種である。自己消火性グリースの耐着火性を低下させず、耐水性（グリースの含水せん断安定性）を向上させるには、これら添加剤を両方添加する必要がある。本発明者らが得た知見によると、これら以外の界面活性剤は、着火温度の低下や燃焼時間の延長を起こし、自己消火性を低下させることがあるため、含まないのが好ましい。
塩基性Ｃａフェネートの塩基価は好ましくは５０〜４００ｍｇＫＯＨ／ｇであり、より好ましくは１００〜２００ｍｇＫＯＨ／ｇである。なお、塩基価は、JIS K 2501に従って測定できる。
本発明の組成物中の前記２種の界面活性剤の総量は、好ましくは０．３〜３．０質量％であり、より好ましくは０．３〜２．７質量％、さらに好ましくは０．４〜２．５質量％、さらにより好ましくは０．５〜１．５質量％である。
本発明の組成物中の塩基性Ｃａフェネートの含有量は、好ましくは０．２５〜２．０質量％であり、より好ましくは０．３〜１．５質量％、さらに好ましくは０．４〜１．０質量％である。
[Surfactant]
The surfactants used in the present invention are two types of basic Ca phenate and polyethylene glycol monooleate. Both of these additives need to be added to improve the water resistance (water-containing shear stability of the grease) without reducing the ignition resistance of the self-extinguishing grease. According to the knowledge obtained by the present inventors, surfactants other than these are preferably not included because they may lower the ignition temperature or extend the combustion time, thereby reducing the self-extinguishing properties.
The base number of the basic Ca phenate is preferably 50 to 400 mgKOH / g, more preferably 100 to 200 mgKOH / g. The base number can be measured according to JIS K 2501.
The total amount of the two surfactants in the composition of the present invention is preferably 0.3 to 3.0% by mass, more preferably 0.3 to 2.7% by mass, and still more preferably 0.8. It is 4-2.5 mass%, More preferably, it is 0.5-1.5 mass%.
Content of basic Ca phenate in the composition of this invention becomes like this. Preferably it is 0.25-2.0 mass%, More preferably, it is 0.3-1.5 mass%, More preferably, it is 0.4- 1.0% by mass.
本発明の組成物中のポリエチレングリコールモノオレートの含有量は、好ましくは０．０５〜１．０質量％であり、より好ましくは０．１〜１．０質量％、さらに好ましくは、０．１〜０．５質量％である。
塩基性Ｃａフェネート及びポリエチレングリコールモノオレートの含有量を前記範囲にすることで、耐着火性および自己消火性を低下させず、耐水性を向上させることができる。総量を０．３質量％以上にすることにより、満足のいく耐水性が得られる。総量が３．０質量％を超えても含水せん断安定性を向上させることはできるが、総量を３．０質量％以下にすることにより、耐着火性および自己消火性を維持しながら耐水性を向上させることができる。
塩基性Ｃａフェネートとポリエチレングリコールモノオレートとの質量比が、塩基性Ｃａフェネート：ポリエチレングリコールモノオレート＝５：１〜１：１であるのが好ましく、３：１〜２：１であるのがより好ましい。両者の含有量が前記範囲であって、かつ両者の質量比が前記範囲であると、含水せん断安定性に非常に優れるので好ましい。
The content of polyethylene glycol monooleate in the composition of the present invention is preferably 0.05 to 1.0% by mass, more preferably 0.1 to 1.0% by mass, and still more preferably 0.1 It is -0.5 mass%.
By making content of basic Ca phenate and polyethyleneglycol monooleate into the said range, water resistance can be improved, without reducing ignition resistance and self-extinguishing property. By making the total amount 0.3% by mass or more, satisfactory water resistance can be obtained. Even if the total amount exceeds 3.0% by mass, the hydrous shear stability can be improved, but by keeping the total amount to 3.0% by mass or less, water resistance is maintained while maintaining ignition resistance and self-extinguishing properties. Can be improved.
