WO2010064347A1 - Flame retardant hydraulic oil composition - Google Patents

Flame retardant hydraulic oil composition Download PDF

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Publication number
WO2010064347A1
WO2010064347A1 PCT/JP2009/004519 JP2009004519W WO2010064347A1 WO 2010064347 A1 WO2010064347 A1 WO 2010064347A1 JP 2009004519 W JP2009004519 W JP 2009004519W WO 2010064347 A1 WO2010064347 A1 WO 2010064347A1
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acid
carbon atoms
group
ester
esters
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PCT/JP2009/004519
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French (fr)
Japanese (ja)
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三本信一
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新日本石油株式会社
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Priority to CN2009801551672A priority Critical patent/CN102292424B/en
Priority to JP2010541195A priority patent/JP5389048B2/en
Publication of WO2010064347A1 publication Critical patent/WO2010064347A1/en

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    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • C10M2207/02Hydroxy compounds
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Definitions

  • the present invention relates to a flame retardant hydraulic fluid composition, particularly high risk of fire occurrence, such as aluminum die-cast extrusion machine or steelworks premises work, optimal for use in high temperature and high pressure, and high pressure
  • a flame-retardant hydraulic fluid composition that is applicable to pumps, has long life, sludge suppression performance, wear resistance, and seizure resistance, and is particularly resistant to hydrolysis and can be used for a long period of time.
  • a flame-retardant hydraulic fluid composition that is applicable to pumps, has long life, sludge suppression performance, wear resistance, and seizure resistance, and is particularly resistant to hydrolysis and can be used for a long period of time.
  • hydraulic fluids used in places where there is a high risk of fire such as aluminum die-cast extrusion processing machines or steelworks premises work, are made of flame retardant hydraulic fluids such as water glycols or fatty acid esters (liquids). )
  • flame retardant hydraulic fluids such as water glycols or fatty acid esters (liquids).
  • water glycol-based hydraulic oil has been mainly used in places where there is a restriction on the fourth petroleum of the Fire Service Act, but it has drawbacks in terms of the complexity of use liquid management and wear resistance.
  • hydraulic oils based on fatty acid esters with a flash point of 250 ° C. or higher have been exempted from the Fire Service Act, and their uses have expanded.
  • the performance of the fatty acid ester varies depending on the composition of the fatty acid constituting the ester, and the ester of a saturated fatty acid is superior in terms of oxidation stability.
  • saturated fatty acids are expensive because they are produced by synthesizing from petroleum raw materials or hydrogenating unsaturated fatty acids obtained from animal and vegetable oils, and are not friendly to the global environment. Therefore, natural synthetic esters and fats and oils using fatty acids mainly composed of unsaturated fatty acids obtained from animal and plant oils that are environmentally friendly and advantageous in terms of cost are also used (Patent Documents 1 to 4). 3).
  • Synthetic esters and vegetable fats and oils contain impurity acids at the new oil stage, which trigger hydrolysis and oxidative degradation, so the use of acid scavengers that capture these acids greatly increases the degradation life. Extension is possible.
  • acid scavenger carbodiimide compounds and epoxy compounds are known (for example, see Document 4).
  • Natural synthetic ester hydraulic fluids using fatty acids mainly composed of unsaturated fatty acids obtained from animal and vegetable oils that are environmentally friendly and cost-effective are inferior in hydrolytic stability, oxidation stability or wear resistance. Yes. For this reason, it is necessary to quickly capture and detoxify the acid that is generated in the initial stage, but if an acid scavenger is used alone, it will adversely affect the wear resistance. . Moreover, since the ester which consists of unsaturated fatty acid has bad oxidation stability, the combination of the additive from which the antioxidant effect outstanding from the past is acquired is required.
  • the present invention has been made in view of such circumstances, and in synthetic esters or animal and vegetable oils and fats obtained from raw materials mainly composed of unsaturated fatty acids, it has sufficient antioxidant performance and wear resistance.
  • synthetic esters or animal and vegetable oils and fats obtained from raw materials mainly composed of unsaturated fatty acids, it has sufficient antioxidant performance and wear resistance.
  • As a result of diligent research aimed at providing a long-life, flame-retardant hydraulic fluid that is compatible with high-pressure and maintenance-free hydraulic systems, it is obtained from hydrocarbon oils, synthetic esters and / or oils, especially natural raw materials.
  • the present inventors have found that the above-mentioned problems can be solved by blending a specific acid scavenger and a specific phosphorus compound with a synthetic ester containing an unsaturated fatty acid as a main component, and have completed the present invention.
  • the present invention comprises (A) at least one base oil selected from hydrocarbon oils, synthetic esters and fats and oils, (B) an epoxy compound and / or a carbodiimide compound represented by the following general formula (1). 0.01 to 2% by mass in total on the basis, and (C) at least one type of antiwear agent selected from sulfur-containing phosphate ester, acidic phosphate ester, acidic phosphate ester amine salt and phosphite ester A flame-retardant hydraulic fluid composition characterized by containing 0.001 to 5% by mass based on the total amount of substances.
  • R 1 and R 2 represent an alkyl group having 4 to 26 carbon atoms, an (alkyl) phenyl group, an aralkyl group, or an (alkyl) cycloalkyl group, which may be the same or different. .
  • the present invention also provides the flame retardant hydraulic fluid composition as described above, wherein the carbodiimide compound represented by the general formula (1) is a compound represented by the following general formula (2).
  • R 3 to R 8 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may be the same or different.
  • the present invention provides the flame retardant hydraulic fluid composition as described above, which contains 0.01 to 5% by mass of an amine-based antioxidant and / or a phenol-based antioxidant based on the total amount of the composition. is there.
  • a flame-retardant hydraulic fluid composition excellent in oxidation resistance stability and wear resistance particularly in fatty acid ester oils mainly composed of unsaturated fatty acids.
  • a flame retardant hydraulic fluid composition having a failure stage of 10 or more in the FZG gear test it is possible to provide a flame retardant hydraulic fluid composition excellent in oxidation resistance stability and wear resistance, particularly in fatty acid ester oils mainly composed of unsaturated fatty acids.
  • the base oil used in the flame retardant hydraulic fluid composition of the present invention at least one selected from hydrocarbon oils, synthetic esters and fats and oils can be used as a base oil, specifically, polyol.
  • examples include esters, diesters, various vegetable oils and fats, animal fats and the like.
  • esters such as polyol esters, rapeseed oil, sunflower oil, soybean oil and the like having a high oleic acid ratio are preferable, and those having a kinematic viscosity at 40 ° C. of 10 to 200 mm 2 / s are particularly preferable.
  • the hydrocarbon oil used in the present invention includes mineral oil and synthetic hydrocarbon oil.
  • specific examples include synthetic hydrocarbon oils such as naphthenic or paraffinic mineral oils, olefin polymers, naphthalene compounds, alkylbenzenes, or mixtures of two or more thereof.
  • Mineral oils include solvent removal, solvent extraction, hydrocracking, solvent removal from lubricating oil fractions obtained by atmospheric distillation and vacuum distillation of paraffinic, intermediate or naphthenic crudes. Mention may be made of paraffinic or naphthenic mineral oils obtained by applying a suitable combination of one or more purification means such as dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment.
  • the highly refined mineral oils used in the present invention are the total number of paraffin carbons determined by a method (ndM ring analysis) based on ASTM D 3238-85, respectively. It means percentage, percentage of naphthene carbon number to total carbon number, and percentage of aromatic carbon number to total carbon number. Moreover, it is preferable that a non-aromatic unsaturated part (unsaturation degree) is 10% or less.
  • the degree of unsaturation is more preferably 5% or less, further preferably 1% or less, and most preferably 0.1% or less.
  • highly refined mineral oil include, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or distillation of residual oil of atmospheric distillation under reduced pressure. Examples include refined oil obtained by refining oil according to a conventional method, deep dewaxed oil obtained by further deep dewaxing after refining, and hydrotreated oil obtained by hydrotreatment. . In this case, the purification method is not particularly limited, and various methods are used.
  • olefin polymer examples include those obtained by polymerizing olefins having 2 to 12 carbon atoms, and those obtained by subjecting this to hydrogenation treatment. Specific examples include polybutene, polyisobutene, ⁇ having 5 to 12 carbon atoms, and the like. Olefin oligomers (poly ⁇ -olefins), ethylene-propylene copolymers, and those obtained by hydrogenating these are preferably used.
  • the naphthalene compound is not particularly limited as long as it has a naphthalene skeleton, but a naphthalene compound represented by the following general formula (3) is preferable.
  • R 9 , R 10 , R 11 and R 12 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms.
  • the hydrocarbon group herein include an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an aralkyl group.
  • the total carbon number of R 9 , R 10 , R 11 and R 12 is preferably 1 to 10.
  • a naphthalene compound not only a compound having a single structure but also a mixture of two or more compounds having different structures may be used.
  • the manufacturing method of the said naphthalene compound is not restrict
  • alkylbenzene can be used as long as the performance as a hydraulic fluid is not impaired.
  • alkylbenzene having 1 to 4 alkyl groups having 1 to 30 carbon atoms and a total carbon number of the alkyl groups of 20 to 30 is more preferable.
  • the alkyl group may be linear or branched, but a branched alkyl group is preferable from the viewpoint of stability, viscosity characteristics, etc., and propylene, Branched alkyl groups derived from olefin oligomers such as butene and isobutylene are more preferred.
  • the alkylbenzene has 1 to 4 alkyl groups. From the viewpoints of stability and availability, alkylbenzene having 1 or 2 alkyl groups, that is, monoalkylbenzene, dialkylbenzene, or a mixture thereof may be used. Most preferably used.
  • the alkylbenzene may be a mixture of two or more alkylbenzenes having different structures as well as a single structure.
  • the manufacturing method of the said alkylbenzene is arbitrary and is not limited at all.
  • Examples of synthetic esters include fatty acid esters, dibasic acid esters, polyol esters, complex esters, aromatic esters, carbonate esters, and mixtures thereof.
  • Fatty acid esters include palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, 8,11-icosadienoic acid and other unsaturated fatty acids, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonane Saturated fatty acid having a linear or branched alkyl group having 5 to 19 carbon atoms such as acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecanoic acid And methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,
  • dibasic acid ester examples include dibasic acids having 5 to 10 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and linear or branched alkyl groups described in the fatty acid ester. And esters of monohydric alcohols having 1 to 15 carbon atoms and mixtures thereof are more preferably used. More specifically, for example, ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, diester -2-ethylhexyl sebacate, and mixtures thereof.
  • an ester of a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 1 to 24 carbon atoms is preferably used.
  • the diol include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5 -Pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propane Diol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11
  • polyol examples include, for example, trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (Pentaerythritol), glycerin, polyglycerin (glycerin 2-20 mer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol, Xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffino S
  • polyols are superior in hydrolytic stability, so neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), penta Hindered alcohols such as erythritol and di- (pentaerythritol) are preferred.