The mass ratio of basic Ca phenate to polyethylene glycol monooleate is preferably basic Ca phenate: polyethylene glycol monooleate = 5: 1 to 1: 1, more preferably 3: 1 to 2: 1. preferable. It is preferable that the content of both is in the above range and the mass ratio of both is in the above range because the hydrous shear stability is very excellent.
〔任意成分〕
本発明の難燃性グリース組成物には、本発明の効果を損なわない限り、グリース組成物に通常用いられる添加剤、例えば、腐食防止剤、酸化防止剤、油性剤などを必要に応じて添加することができる。これらの成分の含有量の合計は、組成物の全質量を基準にして、通常０．１〜１０質量％程度、好ましくは０．５〜５質量％である。
[Optional ingredients]
In the flame-retardant grease composition of the present invention, additives usually used in the grease composition, for example, corrosion inhibitors, antioxidants, oily agents, and the like are added as necessary unless the effects of the present invention are impaired. can do. The total content of these components is usually about 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total mass of the composition.
〔腐食防止剤〕
本発明の難燃性グリース組成物には、グリース組成物に通常用いられる金属腐食防止剤を必要に応じて添加することができる。例えば、酸化亜鉛やベンゾトリアゾールに代表される金属腐食防止剤が挙げられる。
(Corrosion inhibitor)
The flame retardant grease composition of the present invention can be added with a metal corrosion inhibitor usually used in a grease composition as necessary. Examples thereof include metal corrosion inhibitors represented by zinc oxide and benzotriazole.
〔酸化防止剤〕
酸化防止剤は、グリースの酸化劣化抑制剤として知られている。本発明において使用可能な酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤等が挙げられる。フェノール系酸化防止剤としては、２,６-ジ-ターシャリーブチル-ｐ-クレゾール（ＢＨＴ）、２,２’-メチレンビス(４-メチル-６-ターシャリーブチルフェノール)、４,４’-ブチリデンビス(３-メチル-６-ターシャリーブチルフェノール)、２,６-ジ-ターシャリーブチル-フェノール、２,４-ジメチル-６-ターシャリーブチルフェノール、ターシャリーブチルヒドロキシアニソール（ＢＨＡ）、４,４’-ブチリデンビス(３-メチル-６-ターシャリーブチルフェノール)、４,４’-メチレンビス(２,３-ジ-ターシャリーブチルフェノール)、４,４’-チオビス(３-メチル-６-ターシャリーブチルフェノール)等があげられる。アミン系酸化防止剤としては、Ｎ-ｎ-ブチル-ｐ-アミノフェノール、４,４’-テトラメチル-ジ-アミノジフェニルメタン、α-ナフチルアミン、Ｎ-フェニル-α-ナフチルアミン、フェノチアジン等が挙げられる。
〔Antioxidant〕
Antioxidants are known as oxidative degradation inhibitors for grease. Examples of the antioxidant that can be used in the present invention include phenol-based antioxidants and amine-based antioxidants. As the phenolic antioxidant, 2,6-di-tert-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-tertiarybutylphenol), 4,4′-butylidenebis ( 3-methyl-6-tertiarybutylphenol), 2,6-ditertiarybutylphenol, 2,4-dimethyl-6-tertiarybutylphenol, tertiary butylhydroxyanisole (BHA), 4,4'-butylidenebis (3-Methyl-6-tertiary butylphenol), 4,4'-methylenebis (2,3-di-tertiarybutylphenol), 4,4'-thiobis (3-methyl-6-tertiarybutylphenol) It is done. Examples of the amine antioxidant include Nn-butyl-p-aminophenol, 4,4′-tetramethyl-di-aminodiphenylmethane, α-naphthylamine, N-phenyl-α-naphthylamine, phenothiazine and the like.
〔油性剤〕
さらに油性剤を含むことができる。本発明に使用可能な油性剤としては、高級脂肪酸、高級アルコール、油脂、エステル等があげられる。
[Oil-based agent]
Further, an oily agent can be included. Examples of oily agents that can be used in the present invention include higher fatty acids, higher alcohols, fats and esters, and the like.