  • Examples of the fatty acid of the polyol ester include unsaturated fatty acids described in the fatty acid esters, and saturated fatty acids having a linear or branched alkyl group having 5 to 19 carbon atoms, and particularly unsaturated fatty acids described in the fatty acid esters. Is preferably used. Or the neo acid etc. whose (alpha) carbon atom is quaternary are mentioned.
  • Specific examples of branched saturated fatty acids include isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, and the like. Can be mentioned.
  • preferred polyol esters include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, and 2-ethylhexanoic acid.
  • a diester of one or more fatty acids selected from 3,5,5-trimethylhexanoic acid and each polyol of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, Triesters and tetraesters are mentioned.
  • the ester of two or more fatty acids and a polyol may be a mixture of two or more esters of one fatty acid and a polyol, or may be an ester of two or more mixed fatty acids and a polyol.
  • neopentyl glycol trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), penta
  • esters of hindered alcohols such as erythritol, di- (pentaerythritol), tri- (pentaerythritol)
  • esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol are particularly preferred.
  • the ester of trimethylolpropane and pentaerythritol is most preferred because it is particularly excellent in hydrolysis stability. Specifically, trimethylolpropane oleate, pentaerythritol oleate and the like are preferably used.
  • the polyol ester may be a partial ester in which some hydroxyl groups remain without esterification of all hydroxyl groups of the polyol, or may be a complete ester in which all hydroxyl groups are esterified, A mixture of a partial ester and a complete ester may be used, but a complete ester is preferred.
  • the complex ester is an ester of a fatty acid and a dibasic acid, and a monohydric alcohol and a polyol.
  • the fatty acid, the dibasic acid, the monohydric alcohol, and the polyol are described with respect to the dibasic acid ester and the polyol ester. The thing similar to what was illustrated in can be used.
  • aromatic ester examples include esters of 1 to 6 valent, preferably 1 to 4 valent, more preferably 1 to 3 valent aromatic carboxylic acid and aliphatic alcohol having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. Is used.
  • Specific examples of the monovalent to hexavalent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof.
  • the aliphatic alcohol having 1 to 18 carbon atoms include monohydric alcohols having 1 to 15 carbon atoms and linear or branched hexadecanol having a linear or branched alkyl group described in the fatty acid ester.
  • Linear or branched heptadecanol linear or branched octadecanol, and mixtures thereof.
  • aromatic esters include dibutyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, didodecyl phthalate, ditridecyl phthalate, tributyl trimellitic acid, trimethyl trimellitic acid ( 2-ethylhexyl), trinonyl trimellitic acid, tridecyl trimellitic acid, tridodecyl trimellitic acid, tritridecyl trimellitic acid, and the like.
  • a divalent or higher valent aromatic carboxylic acid it may be a simple ester composed of one kind of aliphatic alcohol or a complex ester composed of two or more kinds of aliphatic alcohol. May be.
  • the carbonate ester is a compound having a carbonate ester structure in the molecule.
  • One carbonate ester structure or a plurality of carbonate ester structures may be included in one molecule.
  • alcohol which comprises carbonate ester the above-mentioned aliphatic alcohol, polyol, etc. can be used, and what added polyglycol to polyglycol and polyol can also be used. Moreover, you may use what used carbonic acid and a fatty acid, and / or a dibasic acid.
  • the ester referred to in the present invention may be a single ester having a single structure or a mixture of two or more esters having different structures.
  • these ester base oils a polyol ester is preferable because of excellent hydrolysis stability.
  • one of the ester base oils may be used alone, or two or more may be used in combination.
  • oils used as the base oil of the flame retardant hydraulic fluid composition of the present invention include natural animal and vegetable oils and fats, such as rapeseed oil, sunflower oil, soybean oil, castor oil, coconut oil, corn oil, and cottonseed oil. Olive oil, rice bran oil, coconut oil, palm oil, palm kernel oil, peanut oil, tall oil, beef tallow, lard, or hydrogenated products thereof.
  • oils and fats hyoleic acid type fats and oils having a high proportion of unsaturated fatty acids, particularly oleic acid, among fatty acids constituting the ester are preferable, and hyoleinized vegetable oil having a higher proportion of oleic acid is more preferable.
  • one kind selected from the group consisting of the above-described mineral oil, synthetic hydrocarbon, synthetic ester and oil and fat may be used alone, or a combination of two or more kinds may be used. May be used.
  • the constituent fatty acid may be a saturated fatty acid, an unsaturated fatty acid, a linear fatty acid, or a branched fatty acid, and is represented by the formula (1) of the component (B).
  • an acid scavenger of a carbodiimide compound or an epoxy compound it is preferable to contain an unsaturated fatty acid.
  • the ratio of the unsaturated fatty acid to the fatty acid constituting the ester is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more.
  • the kinematic viscosities of these base oils are not particularly limited and are arbitrary, but are usually 40 from the viewpoints of excellent flame retardancy, wear resistance, seizure resistance, and low friction loss due to stirring resistance.
  • the kinematic viscosity at 0 ° C. is preferably 10 to 200 mm 2 / s, more preferably 15 to 150 mm 2 / s, and still more preferably 20 to 100 mm 2 / s.
  • the viscosity index is arbitrary, but from the viewpoint of maintaining an oil film at a high temperature, the viscosity index is usually preferably from 80 to 500, more preferably from 100 to 300.
  • the pour point is also arbitrary, but is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 15 ° C. or lower, from the viewpoint of pump startability in winter.
  • R 1 and R 2 of the carbodiimide compound represented by the following general formula (1) which is the component (B) in the flame retardant hydraulic oil composition of the present invention, are an alkyl group, a phenyl group, an alkylphenyl group, an aralkyl group, a cyclo A paraffin group or an alkylcycloparaffin group, each of which may be the same or different;
  • the alkyl group is preferably a linear or branched alkyl group having 4 to 26 carbon atoms, more preferably a linear or branched alkyl group having 4 to 12 carbon atoms, such as a butyl group or a pentyl group. Hexyl group, octyl group and the like.
  • R 1 and R 2 are alkylphenyl groups
  • examples of the compound represented by the general formula (1) include diphenylcarbodiimide or dialkylphenylcarbodiimide represented by the following general formula (2).
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may be the same or different.
  • Examples of the cycloparaffin group and the alkylcycloparaffin group include those in which the phenyl group is replaced with a cyclohexyl group in the dialkylphenylcarbodiimide.
  • R 1 and R 2 are an alkylphenyl group, particularly an ethyl group or a branched alkyl group having 3 to 4 carbon atoms because a better acid scavenging effect can be obtained.
  • Preferred are phenyl groups with, for example, diisopropylphenyl group and ditertiarybutylphenyl group, and specific examples include bis (2,6-di-tert-butylphenyl) carbodiimide.
  • R 1 and R 2 each preferably have 4 to 26 carbon atoms, more preferably 4 to 20 carbon atoms, and still more preferably 4 to 12 carbon atoms.
  • R 1 or R 2 has 3 or less carbon atoms, the reactivity becomes high and unstable, which is not preferable, and when it is 27 or more, the proportion of functional groups in the molecule decreases, which adversely affects the acid supplementation effect. There is a risk of giving.
  • alkyl oxirane compounds alkyl oxirane compounds, allyl oxirane compounds, phenyl glycidyl ether type epoxy compounds, alkyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, epoxidized fatty acid monoesters and At least one epoxy compound selected from epoxidized vegetable oils can be used.
  • the alkyl group of the alkyloxirane compound is a linear or branched alkyl group having 4 to 20 carbon atoms, preferably an alkyl group having 8 to 20 carbon atoms, and more preferably an alkyl group having 10 to 18 carbon atoms.
  • the carbon number of the alkyl group is 3 or less, it tends to evaporate and lacks stability.
  • the carbon number of the alkyl group is 21 or more, the low temperature performance and solubility, particularly the solubility after acid capture, are poor.
  • alkyloxirane compound examples include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2- Epoxy nonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2- Examples thereof include epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, and 1,2-epoxyicosane.
  • allyloxirane compound examples include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.
  • phenyl glycidyl ether type epoxy compound examples include phenyl glycidyl ether and alkylphenyl glycidyl ether.
  • alkylphenyl glycidyl ether examples include those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, and those having one alkyl group having 4 to 10 carbon atoms, such as n-butylphenyl glycidyl.
  • Ether i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decylphenyl A glycidyl ether etc. can be illustrated as a preferable thing.
  • alkyl glycidyl ether type epoxy compound examples include decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, Examples thereof include trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, and polyalkylene glycol diglycidyl ether.
  • glycidyl ester type epoxy compound examples include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester and the like, and preferred are glycidyl-2,2-dimethyloctanoate, glycidyl benzoate, glycidyl acrylate. And glycidyl methacrylate.
  • alicyclic epoxy compound examples include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4 -Epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3- Yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methyl Examples include cyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.
  • epoxidized fatty acid monoester examples include esters of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol.
  • esters of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol are preferably used.
  • butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.
  • epoxidized vegetable oil examples include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.
  • alkyl oxirane compounds preferred are alkyl oxirane compounds, phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds and epoxidized fatty acid monoesters.
  • alkyl oxirane compounds, phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds are more preferred, and 1,2-epoxytetradecane, phenyl glycidyl ether, butylphenyl glycidyl ether, alkyl glycidyl esters or mixtures thereof are particularly preferred.
  • the upper limit of the content of the component (B) in the flame retardant hydraulic fluid composition of the present invention is 2% by mass, preferably 1.5% by mass, more preferably 1.0% by mass based on the total amount of the composition. %.
  • the content exceeds 2% by mass the solubility after acid trapping is inferior, causing sludge generation, which is not preferable.
  • the lower limit of the content of component (B) is 0.01% by mass, preferably 0.05% by mass, more preferably 0.1% by mass, based on the total amount of the composition.
  • the content of the component (B) is less than 0.01% by mass, the acid scavenging effect is insufficient, which is not preferable.
  • the flame-retardant hydraulic fluid composition of the present invention has at least one selected from the group consisting of a sulfur-containing phosphate ester, an acidic phosphate ester, an acidic phosphate amine salt, and a phosphite ester as the component (C). Contains various types of antiwear agents.
  • sulfur-containing phosphate ester examples include trialkyl phosphorothioate, trioleyl phosphorothioate, triphenyl phosphorothioate, tricresyl phosphorothioate having an alkyl group of 4 to 18 carbon atoms.
  • Trixylenyl phosphorothioate cresyl diphenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phosphorothioate, tris (N-butylphenyl) phosphothionate, tris (isobutylphenyl) phosphothionate, tris (s-butylphenyl) phosphothionate, tris (t-butylphenyl) phosphothionate, etc. It is.
  • acidic phosphate esters include alkyl acid phosphates and dioleyl acid phosphates having an alkyl group of 4 to 22 carbon atoms, diphenyl acid phosphates and dicresyl ester acid phosphates which are aromatic acid phosphate esters. Fate etc. are mentioned. Of these, dialkyl acid phosphates that do not contain aromatics and have an alkyl group with 4 to 22 carbon atoms are preferred, and dialkyl acid phosphates with an alkyl group with 6 to 18 carbon atoms are more preferred.
  • the acid phosphate ester amine salt includes the acid phosphate ester, an amine having an alkyl group having 1 to 8 carbon atoms, an amine having two alkyl groups having 1 to 8 carbon atoms, and the number of carbon atoms.
  • Examples thereof include salts with amines selected from amines having 3 alkyl groups of 1-8.
  • phosphite ester examples include dialkyl phosphites, dioleyl phosphites, diphenyl phosphites, dicresyl phosphites having 4 to 12 carbon atoms, and alkyl groups having 4 to 12 carbon atoms. And trialkyl phosphites, trioleyl phosphites, triphenyl phosphites, and tricresyl phosphites.
  • sulfur-containing phosphate esters, acidic phosphate esters, and acidic phosphate ester amine salts are preferably used because of their high effects in synthetic esters and fats and oils.
  • the upper limit of the content of the component (C) in the flame-retardant hydraulic fluid composition of the present invention is 5% by mass, preferably 2% by mass, more preferably 1.5% by mass based on the total amount of the composition. is there. When the content exceeds 5% by mass, the thermal stability is inferior and sludge is generated, which is not preferable.
  • the lower limit of the content of the component (C) is 0.001% by mass, preferably 0.005% by mass, more preferably 0.01% by mass based on the total amount of the composition. When the content of the component (C) is less than 0.001% by mass, the wear resistance and seizure resistance are insufficient, which is not preferable.
  • the flame retardant hydraulic fluid composition of the present invention preferably further contains an amine-based antioxidant and / or a phenol-based antioxidant.
  • an antioxidant in combination, higher antioxidant properties and sludge suppression properties can be added.
  • the antioxidant any amine compound or phenol used as an antioxidant for lubricating oil can be used, and it is not particularly limited.
  • Representative amine antioxidants include phenyl- ⁇ -naphthylamines represented by the following formula (4) or p, p'-dialkylated diphenylamine represented by the following formula (5).
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.
  • R 14 and R 15 each independently represents an alkyl group having 1 to 16 carbon atoms.
  • R 13 is a branched alkyl group having 8 to 16 carbon atoms. Further, a branched alkyl group having 8 to 16 carbon atoms derived from an oligomer of an olefin having 3 or 4 carbon atoms is more preferable. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene and isobutylene, but propylene or isobutylene is preferable in order to obtain a more excellent sludge formation suppressing effect.
  • R 13 represents a branched octyl group derived from an isobutylene dimer, a branched nonyl group derived from a propylene trimer, and an isobutylene trimer.
  • a branched dodecyl group derived from a propylene tetramer, a branched dodecyl group derived from a propylene tetramer, or a branched pentadecyl group derived from a propylene pentamer is more preferred, and a branch derived from a dimer of isobutylene.
  • a branched dodecyl group derived from a branched octyl group, a trimer of isobutylene or a branched dodecyl group derived from a tetramer of propylene is more preferred, and a branched dodecyl group is most preferred.
  • R 14 and R 15 of p, p′-dialkyldiphenylamine represented by the general formula (5) are each independently a branched alkyl group having 3 to 16 carbon atoms in order to obtain a more excellent sludge generation inhibiting effect. Further, a branched alkyl group having 3 to 16 carbon atoms derived from an olefin having 3 or 4 carbon atoms or an oligomer thereof is more preferable. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene, and isobutylene, but propylene or isobutylene is preferable in order to obtain a more excellent sludge generation suppressing effect.
  • R 14 or R 15 is most preferably a tert-butyl group derived from isobutylene or a branched octyl group derived from a dimer of isobutylene in order to obtain a better antioxidant effect.
  • the synthesized product is a halogenated alkyl compound having 1 to 16 carbon atoms and diphenylamine, or an olefin having 2 to 16 carbon atoms or an alkyl having 2 to 16 carbon atoms.
  • a Friedel-Crafts catalyst any synthesis method may be used.
  • the upper limit of the content of the amine-based antioxidant is preferably 2% by mass based on the total amount of the composition, more preferably 1.5% by mass, and even more preferably 1% by mass. If the content exceeds 2% by mass, sludge is generated, which is not preferable.
  • the lower limit of the content of the amine antioxidant is preferably 0.001% by mass, more preferably 0.05% by mass, and still more preferably 0.1% by mass based on the total amount of the composition. When the content of the antioxidant is less than 0.001% by mass, the antioxidant effect is insufficient, which is not preferable.
  • any alkylphenolic compound used as an antioxidant for lubricating oils can be used, and is not particularly limited.
  • the following general formula (6) or general formula One or more alkylphenol compounds selected from the compounds represented by (7) are preferred.
  • R 16 represents an alkyl group having 1 to 4 carbon atoms
  • R 17 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 18 represents a hydrogen atom, and has 1 to 4 carbon atoms.
  • An alkyl group, a group represented by the following general formula (i) or a group represented by the following general formula (ii) is shown.
  • R 19 represents an alkylene group having 1 to 6 carbon atoms
  • R 20 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms
  • R 21 represents an alkylene group having 1 to 6 carbon atoms
  • R 22 represents an alkyl group having 1 to 4 carbon atoms
  • R 23 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • N represents an integer of 0 or 1.
  • R 24 and R 28 each independently represent an alkyl group having 1 to 4 carbon atoms
  • R 25 and R 29 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 26 and R 27 each independently represents an alkylene group having 1 to 6 carbon atoms
  • Y represents an alkylene group having 1 to 18 carbon atoms or a group represented by the following general formula (iii): Show. -R 30 -S-R 31 - ( iii) In the above formula (iii), R 30 and R 31 each independently represents an alkylene group having 1 to 6 carbon atoms.
  • R 16 represents an alkyl group having 1 to 4 carbon atoms. Of these, a tert-butyl group is preferred because it is more excellent in sludge resistance.
  • R 17 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Among these, a hydrogen atom, a methyl group, or a tert-butyl group is preferable because it is more excellent in sludge resistance.
  • R 18 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a group represented by the above formula (i), or a group represented by the above formula (ii).
  • the alkyl group having 1 to 4 carbon atoms represented by R 18 is preferably a methyl group or an ethyl group from the viewpoint of superior sludge resistance.
  • the compound represented by the general formula (6) includes various compounds as described above. Preferred examples of these compounds include compounds in which R 18 is an alkyl group having 1 to 4 carbon atoms. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, etc .; as a compound when R 18 is a group represented by formula (i) N-hexyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, isohexyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, (3,5-di-tert -Butyl-4-hydroxyphenyl) acetic acid n-heptyl, (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid 2-ethylhexyl, (3,5-di-tert) Butyl-4-hydroxyphenyl) isododecyl prop
  • Y represents an alkylene group having 1 to 18 carbon atoms or a group represented by the above formula (iii).
  • the alkylene group having 1 to 18 carbon atoms represented by Y may be linear or branched.
  • An alkylene group having 1 to 6 carbon atoms is more preferable from the viewpoint of easy availability of raw materials, and includes an ethylene group (dimethylene group), a trimethylene group, a linear butylene group (tetramethylene group), a linear pentylene group (pentamethylene group),
  • a straight-chain alkylene group having 2 to 6 carbon atoms such as a straight-chain hexylene group (hexamethylene group) is particularly preferred.
  • the upper limit of the content of the phenolic antioxidant is preferably 5% by mass, more preferably 2% by mass, and even more preferably 1.5% by mass based on the total amount of the composition. When the content exceeds 5% by mass, sludge is generated, which is not preferable.
  • the lower limit of the content of the phenolic antioxidant is preferably 0.01% by mass, more preferably 0.05% by mass, and still more preferably 0.1% by mass based on the total amount of the composition. When the content of the antioxidant is less than 0.01% by mass, the antioxidant effect is insufficient, which is not preferable.
  • At least one base oil selected from the group consisting of hydrocarbon oils, synthetic esters and fats and oils, (B) component, (C) component, and further an amine-based antioxidant and / or
  • a phenolic antioxidant By adding a phenolic antioxidant, a flame-retardant hydraulic fluid with excellent antioxidant performance and wear resistance can be obtained.
  • other antioxidants are added as necessary. Agent, rust inhibitor, metal deactivator, antiwear agent, viscosity index improver, pour point depressant, antifoaming agent, anti-emulsifier, stick-slip inhibitor, oily agent, etc. Or in combination of several kinds.
  • rust inhibitors include amino acid derivatives, partial esters of polyhydric alcohols; esters such as lanolin fatty acid esters, alkyl succinic acid esters, and alkenyl succinic acid esters; sarcosine; polyhydric alcohol moieties such as sorbitan fatty acid esters.
  • amino acid derivatives are preferred because of their high rust prevention effect.
  • A is a group represented by the formula (9) or the formula (10), and B is an alkyl group having 1 to 12 carbon atoms or the residue of the monovalent carboxylic acid ester represented by the formula (11).
  • R 32 is an alkyl group having 4 to 12 carbon atoms, and R 33 is an alkyl group having 1 to 10 carbon atoms.
  • R 35 O—CO—R 34 — (9)
  • R 37 O—CO—R 36 —CO— (10) -C-CO-O-R 38 (11)
  • R 34 is an alkylene group having 1 to 12 carbon atoms
  • R 36 is an alkylene group having 1 to 10 carbon atoms
  • R 35 and R 37 are each a hydrogen atom or (It is an alkyl group having 1 to 10 carbon atoms
  • R 38 is an alkyl group having 1 to 10 carbon atoms.
  • R 32 is an alkyl group having 4 to 12 carbon atoms, preferably an alkyl group having 4 to 10 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms.
  • R 33 and R 38 are each independently an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • R 37 is hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • one or two or more compounds arbitrarily selected from these rust inhibitors can be contained in the hydraulic fluid composition in any amount, but usually the content is
  • the total amount of the hydraulic fluid composition is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.5% by mass, and still more preferably 0.05 to 1% by mass.
  • the metal deactivator examples include benzotriazole, thiadiazole, and imidazole compounds.
  • one kind or two or more kinds of compounds arbitrarily selected from these metal deactivators can be contained in any amount, but the content thereof is usually hydraulic oil.
  • the content is desirably 0.001 to 1% by mass based on the total amount of the composition.
  • the viscosity index improver include a copolymer of one or more monomers selected from various methacrylic esters or a hydride thereof, an ethylene- ⁇ -olefin copolymer (as an ⁇ -olefin).
  • Non-dispersed viscosity index improvers such as propylene, 1-butene, 1-pentene, etc.) or hydrides thereof, polyisobutylene or hydrogenated products thereof, hydrides of styrene-diene copolymers, and polyalkylstyrenes Etc. can be illustrated.
  • one or two or more compounds arbitrarily selected from these viscosity index improvers can be contained in any amount, but the content is usually determined by the hydraulic fluid composition. It is desirable that the content is 0.01 to 10% by mass based on the total amount of the product.
  • the pour point depressant include copolymers of one or more monomers selected from various acrylic esters and methacrylic esters or hydrogenated products thereof.
  • one or two or more compounds arbitrarily selected from these pour point depressants can be contained in any amount, but the content is usually determined by the hydraulic fluid composition. It is desirable that the content is 0.01 to 5% by mass based on the total amount of the product.