本発明の組成物のちょう度は、６０回混和ちょう度であり、ＪＩＳ Ｋ ２２２０に従って測定することができ、好ましくは２２０〜４３０、より好ましくは２６５〜４３０であると、機械設備の集中給脂ではグリースの圧送が容易なので好ましい。
本発明の難燃性グリース組成物は、グリース組成物の通常の製造方法に従って製造できる。例えば、増ちょう剤として金属石けんを使用する場合、基油中で油脂又は脂肪酸等とアルカリを反応させ、生成した石けんを基油中に加熱分散させるケン化法、既に合成された金属石けんを基油中に加熱分散させる混合法などを用いて製造することができる。増ちょう剤がウレア化合物の場合、基油中で相当するアミンとイソシアネートを反応させ、その後加熱分散させる方法を用いて製造することができる。さらに、製造工程途中に添加剤を添加することができる。
本発明の難燃性グリース組成物は、軸受又は歯車に封入して用いることができる。集中給脂用として使用するのに好適であり、特に製鉄設備用グリース組成物として使用するのに好適である。さらに特に、製鉄設備用の軸受又は歯車に封入して用いるのが好ましい。
The consistency of the composition of the present invention is 60 times, and can be measured according to JIS K 2220, preferably 220 to 430, more preferably 265 to 430. Then, it is preferable because the grease can be easily pumped.
The flame retardant grease composition of the present invention can be produced according to a usual production method of a grease composition. For example, when metal soap is used as a thickener, a saponification method in which a fat or fatty acid or the like is reacted with an alkali in a base oil and the resulting soap is heated and dispersed in the base oil, or a metal soap already synthesized is used. It can be produced using a mixing method in which heat is dispersed in oil. When the thickener is a urea compound, it can be produced by a method in which the corresponding amine and isocyanate are reacted in the base oil and then heated and dispersed. Furthermore, additives can be added during the manufacturing process.
The flame retardant grease composition of the present invention can be used by being enclosed in a bearing or gear. Suitable for use as a centralized greasing, and particularly suitable for use as a grease composition for steelmaking facilities. More particularly, it is preferably used by being enclosed in a bearing or gear for a steelmaking facility.
表１〜５に示す増ちょう剤、基油、耐荷重添加剤、さび止め剤、界面活性剤を、各表に示す量（質量％）で実施例および比較例のグリース組成物を製造した。そのグリース組成物を試験サンプルとして、難燃性、耐荷重性、さび止め性および耐水性を評価した。なお、基油の４０℃における動粘度は、ＪＩＳ Ｋ２２８３に準じて測定した。 The grease compositions of Examples and Comparative Examples were produced with the thickeners, base oils, load bearing additives, rust inhibitors, and surfactants shown in Tables 1 to 5 in the amounts (mass%) shown in each table. Using the grease composition as a test sample, flame retardancy, load resistance, rust resistance and water resistance were evaluated. The kinematic viscosity at 40 ° C. of the base oil was measured according to JIS K2283.
１．難燃性の評価
難燃性（着火温度及び自己消火性）は、グリース燃焼性試験により評価した。グリース燃焼性試験は、グリース組成物２０ｇを内径６５ｍｍ、深さ１３ｍｍの筒型の金属容器（軟膏缶）に入れ、これに各温度（９００、９５０℃）に加熱した鋼球（直径１９．０５mm）を入れ、着火の有無、及び着火した場合は燃焼が終わるまでの時間を測定した。燃焼時間が３００秒を越えた場合は難燃性なしと判断して消火し、試験を中止した。
1. Evaluation of flame retardancy Flame retardancy (ignition temperature and self-extinguishing property) was evaluated by a grease flammability test. In the grease flammability test, 20 g of the grease composition was placed in a cylindrical metal container (ointment can) having an inner diameter of 65 mm and a depth of 13 mm, and a steel ball (diameter 19.05 mm having a diameter of 19.05 mm) heated to each temperature (900, 950 ° C.). ), And the presence or absence of ignition and, when ignited, the time until the end of combustion was measured. When the burning time exceeded 300 seconds, it was judged that there was no flame retardancy, the fire was extinguished, and the test was stopped.