  • the antifoaming agent examples include silicones such as dimethyl silicone and fluorosilicone.
  • one kind or two or more kinds of compounds arbitrarily selected from these antifoaming agents can be contained in any amount, but the content thereof is usually a hydraulic fluid composition. It is desirable that the content is 0.001 to 0.05% by mass based on the total amount.
  • the demulsifier examples include polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, polyoxyalkylene fatty acid ester and the like.
  • Specific examples of the stick-slip preventing agent include polyhydric alcohol esters (complete esters and partial esters).
  • Specific examples of the oily agent include fatty acids, esters, alcohols and the like. Usually, the content is desirably 0.01 to 0.5% by mass based on the total amount of the hydraulic fluid composition.
  • A1 Trioleic propane oleate (kinematic viscosity at 40 ° C. 47.2 mm 2 / s, viscosity index 190)
  • A2 High oleic acid-containing rapeseed oil (kinematic viscosity at 40 ° C. 35 mm 2 / s, viscosity index 190, ratio of oleic acid to all fatty acids constituting the ester, 75 mol%, unsaturated fatty acid ratio to all fatty acids constituting the ester 90 mol%)
  • A3 Poly ⁇ -olefin oligomer (kinematic viscosity at 40 ° C. 44.5 mm 2 / s, viscosity index 145)
  • B1 Bis (2,6-di-tert-butylphenyl) carbodiimide represented by the following formula (R 3 and R 8 are hydrogen, and R 4 , R 5 , R 6 and R 7 are tert-butyl groups.)
  • B2 1,2-epoxytetradecane
  • D1 Np-isododecylphenyl- ⁇ -naphthylamine
  • D2 p, p′-dioctyldiphenylamine
  • D3 Bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane
  • E1 Amino acid derivative compound represented by the following formula. (Here, R 1 represents an octyl group, R 2 represents a butyl group, and R 3 represents a butylene group.)
  • E2 Sorbitan monooleate
  • the prepared hydraulic fluid composition was subjected to a flash point, an RPVOT test, a four-ball test, an FZG gear test, a V104C vane pump test, a rust prevention test, and the like.
  • the results are shown in Tables 1 to 4.
  • each property, a test, etc. were based on the following.
  • V104C test A vane pump test defined in ASTM D 2882 was conducted, the weight of the vane and the ring before and after the test was measured, and the amount of wear was measured. The test time was 100 hours.
  • Rust prevention test Rust prevention test using general steel materials for polished steel bars specified in JIS K 2510. There are two types of test methods, distilled water and artificial seawater, depending on the water used, but this time the test was conducted with more severe artificial seawater. The test time is 24 hours and the test oil temperature wave is 60 ° C.
  • Acid value This is defined by the titration amount of potassium hydroxide required for neutralizing acidic components contained in a certain amount of sample as defined in JIS K 2501. That is, 1 (KOH / mg) indicates the amount of acidic component contained in 1 mg that can be measured with a KOH solution.
  • the present invention provides a flame-retardant hydraulic fluid composition that is excellent in long life, sludge suppression performance, abrasion resistance, and seizure resistance, and is particularly resistant to hydrolysis and usable for a long period of time.

Abstract

As a flame retardant hydraulic oil composition which is most suitable for use at a place where the risk of fire breakout is high under high-temperature and high-pressure conditions, can be applied to a high-pressure pump, has high wear resistance, seize resistance, and sludge inhibiting performance, and can be used for a long period of time, a flame retardant hydraulic oil composition containing (A) at least one base oil selected from hydrocarbon oils, synthetic esters, oils and fats; (B) a carbodiimide compound represented by formula (1) and/or an epoxy compound in an amount of 0.01 to 2% by mass based on the total amount of the composition; and (C) at least one anti-wear agent selected from sulfur-containing phosphoric acid esters, acidic phosphoric acid esters, acidic phosphoric acid ester amine salts, and phosphorous acid esters in an amount of 0.001 to 5% by mass based on the total amount of the composition is provided.

Description

難燃性油圧作動油組成物Flame retardant hydraulic fluid composition
 本発明は難燃性油圧作動油組成物に関し、特にアルミダイキャスト押し出し加工機あるいは製鉄所構内作業など、火災発生の危険性が高く、高温かつ高圧下で使用される用途に最適で、かつ高圧ポンプへの適用が可能な、長寿命性、スラッジ抑制性能、耐摩耗性、耐焼き付き性に優れ、特に加水分解しにくく長期間使用可能であることを特徴とする難燃性油圧作動油組成物に関する。 The present invention relates to a flame retardant hydraulic fluid composition, particularly high risk of fire occurrence, such as aluminum die-cast extrusion machine or steelworks premises work, optimal for use in high temperature and high pressure, and high pressure A flame-retardant hydraulic fluid composition that is applicable to pumps, has long life, sludge suppression performance, wear resistance, and seizure resistance, and is particularly resistant to hydrolysis and can be used for a long period of time. About.
 従来よりアルミダイキャスト押し出し加工機あるいは製鉄所構内作業など、火災発生の危険性が高い場所で使用される作動液は、安全性を保つため水グリコールあるいは脂肪酸エステルなどの難燃性作動油(液)が使用されてきた。その中でも消防法の第四石油類の規制がある場所では、水グリコール系作動油が主に使用されてきたが、使用液管理の煩雑さ、耐摩耗性などについて欠点を有していた。ところが、2002年の消防法の改正により引火点250℃以上の脂肪酸エステルを基油とする作動油が消防法の適用外となり、その用途が広がることとなった。 Conventionally, hydraulic fluids used in places where there is a high risk of fire, such as aluminum die-cast extrusion processing machines or steelworks premises work, are made of flame retardant hydraulic fluids such as water glycols or fatty acid esters (liquids). ) Has been used. Among them, water glycol-based hydraulic oil has been mainly used in places where there is a restriction on the fourth petroleum of the Fire Service Act, but it has drawbacks in terms of the complexity of use liquid management and wear resistance. However, as a result of the revision of the Fire Service Act in 2002, hydraulic oils based on fatty acid esters with a flash point of 250 ° C. or higher have been exempted from the Fire Service Act, and their uses have expanded.
 脂肪酸エステルの性能は、エステルを構成する脂肪酸の組成により異なり、酸化安定性については飽和脂肪酸のエステルが優れている。しかしながら、飽和脂肪酸は石油原料からの合成あるいは動植物油から得られた不飽和脂肪酸を水添して製造されるため高価であり、地球環境に対して優しくない原料である。そのため、環境に優しく、コスト的にも有利な動植物油から得られた不飽和脂肪酸を主体とした脂肪酸を用いた天然系合成エステルや油脂も使用されているのが現状である(特許文献1~3参照)。 The performance of the fatty acid ester varies depending on the composition of the fatty acid constituting the ester, and the ester of a saturated fatty acid is superior in terms of oxidation stability. However, saturated fatty acids are expensive because they are produced by synthesizing from petroleum raw materials or hydrogenating unsaturated fatty acids obtained from animal and vegetable oils, and are not friendly to the global environment. Therefore, natural synthetic esters and fats and oils using fatty acids mainly composed of unsaturated fatty acids obtained from animal and plant oils that are environmentally friendly and advantageous in terms of cost are also used (Patent Documents 1 to 4). 3).
 一方、最近は油圧システムの高圧化、メンテナンスフリー化が進み、このような環境下で使用される作動油には長寿命性と優れた耐摩耗性が要求されるようになってきたが、エステルは水分存在下において加水分解されることが最大の欠点であった。加水分解により生成した酸は、各種金属の腐食、摺動部での摩耗を促進することから、寿命のみならず耐摩耗性にも悪影響を及ぼす。この加水分解は、金属などが触媒として作用するが、加水分解で生成した酸自身が触媒となり得るために、加水分解が発生し始めると加速度的に進行することから、初期に発生する酸をすばやく捕捉し無害化することが極めて重要である。
 なお、天然系素材を原料とする天然系合成エステルは、脂肪酸が不飽和脂肪酸を主体であるため、地球環境に優しくコスト的にも有利であるが、酸化安定性が飽和脂肪酸の合成エステルや合成系の炭化水素油などより大きく劣るのが欠点であった。
 合成エステル及び植物油脂には、新油段階で不純物の酸が存在し、これが加水分解や酸化劣化の引き金となるので、これらの酸を捕捉する酸捕捉剤を使用することで、劣化寿命の大幅な延長が可能となる。この酸捕捉剤としては、カルボジイミド化合物、エポキシ化合物が知られている(例えば文献4参照)。
On the other hand, the hydraulic system has recently been increased in pressure and maintenance-free, and hydraulic oils used in such an environment have been required to have long life and excellent wear resistance. The biggest drawback was that it was hydrolyzed in the presence of moisture. The acid generated by hydrolysis promotes corrosion of various metals and wear at the sliding portion, and thus adversely affects not only the life but also the wear resistance. In this hydrolysis, metal or the like acts as a catalyst, but the acid itself generated by hydrolysis can act as a catalyst. Capturing and detoxifying is extremely important.
Natural synthetic esters made from natural raw materials are unsaturated fatty acids, and the fatty acids are mainly environmentally friendly and cost-effective. It was a disadvantage that it was greatly inferior to other hydrocarbon oils.
Synthetic esters and vegetable fats and oils contain impurity acids at the new oil stage, which trigger hydrolysis and oxidative degradation, so the use of acid scavengers that capture these acids greatly increases the degradation life. Extension is possible. As this acid scavenger, carbodiimide compounds and epoxy compounds are known (for example, see Document 4).
 しかしながらこれら酸捕捉剤を単独で使用すると、耐摩耗性に悪影響を及ぼすことが知られており、油圧作動油に使用される代表的なリン系摩耗防止剤、例えばトリクレジルフォスフェートを配合しても、耐摩耗性は改善されなかった。
 また、不飽和脂肪酸からなるエステルは酸化安定性が悪いが、炭化水素油に使用されてきた従来のフェノール系酸化防止剤やアミン系酸化防止剤単独ではそれらのエステル油に対しては十分な酸化防止効果が得られなかった。
However, when these acid scavengers are used alone, they are known to have an adverse effect on abrasion resistance, and typical phosphorus-based antiwear agents used in hydraulic fluids such as tricresyl phosphate are blended. However, the wear resistance was not improved.
In addition, esters composed of unsaturated fatty acids have poor oxidation stability, but conventional phenolic antioxidants and amine antioxidants that have been used in hydrocarbon oils alone are sufficient to oxidize those ester oils. The prevention effect was not obtained.
特開2001-214187号公報JP 2001-214187 A 特許第3548591号公報Japanese Patent No. 3548591 特許第2888747号公報Japanese Patent No. 2888747 特開2001-316687号公報JP 2001-316687 A
 環境に優しくコスト的にも有利な動植物油から得られた不飽和脂肪酸を主体とした脂肪酸を用いた天然系合成エステル系作動油は、加水分解安定性、酸化安定性あるいは耐摩耗性に劣っている。そのため、初期に発生する酸をすばやく捕捉し無害化する必要があるが、酸捕捉剤を単独で使用すると耐摩耗性に悪影響を与えるため、従来にない優れた摩耗防止剤の併用が必要である。また、不飽和脂肪酸からなるエステルは酸化安定性が悪いため、従来より優れた酸化防止効果が得られる添加剤の組み合わせが必要である。 Natural synthetic ester hydraulic fluids using fatty acids mainly composed of unsaturated fatty acids obtained from animal and vegetable oils that are environmentally friendly and cost-effective are inferior in hydrolytic stability, oxidation stability or wear resistance. Yes. For this reason, it is necessary to quickly capture and detoxify the acid that is generated in the initial stage, but if an acid scavenger is used alone, it will adversely affect the wear resistance. . Moreover, since the ester which consists of unsaturated fatty acid has bad oxidation stability, the combination of the additive from which the antioxidant effect outstanding from the past is acquired is required.
 本発明は、このような実情に鑑みてなされたものであり、不飽和脂肪酸を主体とする原料から得た合成エステルあるいは動植物油脂において、十分な酸化防止性能及び耐摩耗性を有し、最近の油圧システムの高圧化、メンテナンスフリー化に対応した長寿命の難燃性油圧作動油を提供することを目的として鋭意研究した結果、炭化水素油、合成エステル及び/又は油脂、特に天然原料から得られた不飽和脂肪酸を主成分としてなる合成エステルに対して、特定の酸捕捉剤及び特定のリン化合物を配合することによって、上記課題を解決できることを見出し、本発明を完成するに至った。 The present invention has been made in view of such circumstances, and in synthetic esters or animal and vegetable oils and fats obtained from raw materials mainly composed of unsaturated fatty acids, it has sufficient antioxidant performance and wear resistance. As a result of diligent research aimed at providing a long-life, flame-retardant hydraulic fluid that is compatible with high-pressure and maintenance-free hydraulic systems, it is obtained from hydrocarbon oils, synthetic esters and / or oils, especially natural raw materials. The present inventors have found that the above-mentioned problems can be solved by blending a specific acid scavenger and a specific phosphorus compound with a synthetic ester containing an unsaturated fatty acid as a main component, and have completed the present invention.
 すなわち、本発明は、(A)炭化水素油、合成エステル及び油脂から選ばれる少なくとも1種の基油、(B)エポキシ化合物及び/又は下記一般式(1)で示されるカルボジイミド化合物を組成物全量基準で合計で0.01~2質量%、および(C)硫黄含有リン酸エステル、酸性リン酸エステル、酸性リン酸エステルアミン塩及び亜リン酸エステルから選ばれる少なくとも1種類の摩耗防止剤を組成物全量基準で0.001~5質量%、を含有することを特徴とする難燃性油圧作動油組成物である。
Figure JPOXMLDOC01-appb-C000001
(式(1)中、RおよびRは、炭素数4~26のアルキル基、(アルキル)フェニル基、アラルキル基、または(アルキル)シクロアルキル基を示し、それぞれ同一でも異なっていてもよい。)
That is, the present invention comprises (A) at least one base oil selected from hydrocarbon oils, synthetic esters and fats and oils, (B) an epoxy compound and / or a carbodiimide compound represented by the following general formula (1). 0.01 to 2% by mass in total on the basis, and (C) at least one type of antiwear agent selected from sulfur-containing phosphate ester, acidic phosphate ester, acidic phosphate ester amine salt and phosphite ester A flame-retardant hydraulic fluid composition characterized by containing 0.001 to 5% by mass based on the total amount of substances.
Figure JPOXMLDOC01-appb-C000001
(In the formula (1), R 1 and R 2 represent an alkyl group having 4 to 26 carbon atoms, an (alkyl) phenyl group, an aralkyl group, or an (alkyl) cycloalkyl group, which may be the same or different. .)
 また本発明は、一般式(1)で示されるカルボジイミド化合物が、下記の一般式(2)で示される化合物であることを特徴とする前記記載の難燃性油圧作動油組成物である。
Figure JPOXMLDOC01-appb-C000002
(式(2)中、R~Rは、水素もしくは炭素数1~8のアルキル基を示し、それぞれ同一でも異なっていてもよい。)
The present invention also provides the flame retardant hydraulic fluid composition as described above, wherein the carbodiimide compound represented by the general formula (1) is a compound represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000002
(In formula (2), R 3 to R 8 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may be the same or different.)
 さらに本発明は、アミン系酸化防止剤及び/又はフェノール系酸化防止剤を組成物全量基準で0.01~5質量%含有することを特徴とする前記記載の難燃性油圧作動油組成物である。 Furthermore, the present invention provides the flame retardant hydraulic fluid composition as described above, which contains 0.01 to 5% by mass of an amine-based antioxidant and / or a phenol-based antioxidant based on the total amount of the composition. is there.
 本発明によれば、特に不飽和脂肪酸を主体とした脂肪酸のエステル油において、耐酸化安定性及び耐摩耗性に優れた難燃性油圧作動油組成物を提供することが可能となる。また、FZGギヤ試験において不合格ステージが10以上である難燃性油圧作動油組成物を提供することが可能となる。 According to the present invention, it is possible to provide a flame-retardant hydraulic fluid composition excellent in oxidation resistance stability and wear resistance, particularly in fatty acid ester oils mainly composed of unsaturated fatty acids. In addition, it is possible to provide a flame retardant hydraulic fluid composition having a failure stage of 10 or more in the FZG gear test.
 以下、本発明の好適な実施形態について詳細に説明する。
 本発明の難燃性油圧作動油組成物に使用される基油としては、炭化水素油、合成エステル及び油脂の中から選ばれる少なくとも1種を基油として用いることができ、具体的にはポリオールエステル、ジエステル、各種植物油脂、動物油脂などが例示される。中でもポリオールエステル、オレイン酸比率の高い菜種油、ひまわり油、大豆油などのエステルが好ましく、特に、40℃における動粘度が10~200mm/sのものが好ましく用いられる。
Hereinafter, preferred embodiments of the present invention will be described in detail.
As the base oil used in the flame retardant hydraulic fluid composition of the present invention, at least one selected from hydrocarbon oils, synthetic esters and fats and oils can be used as a base oil, specifically, polyol. Examples include esters, diesters, various vegetable oils and fats, animal fats and the like. Among them, esters such as polyol esters, rapeseed oil, sunflower oil, soybean oil and the like having a high oleic acid ratio are preferable, and those having a kinematic viscosity at 40 ° C. of 10 to 200 mm 2 / s are particularly preferable.
 本発明において使用される炭化水素油としては、鉱油及び合成系炭化水素油が挙げられる。具体的には、ナフテン系やパラフィン系の鉱油、オレフィン重合体、ナフタレン化合物、アルキルベンゼンあるいはこれらの2種以上の混合物などの合成系炭化水素油が挙げられる。 The hydrocarbon oil used in the present invention includes mineral oil and synthetic hydrocarbon oil. Specific examples include synthetic hydrocarbon oils such as naphthenic or paraffinic mineral oils, olefin polymers, naphthalene compounds, alkylbenzenes, or mixtures of two or more thereof.
 鉱油としては、パラフィン基系原油、中間基系原油あるいはナフテン基系原油を常圧蒸留及び減圧蒸留して得られた潤滑油留分に対して、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄、白土処理等の1種もしくは2種以上の精製手段を適宜組み合わせて適用して得られるパラフィン系又はナフテン系の鉱油を挙げることができる。 Mineral oils include solvent removal, solvent extraction, hydrocracking, solvent removal from lubricating oil fractions obtained by atmospheric distillation and vacuum distillation of paraffinic, intermediate or naphthenic crudes. Mention may be made of paraffinic or naphthenic mineral oils obtained by applying a suitable combination of one or more purification means such as dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment.
 これらの鉱油の中でも、安定性により優れる点から、高度に精製された鉱油を用いることが好ましい。本発明において用いられる高度精製鉱油としては、%Cが2以下、%C/%Cが6以上、ヨウ素価が2.5以上が好ましい。なお、本発明でいう%C、%C及び%Cとは、それぞれASTM D 3238-85に準拠した方法(n-d-M環分析)により求められるパラフィン炭素数の全炭素数に対する百分率、ナフテン炭素数の全炭素数に対する百分率、及び芳香族炭素数の全炭素数に対する百分率を意味する。
 また、非芳香族不飽和分(不飽和度)が10%以下であることが好ましい。この不飽和度が10%より多い場合はスラッジ発生の原因となる可能性がある。このような点から本発明においては、上記不飽和度をより好ましくは5%以下、更に好ましくは1%以下、最も好ましくは0.1%以下とする。このような高度精製鉱油の具体例としては、例えば、パラフィン基系原油、中間基系原油あるいはナフテン基系原油を常圧蒸留するかあるいは常圧蒸留の残渣油を減圧蒸留して得られる留出油を常法に従って精製することによって得られる精製油、あるいは精製後更に深脱ロウ処理することによって得られる深脱ろう油、更には水素化処理によって得られる水添処理油などを挙げることができる。この際の精製法は特に制限はなく様々な方法が使用される。
Among these mineral oils, it is preferable to use highly refined mineral oil from the viewpoint of superior stability. The highly refined mineral oils used in the present invention,% C A of 2 or less,% C P /% C N is 6 or more, an iodine value of 2.5 or more is preferable. In the present invention,% C P ,% C N, and% C A are the total number of paraffin carbons determined by a method (ndM ring analysis) based on ASTM D 3238-85, respectively. It means percentage, percentage of naphthene carbon number to total carbon number, and percentage of aromatic carbon number to total carbon number.
Moreover, it is preferable that a non-aromatic unsaturated part (unsaturation degree) is 10% or less. If this degree of unsaturation is more than 10%, sludge may be generated. From this point, in the present invention, the degree of unsaturation is more preferably 5% or less, further preferably 1% or less, and most preferably 0.1% or less. Specific examples of such highly refined mineral oil include, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or distillation of residual oil of atmospheric distillation under reduced pressure. Examples include refined oil obtained by refining oil according to a conventional method, deep dewaxed oil obtained by further deep dewaxing after refining, and hydrotreated oil obtained by hydrotreatment. . In this case, the purification method is not particularly limited, and various methods are used.
 オレフィン重合体としては、炭素数2~12のオレフィンを重合させて得られるもの、及びこれを水素化処理したものが挙げられ、具体的には例えば、ポリブテン、ポリイソブテン、炭素数5~12のα-オレフィンのオリゴマー(ポリα-オレフィン)、エチレン-プロピレン共重合体、及びこれらを水素化処理したものなどが好ましく用いられる。 Examples of the olefin polymer include those obtained by polymerizing olefins having 2 to 12 carbon atoms, and those obtained by subjecting this to hydrogenation treatment. Specific examples include polybutene, polyisobutene, α having 5 to 12 carbon atoms, and the like. Olefin oligomers (poly α-olefins), ethylene-propylene copolymers, and those obtained by hydrogenating these are preferably used.