２．耐荷重性の評価
耐荷重性は、ＡＳＴＭ Ｄ２５９６に規定された高速四球試験により評価した。高速四球試験は、融着が生じたときの荷重（融着荷重）を測定した。
2. Evaluation of load resistance The load resistance was evaluated by a high-speed four-ball test specified in ASTM D2596. In the high-speed four-ball test, the load (fusion load) when fusion occurred was measured.
３．さび止め性の評価
さび止め性は軸受防錆試験（ASTM D 1743-73）により、52℃×48h後の発錆の有無を確認した。
3. Evaluation of anti-rust property Anti-rust property was confirmed by the bearing anti-rust test (ASTM D 1743-73) for rust after 52 ° C x 48h.
４．耐水性の評価
耐水性は、ＡＳＴＭ Ｄ１８３１のロール安定度試験方法に用いる装置を使用して、グリース中に蒸留水を１０％含ませたものを試料とし、温度８０℃で２４時間運転し、試験前後のグリースの不混和ちょう度の差により評価をした。不混和ちょう度の差が９０以下であることが耐水性に優れる。９０を超える場合は耐水性に劣る。
4). Evaluation of water resistance Water resistance was tested by using an apparatus used for the roll stability test method of ASTM D1831, using a sample containing 10% distilled water in grease and operating at a temperature of 80 ° C for 24 hours. The evaluation was made based on the difference in the penetration of grease before and after the grease. It is excellent in water resistance that the difference in immiscibility is 90 or less. When it exceeds 90, it is inferior to water resistance.
５．総合判定
次の内容を全て満たす場合に合格とした。
・難燃性の評価は、グリース燃焼性試験において、９００℃で着火しないこと、かつ自己消火性評価は３００秒以内に自己消火すること。
・耐荷重性の評価は、ＡＳＴＭ Ｄ２５９６の試験で、融着荷重が２４５２Ｎ以上であること。
・さび止め性の評価は、発錆が無いこと。
・耐水性の評価において、試験前後のグリースの混和ちょう度差が９０以下であること。
5. Comprehensive judgment Passed when all the following contents were satisfied.
・ As for the evaluation of flame retardancy, the grease flammability test shall not be ignited at 900 ° C., and the self-extinguishing evaluation shall be self-extinguishing within 300 seconds.
・ Evaluation of load resistance is a test of ASTM D2596 and the fusion load is 2452N or more.
・ Rust prevention is evaluated for rusting.
-In the water resistance evaluation, the grease penetration difference before and after the test must be 90 or less.
Claims (12)
基油として、４０℃における動粘度が３００〜１０００ｍｍ2／ｓの鉱物油と、
耐荷重添加剤として、硫化オレフィンおよびポリスルフィドから選ばれる少なくとも１種と、
さび止め剤として、ナフテン酸亜鉛及びソルビタントリオレートから選ばれる少なくとも１種と、
界面活性剤として、塩基性カルシウムフェネートとポリエチレングリコールモノオレートの２種とを含み、
グリース燃焼性試験において、９００℃で着火しない難燃性グリース組成物。 As a thickener, at least one selected from the group consisting of metal soaps and ureas,
As a base oil, a mineral oil having a kinematic viscosity at 40 ° C. of 300 to 1000 mm 2 / s,
As a load-bearing additive, at least one selected from sulfurized olefins and polysulfides,
As a rust inhibitor, at least one selected from zinc naphthenate and sorbitan trioleate,
As a surfactant, two kinds of basic calcium phenate and polyethylene glycol monooleate are included,
A flame retardant grease composition that does not ignite at 900 ° C. in a grease flammability test.
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| WO2018012639A1 (en) | 2018-01-18 |
| CN109415653B (en) | 2021-10-15 |
| JP6660836B2 (en) | 2020-03-11 |
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