 ナフタレン化合物としては、ナフタレン骨格を有するものであれば特に限定はないが、下記一般式(3)で表されるナフタレン化合物が好ましい。
Figure JPOXMLDOC01-appb-C000003
The naphthalene compound is not particularly limited as long as it has a naphthalene skeleton, but a naphthalene compound represented by the following general formula (3) is preferable.
Figure JPOXMLDOC01-appb-C000003
 上記一般式(3)中、R、R10、R11及びR12は、それぞれ同一でも異なっていても良く、水素原子又は炭素数1~10、好ましくは1~8の炭化水素基を示す。ここでいう炭化水素基としては、アルキル基、アルケニル基、アリール基、アルキルアリール基、アラルキル基等が挙げられる。なお、R、R10、R11及びR12の合計炭素数は1~10であることが好ましい。
 ナフタレン化合物としては、単一の構造の化合物だけでなく、異なる構造を有する化合物の2種以上の混合物であっても良い。
 また、上記ナフタレン化合物の製造方法は特に制限されず、種々の公知の方法で製造できるが、熱・酸化安定性に優れる点から硫黄含有量が500質量ppm以下のものが好ましく用いられる。
In the general formula (3), R 9 , R 10 , R 11 and R 12 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. . Examples of the hydrocarbon group herein include an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an aralkyl group. The total carbon number of R 9 , R 10 , R 11 and R 12 is preferably 1 to 10.
As a naphthalene compound, not only a compound having a single structure but also a mixture of two or more compounds having different structures may be used.
Moreover, the manufacturing method of the said naphthalene compound is not restrict | limited in particular, Although it can manufacture by various well-known methods, the thing whose sulfur content is 500 mass ppm or less is used preferably from the point which is excellent in thermal and oxidation stability.
 アルキルベンゼンとしては、油圧作動油としての性能を損なわない限り任意のものが使用可能である。中でも炭素数1~30のアルキル基を1~4個有し、かつアルキル基の合計炭素数が20~30であるアルキルベンゼンであることがより好ましい。
 このアルキル基としては直鎖状であっても、分枝状であっても良いが、安定性、粘度特性などの点から分枝状アルキル基が好ましく、特に入手可能性の点から、プロピレン、ブテン、イソブチレンなどのオレフィンのオリゴマーから誘導される分枝状アルキル基がより好ましい。
Any alkylbenzene can be used as long as the performance as a hydraulic fluid is not impaired. Of these, alkylbenzene having 1 to 4 alkyl groups having 1 to 30 carbon atoms and a total carbon number of the alkyl groups of 20 to 30 is more preferable.
The alkyl group may be linear or branched, but a branched alkyl group is preferable from the viewpoint of stability, viscosity characteristics, etc., and propylene, Branched alkyl groups derived from olefin oligomers such as butene and isobutylene are more preferred.
 上記アルキルベンゼンが有するアルキル基の個数は1~4個であるが、安定性、入手可能性の点から1個又は2個のアルキル基を有するアルキルベンゼン、すなわちモノアルキルベンゼン、ジアルキルベンゼン、又はこれらの混合物が最も好ましく用いられる。
 また、アルキルベンゼンとしては、単一の構造のアルキルベンゼンだけでなく、異なる構造を有するアルキルベンゼンの2種以上の混合物であっても良い。
 上記アルキルベンゼンの製造方法は任意であり、何ら限定されるものでない。
The alkylbenzene has 1 to 4 alkyl groups. From the viewpoints of stability and availability, alkylbenzene having 1 or 2 alkyl groups, that is, monoalkylbenzene, dialkylbenzene, or a mixture thereof may be used. Most preferably used.
The alkylbenzene may be a mixture of two or more alkylbenzenes having different structures as well as a single structure.
The manufacturing method of the said alkylbenzene is arbitrary and is not limited at all.
 合成エステルとしては、例えば、脂肪酸エステル、二塩基酸エステル、ポリオールエステル、コンプレックスエステル、芳香族エステル、炭酸エステル及びこれらの混合物などが例示される。 Examples of synthetic esters include fatty acid esters, dibasic acid esters, polyol esters, complex esters, aromatic esters, carbonate esters, and mixtures thereof.
 脂肪酸エステルとしては、パルミトレイン酸、オレイン酸、バクセン酸、リノール酸、リノレン酸、エレオステアリン酸、8,11-イコサジエン酸などの不飽和脂肪酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、トリデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸、ノナデカン酸などの炭素数5~19の直鎖又は分枝アルキル基を有する飽和脂肪酸と、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ウンデカノール、ドデカノール、トリデカノール、テトラデカノール、ペンタデカノール、ヘキサデカノール、ヘプタデカノール、オクタデカノール、ノナデカノールの直鎖又は分枝アルキル基を有する炭素数119の一価アルコールとのエステル及びこれらの混合物が好ましく用いられる。具体的には、オレイルステアレート、オレイルラウレートなどの脂肪酸エステルが好ましい。  Fatty acid esters include palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, 8,11-icosadienoic acid and other unsaturated fatty acids, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonane Saturated fatty acid having a linear or branched alkyl group having 5 to 19 carbon atoms such as acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecanoic acid And methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol , Octadecanol, esters and mixtures thereof with monohydric alcohols having a carbon number of 119 with a straight-chain or branched alkyl group nonadecanol is preferably used. Specifically, fatty acid esters such as oleyl stearate and oleyl laurate are preferred. *
 二塩基酸エステルとしては、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸などの炭素数5~10の二塩基酸と、前記脂肪酸エステルに記載の直鎖又は分枝アルキル基を有する炭素数1~15の一価アルコールとのエステル及びこれらの混合物が好ましく用いられ、より具体的には例えば、ジトリデシルグルタレート、ジ-2-エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ-2-エチルヘキシルセバケート、及びこれらの混合物などが挙げられる。 Examples of the dibasic acid ester include dibasic acids having 5 to 10 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and linear or branched alkyl groups described in the fatty acid ester. And esters of monohydric alcohols having 1 to 15 carbon atoms and mixtures thereof are more preferably used. More specifically, for example, ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, diester -2-ethylhexyl sebacate, and mixtures thereof.
 ポリオールエステルとしては、ジオールあるいは水酸基を3~20個有するポリオールと、炭素数1~24の脂肪酸とのエステルが好ましく用いられる。
 ジオールとしては、具体的には例えば、エチレングリコール、1,3-プロパンジオール、プロピレングリコール、1,4-ブタンジオール、1,2-ブタンジオール、2ーメチル-1,3-プロパンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール、2-エチル-2-メチル-1,3-プロパンジオール、1,7-ヘプタンジオール、2-メチル-2-プロピル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,11-ウンデカンジオール、1,12-ドデカンジオールなどが挙げられる。
As the polyol ester, an ester of a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 1 to 24 carbon atoms is preferably used.
Specific examples of the diol include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5 -Pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propane Diol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. Is mentioned.
 ポリオールとしては、具体的には例えば、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ジ-(トリメチロールプロパン)、トリ-(トリメチロールプロパン)、ペンタエリスリトール、ジ-(ペンタエリスリトール)、トリ-(ペンタエリスリトール)、グリセリン、ポリグリセリン(グリセリンの2~20量体)、1,3,5ーペンタントリオール、ソルビトール、ソルビタン、ソルビトールグリセリン縮合物、アドニトール、アラビトール、キシリトール、マンニトールなどの多価アルコール、キシロース、アラビノース、リボース、ラムノース、グルコース、フルクトース、ガラクトース、マンノース、ソルボース、セロビオース、マルトース、イソマルトース、トレハロース、シュクロース、ラフィノース、ゲンチアノース、メレジトースなどの糖類、ならびにこれらの部分エーテル化物、及びメチルグルコシド(配糖体)などが挙げられる。
 これらの中でもポリオールとしては、より加水分解安定性に優れることから、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ジ-(トリメチロールプロパン)、トリ-(トリメチロールプロパン)、ペンタエリスリトール、ジ-(ペンタエリスリトール)などのヒンダードアルコールが好ましい。
Specific examples of the polyol include, for example, trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (Pentaerythritol), glycerin, polyglycerin (glycerin 2-20 mer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol, Xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffino Scan, gentianose, sugars such as melezitose, and their partially etherified products and methyl glucosides (glycosides) and the like.
Among these, polyols are superior in hydrolytic stability, so neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), penta Hindered alcohols such as erythritol and di- (pentaerythritol) are preferred.
 前記ポリオールエステルの脂肪酸としては、前記脂肪酸エステルに記載の不飽和脂肪酸、及び炭素数5~19の直鎖又は分枝アルキル基を有する飽和脂肪酸が例示され、特に前記脂肪酸エステルに記載の不飽和脂肪酸が好ましく用いられる。あるいはα炭素原子が4級であるネオ酸などが挙げられる。さらに分岐の飽和脂肪酸として、具体的には、イソペンタン酸(3-メチルブタン酸)、2-メチルヘキサン酸、2-エチルペンタン酸、2-エチルヘキサン酸、3,5,5-トリメチルヘキサン酸などが挙げられる。 Examples of the fatty acid of the polyol ester include unsaturated fatty acids described in the fatty acid esters, and saturated fatty acids having a linear or branched alkyl group having 5 to 19 carbon atoms, and particularly unsaturated fatty acids described in the fatty acid esters. Is preferably used. Or the neo acid etc. whose (alpha) carbon atom is quaternary are mentioned. Specific examples of branched saturated fatty acids include isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, and the like. Can be mentioned.
 好ましいポリオールエステルの具体例としては、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、オレイン酸、イソペンタン酸、2-メチルヘキサン酸、2-エチルペンタン酸、2-エチルヘキサン酸、3,5,5-トリメチルヘキサン酸の中から選ばれる1種又は2種以上の脂肪酸と、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン及びペンタエリスリトールの各ポリオールとのジエステル、トリエステルおよびテトラエステルが挙げられる。
 なお、2種以上の脂肪酸とポリオールとのエステルとは、1種の脂肪酸とポリオールのエステルを2種以上混合したものでも良く、2種以上の混合脂肪酸とポリオールのエステルであっても良い。
Specific examples of preferred polyol esters include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, and 2-ethylhexanoic acid. A diester of one or more fatty acids selected from 3,5,5-trimethylhexanoic acid and each polyol of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, Triesters and tetraesters are mentioned.
The ester of two or more fatty acids and a polyol may be a mixture of two or more esters of one fatty acid and a polyol, or may be an ester of two or more mixed fatty acids and a polyol.
 また、ポリオールエステルの中でも、より加水分解安定性に優れることから、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ジ-(トリメチロールプロパン)、トリ-(トリメチロールプロパン)、ペンタエリスリトール、ジ-(ペンタエリスリトール)、トリ-(ペンタエリスリトール)などのヒンダードアルコールのエステルがより好ましく、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン及びペンタエリスリトールのエステルがさらにより好ましく、加水分解安定性に特に優れることからトリメチロールプロパン、ペンタエリスリトールのエステルが最も好ましい。具体的には、トリメチロールプロパンオレエート、ペンタエリスリトールオレエート等が好ましく用いられる。 Among the polyol esters, since they are more excellent in hydrolysis stability, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), penta More preferred are esters of hindered alcohols such as erythritol, di- (pentaerythritol), tri- (pentaerythritol), and even more preferred are esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol. The ester of trimethylolpropane and pentaerythritol is most preferred because it is particularly excellent in hydrolysis stability. Specifically, trimethylolpropane oleate, pentaerythritol oleate and the like are preferably used.
 なお、ポリオールエステルとしては、ポリオールの全ての水酸基がエステル化されずに一部の水酸基が残った部分エステルであっても良く、全ての水酸基がエステル化された完全エステルであっても良く、また部分エステルと完全エステルの混合物であっても良いが、完全エステルであることが好ましい。 The polyol ester may be a partial ester in which some hydroxyl groups remain without esterification of all hydroxyl groups of the polyol, or may be a complete ester in which all hydroxyl groups are esterified, A mixture of a partial ester and a complete ester may be used, but a complete ester is preferred.
 コンプレックスエステルとは、脂肪酸及び二塩基酸と、一価アルコール及びポリオールとのエステルのことであり、脂肪酸、二塩基酸、一価アルコール、ポリオールとしては、前述の二塩基酸エステル及びポリオールエステルに関する説明において例示したものと同様のものが使用できる。 The complex ester is an ester of a fatty acid and a dibasic acid, and a monohydric alcohol and a polyol. The fatty acid, the dibasic acid, the monohydric alcohol, and the polyol are described with respect to the dibasic acid ester and the polyol ester. The thing similar to what was illustrated in can be used.
 芳香族エステルとしては、1~6価、好ましくは1~4価、より好ましくは1~3価の芳香族カルボン酸と炭素数1~18、好ましくは1~12の脂肪族アルコールとのエステルなどが用いられる。1~6価の芳香族カルボン酸としては、具体的には例えば、安息香酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸及びこれらの混合物などが挙げられる。また、炭素数1~18の脂肪族アルコールとしては、前記脂肪酸エステルに記載の直鎖又は分枝アルキル基を有する炭素数1~15の一価アルコール、直鎖状又は分枝状のヘキサデカノール、直鎖状又は分枝状のヘプタデカノール、直鎖状又は分枝状のオクタデカノール及びこれらの混合物などが挙げられる。
 芳香族エステルとして、具体的には例えば、フタル酸ジブチル、フタル酸ジ(2-エチルヘキシル)、フタル酸ジノニル、フタル酸ジデシル、フタル酸ジドデシル、フタル酸ジトリデシル、トリメリット酸トリブチル、トリメリット酸トリ(2-エチルヘキシル)、トリメリット酸トリノニル、トリメリット酸トリデシル、トリメリット酸トリドデシル、トリメリット酸トリトリデシルなどが挙げられる。なお、当然のことながら、2価以上の芳香族カルボン酸を用いた場合、1種の脂肪族アルコールからなる単純エステルであってもよいし、2種以上の脂肪族アルコールからなる複合エステルであってもよい。
Examples of the aromatic ester include esters of 1 to 6 valent, preferably 1 to 4 valent, more preferably 1 to 3 valent aromatic carboxylic acid and aliphatic alcohol having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. Is used. Specific examples of the monovalent to hexavalent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof. Examples of the aliphatic alcohol having 1 to 18 carbon atoms include monohydric alcohols having 1 to 15 carbon atoms and linear or branched hexadecanol having a linear or branched alkyl group described in the fatty acid ester. , Linear or branched heptadecanol, linear or branched octadecanol, and mixtures thereof.
Specific examples of aromatic esters include dibutyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, didodecyl phthalate, ditridecyl phthalate, tributyl trimellitic acid, trimethyl trimellitic acid ( 2-ethylhexyl), trinonyl trimellitic acid, tridecyl trimellitic acid, tridodecyl trimellitic acid, tritridecyl trimellitic acid, and the like. Of course, when a divalent or higher valent aromatic carboxylic acid is used, it may be a simple ester composed of one kind of aliphatic alcohol or a complex ester composed of two or more kinds of aliphatic alcohol. May be.
 また、炭酸エステルとは、分子内に炭酸エステル構造を有する化合物である。なお、炭酸エステル構造は一分子内に1つでも良いし複数有していても良い。
 炭酸エステルを構成するアルコールとしては、前述の脂肪族アルコール、ポリオールなどが使用でき、またポリグリコールやポリオールにポリグリコールを付加させたものも使用できる。また、炭酸と脂肪酸及び/又は二塩基酸を用いたものを使用しても良い。
The carbonate ester is a compound having a carbonate ester structure in the molecule. One carbonate ester structure or a plurality of carbonate ester structures may be included in one molecule.
As alcohol which comprises carbonate ester, the above-mentioned aliphatic alcohol, polyol, etc. can be used, and what added polyglycol to polyglycol and polyol can also be used. Moreover, you may use what used carbonic acid and a fatty acid, and / or a dibasic acid.
 また、当然のことながら本発明でいうエステルとしては、単一の構造のエステル1種からなるものであっても良く、構造の異なる2種以上のエステルの混合物であっても良い。
 これらのエステル系基油の中でも、加水分解安定性に優れることから、ポリオールエステルが好ましい。
 本発明においては、上記のエステル系基油のうちの1種を単独で用いてもよく、また2種以上を組み合わせて用いてもよい。
As a matter of course, the ester referred to in the present invention may be a single ester having a single structure or a mixture of two or more esters having different structures.
Among these ester base oils, a polyol ester is preferable because of excellent hydrolysis stability.
In the present invention, one of the ester base oils may be used alone, or two or more may be used in combination.
 また、本発明の難燃性油圧作動油組成物の基油として用いられる油脂としては、天然の動植物油脂が挙げられ、例えば、菜種油、ひまわり油、大豆油、ひまし油、ココナッツ油、コーン油、綿実油、オリーブ油、米ぬか油、ヤシ油、パーム油、パーム核油、ピーナッツ油、トール油、牛脂、豚脂、あるいはこれらの水素添加物等が挙げられる。油脂の中では、エステルを構成する脂肪酸のうち不飽和脂肪酸、特にオレイン酸の比率が高いハイオレイン酸タイプの油脂類が好ましく、さらにオレイン酸の比率を高めたハイオレイン化植物油がさらに好ましい。 Examples of the oil used as the base oil of the flame retardant hydraulic fluid composition of the present invention include natural animal and vegetable oils and fats, such as rapeseed oil, sunflower oil, soybean oil, castor oil, coconut oil, corn oil, and cottonseed oil. Olive oil, rice bran oil, coconut oil, palm oil, palm kernel oil, peanut oil, tall oil, beef tallow, lard, or hydrogenated products thereof. Among the oils and fats, hyoleic acid type fats and oils having a high proportion of unsaturated fatty acids, particularly oleic acid, among fatty acids constituting the ester are preferable, and hyoleinized vegetable oil having a higher proportion of oleic acid is more preferable.
 本発明の難燃性作動油組成物の基油としては、上記した鉱油、合成系炭化水素、合成エステル及び油脂からなる群より選ばれる1種を単独で用いてもよいし、2種以上組み合わせて用いてもよい。 As the base oil of the flame retardant hydraulic oil composition of the present invention, one kind selected from the group consisting of the above-described mineral oil, synthetic hydrocarbon, synthetic ester and oil and fat may be used alone, or a combination of two or more kinds may be used. May be used.
 前記合成エステル及び/または油脂において、構成脂肪酸は、飽和脂肪酸、不飽和脂肪酸、また直鎖状脂肪酸、分枝状脂肪酸の何れであってもよいが、(B)成分の式(1)で示されるカルボジイミド化合物あるいはエポキシ化合物の酸捕捉剤の添加効果からは、不飽和脂肪酸を含有した方が好ましい。エステルを構成する脂肪酸に占める不飽和脂肪酸の比率は30モル%以上、好ましくは50モル%以上、さらに好ましくは70モル%以上であることが望ましい。
 エステルを構成する脂肪酸に占める不飽和脂肪酸の比率が30モル%未満であると、(B)成分を配合しても、油圧作動油の使用の初期段階では粘度上昇・酸価増加の抑制効果があるが、使用が進むと劣化生成物が急にスラッジ化し易く、油圧システム内でトラブルが発生することがある。
In the synthetic ester and / or fat and oil, the constituent fatty acid may be a saturated fatty acid, an unsaturated fatty acid, a linear fatty acid, or a branched fatty acid, and is represented by the formula (1) of the component (B). From the addition effect of an acid scavenger of a carbodiimide compound or an epoxy compound, it is preferable to contain an unsaturated fatty acid. The ratio of the unsaturated fatty acid to the fatty acid constituting the ester is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more.
When the ratio of unsaturated fatty acid in the fatty acid constituting the ester is less than 30 mol%, even if the component (B) is blended, the effect of suppressing the increase in viscosity and the increase in acid value is obtained at the initial stage of use of the hydraulic fluid. However, as the use proceeds, the deteriorated product tends to become sludge suddenly, and troubles may occur in the hydraulic system.
 なお、これら基油の動粘度は、特に限定されず任意であるが、難燃性、耐摩耗性、耐焼き付性に優れ、かつ攪拌抵抗による摩擦ロスが少ない等の点から、通常、40℃における動粘度は、好ましくは10~200mm/s、より好ましくは15~150mm/sであり、さらにより好ましくは20~100mm/sである。またその粘度指数も任意であるが、高温における油膜維持等の点から、通常、その粘度指数は好ましくは80~500、より好ましくは100~300である。さらにその流動点も任意であるが、冬期におけるポンプ始動性等の点から、好ましくは-5℃以下、より好ましくは-15℃以下である。 The kinematic viscosities of these base oils are not particularly limited and are arbitrary, but are usually 40 from the viewpoints of excellent flame retardancy, wear resistance, seizure resistance, and low friction loss due to stirring resistance. The kinematic viscosity at 0 ° C. is preferably 10 to 200 mm 2 / s, more preferably 15 to 150 mm 2 / s, and still more preferably 20 to 100 mm 2 / s. The viscosity index is arbitrary, but from the viewpoint of maintaining an oil film at a high temperature, the viscosity index is usually preferably from 80 to 500, more preferably from 100 to 300. The pour point is also arbitrary, but is preferably −5 ° C. or lower, more preferably −15 ° C. or lower, from the viewpoint of pump startability in winter.
 本発明の難燃性作動油組成物における(B)成分である下記一般式(1)で示されるカルボジイミド化合物のRおよびRは、アルキル基、フェニル基、アルキルフェニル基、アラルキル基、シクロパラフィン基、またはアルキルシクロパラフィン基を示し、それぞれ同一でも異なっていてもよい。 R 1 and R 2 of the carbodiimide compound represented by the following general formula (1), which is the component (B) in the flame retardant hydraulic oil composition of the present invention, are an alkyl group, a phenyl group, an alkylphenyl group, an aralkyl group, a cyclo A paraffin group or an alkylcycloparaffin group, each of which may be the same or different;
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
 アルキル基としては、炭素数が4~26の直鎖または分岐鎖のアルキル基が好ましく、より好ましくは炭素数が4~12の直鎖または分岐鎖のアルキル基であり、例えばブチル基、ペンチル基、ヘキシル基、オクチル基等が挙げられる。
 R、Rがアルキルフェニル基の場合は、一般式(1)で示される化合物として、下記一般式(2)で表されるジフェニルカルボジイミドまたはジアルキルフェニルカルボジイミドが挙げられる。一般式(2)中、R、R、R、R、RおよびRは、水素または炭素数1~8のアルキル基を示し、それぞれ同一でも異なっていてもよい。
 また、シクロパラフィン基、アルキルシクロパラフィン基としては、前記ジアルキルフェニルカルボジイミドにおいてフェニル基がシクロヘキシル基に置き換わったものが挙げられる。
The alkyl group is preferably a linear or branched alkyl group having 4 to 26 carbon atoms, more preferably a linear or branched alkyl group having 4 to 12 carbon atoms, such as a butyl group or a pentyl group. Hexyl group, octyl group and the like.
When R 1 and R 2 are alkylphenyl groups, examples of the compound represented by the general formula (1) include diphenylcarbodiimide or dialkylphenylcarbodiimide represented by the following general formula (2). In general formula (2), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may be the same or different.
Examples of the cycloparaffin group and the alkylcycloparaffin group include those in which the phenyl group is replaced with a cyclohexyl group in the dialkylphenylcarbodiimide.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
 一般式(1)で表される化合物の中でも、より優れた酸捕捉効果が得られることから、R、Rは、アルキルフェニル基、中でもエチル基又は炭素数3~4の分枝アルキル基が付いたフェニル基が好ましく、例えばジイソプロピルフェニル基、ジターシャリーブチルフェニル基が好ましく、具体的にはビス(2,6-ジ-tert-ブチルフェニル)カルボジイミドが挙げられる。
 また、R、Rの炭素数は、それぞれ4~26が好ましく、4~20がより好ましく、4~12がさらに好ましい。RまたはRの炭素数が3以下であると反応性が高くなり不安定となって好ましくなく、27以上であると分子中に占める官能基の割合が小さくなり、酸補足効果に悪影響を与える恐れがある。
Among the compounds represented by the general formula (1), R 1 and R 2 are an alkylphenyl group, particularly an ethyl group or a branched alkyl group having 3 to 4 carbon atoms because a better acid scavenging effect can be obtained. Preferred are phenyl groups with, for example, diisopropylphenyl group and ditertiarybutylphenyl group, and specific examples include bis (2,6-di-tert-butylphenyl) carbodiimide.
In addition, R 1 and R 2 each preferably have 4 to 26 carbon atoms, more preferably 4 to 20 carbon atoms, and still more preferably 4 to 12 carbon atoms. When R 1 or R 2 has 3 or less carbon atoms, the reactivity becomes high and unstable, which is not preferable, and when it is 27 or more, the proportion of functional groups in the molecule decreases, which adversely affects the acid supplementation effect. There is a risk of giving.
 (B)成分のエポキシ化合物としては、アルキルオキシラン化合物、アリルオキシラン化合物、フェニルグリシジルエーテル型エポキシ化合物、アルキルグリシジルエーテル型エポキシ化合物、グリシジルエステル型エポキシ化合物、脂環式エポキシ化合物、エポキシ化脂肪酸モノエステルおよびエポキシ化植物油から選ばれる少なくとも1種のエポキシ化合物を用いることができる。 As the epoxy compound of component (B), alkyl oxirane compounds, allyl oxirane compounds, phenyl glycidyl ether type epoxy compounds, alkyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, epoxidized fatty acid monoesters and At least one epoxy compound selected from epoxidized vegetable oils can be used.
 アルキルオキシラン化合物のアルキル基は、炭素数4~20の直鎖もしくは分岐のアルキル基であり、炭素数8~20のアルキル基が好ましく、炭素数10~18のアルキル基が更に好ましい。アルキル基の炭素数が3以下であると蒸発しやすく安定性に欠ける。一方アルキル基の炭素数が21以上であると低温性能、溶解性特に酸捕捉後の溶解性に劣る。 The alkyl group of the alkyloxirane compound is a linear or branched alkyl group having 4 to 20 carbon atoms, preferably an alkyl group having 8 to 20 carbon atoms, and more preferably an alkyl group having 10 to 18 carbon atoms. When the carbon number of the alkyl group is 3 or less, it tends to evaporate and lacks stability. On the other hand, when the carbon number of the alkyl group is 21 or more, the low temperature performance and solubility, particularly the solubility after acid capture, are poor.
 アルキルオキシラン化合物としては、具体的には、1,2-エポキシブタン、1,2-エポキシペンタン、1,2-エポキシヘキサン、1,2-エポキシヘプタン、1,2-エポキシオクタン、1,2-エポキシノナン、1,2-エポキシデカン、1,2-エポキシウンデカン、1,2-エポキシドデカン、1,2-エポキシトリデカン、1,2-エポキシテトラデカン、1,2-エポキシペンタデカン、1,2-エポキシヘキサデカン、1,2-エポキシヘプタデカン、1,1,2-エポキシオクタデカン、2-エポキシノナデカン、1,2-エポキシイコサンなどが例示できる。 Specific examples of the alkyloxirane compound include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2- Epoxy nonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2- Examples thereof include epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, and 1,2-epoxyicosane.
 アリルオキシラン化合物としては、具体的には、1,2-エポキシスチレン、アルキル-1,2-エポキシスチレンなどが例示できる。 Specific examples of the allyloxirane compound include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.
 フェニルグリシジルエーテル型エポキシ化合物としては、具体的には、フェニルグリシジルエーテルまたはアルキルフェニルグリシジルエーテルが例示できる。ここでいうアルキルフェニルグリシジルエーテルとは、炭素数1~13のアルキル基を1~3個有するものが挙げられ、中でも炭素数4~10のアルキル基を1個有するもの、例えばn-ブチルフェニルグリシジルエーテル、i-ブチルフェニルグリシジルエーテル、sec-ブチルフェニルグリシジルエーテル、tert-ブチルフェニルグリシジルエーテル、ペンチルフェニルグリシジルエーテル、ヘキシルフェニルグリシジルエーテル、ヘプチルフェニルグリシジルエーテル、オクチルフェニルグリシジルエーテル、ノニルフェニルグリシジルエーテル、デシルフェニルグリシジルエーテルなどが好ましいものとして例示できる。 Specific examples of the phenyl glycidyl ether type epoxy compound include phenyl glycidyl ether and alkylphenyl glycidyl ether. Examples of the alkylphenyl glycidyl ether herein include those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, and those having one alkyl group having 4 to 10 carbon atoms, such as n-butylphenyl glycidyl. Ether, i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decylphenyl A glycidyl ether etc. can be illustrated as a preferable thing.
 アルキルグリシジルエーテル型エポキシ化合物としては、具体的には、デシルグリシジルエーテル、ウンデシルグリシジルエーテル、ドデシルグリシジルエーテル、トリデシルグリシジルエーテル、テトラデシルグリシジルエーテル、2-エチルヘキシルグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリアルキレングリコールモノグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテルなどが例示できる。 Specific examples of the alkyl glycidyl ether type epoxy compound include decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, Examples thereof include trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, and polyalkylene glycol diglycidyl ether.
 グリシジルエステル型エポキシ化合物としては、具体的には、フェニルグリシジルエステル、アルキルグリシジルエステル、アルケニルグリシジルエステルなどが挙げられ、好ましいものとしては、グリシジル-2,2-ジメチルオクタノエート、グリシジルベンゾエート、グリシジルアクリレート、グリシジルメタクリレートなどが例示できる。 Specific examples of the glycidyl ester type epoxy compound include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester and the like, and preferred are glycidyl-2,2-dimethyloctanoate, glycidyl benzoate, glycidyl acrylate. And glycidyl methacrylate.
 脂環式エポキシ化合物としては、具体的には、1,2-エポキシシクロヘキサン、1,2-エポキシシクロペンタン、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、ビス(3,4-エポキシシクロヘキシルメチル)アジペート、エキソ-2,3-エポキシノルボルナン、ビス(3,4-エポキシ-6-メチルシクロヘキシルメチル)アジペート、2-(7-オキサビシクロ[4.1.0]ヘプト-3-イル)-スピロ(1,3-ジオキサン-5,3’-[7]オキサビシクロ[4.1.0]ヘプタン、4-(1’-メチルエポキシエチル)-1,2-エポキシ-2-メチルシクロヘキサン、4-エポキシエチル-1,2-エポキシシクロヘキサンなどが例示できる。 Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4 -Epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3- Yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methyl Examples include cyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.
 エポキシ化脂肪酸モノエステルとしては、具体的には、エポキシ化された炭素数12~20の脂肪酸と炭素数1~8のアルコールまたはフェノール、アルキルフェノールとのエステルなどが例示できる。特にエポキシステアリン酸のブチル、ヘキシル、ベンジル、シクロヘキシル、メトキシエチル、オクチル、フェニルおよびブチルフェニルエステルが好ましく用いられる。 Specific examples of the epoxidized fatty acid monoester include esters of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.
 エポキシ化植物油としては、具体的には、大豆油、アマニ油、綿実油等の植物油のエポキシ化合物などが例示できる。 Specific examples of the epoxidized vegetable oil include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.
 これらのエポキシ化合物の中でも好ましいものは、アルキルオキシラン化合物、フェニルグリシジルエーテル型エポキシ化合物、グリシジルエステル型エポキシ化合物、脂環式エポキシ化合物およびエポキシ化脂肪酸モノエステルである。中でも、アルキルオキシラン化合物、フェニルグリシジルエーテル型エポキシ化合物およびグリシジルエステル型エポキシ化合物がより好ましく、1,2-エポキシテトラデカン、フェニルグリシジルエーテル、ブチルフェニルグリシジルエーテル、アルキルグリシジルエステルもしくはこれらの混合物が特に好ましい。 Among these epoxy compounds, preferred are alkyl oxirane compounds, phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds and epoxidized fatty acid monoesters. Of these, alkyl oxirane compounds, phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds are more preferred, and 1,2-epoxytetradecane, phenyl glycidyl ether, butylphenyl glycidyl ether, alkyl glycidyl esters or mixtures thereof are particularly preferred.
 本発明の難燃性油圧作動油成物における(B)成分の含有量の上限値は、組成物全量基準で2質量%であり、好ましくは1.5質量%、より好ましくは1.0質量%である。含有量が2質量%を超える場合、酸捕捉後の溶解性に劣り、スラッジ発生の原因となるので好ましくない。一方、(B)成分の含有量の下限値は、組成物全量基準で0.01質量%であり、好ましくは0.05質量%、より好ましくは0.1質量%である。(B)成分の含有量が0.01質量%に満たない場合は、酸捕捉効果が不足するので好ましくない。 The upper limit of the content of the component (B) in the flame retardant hydraulic fluid composition of the present invention is 2% by mass, preferably 1.5% by mass, more preferably 1.0% by mass based on the total amount of the composition. %. When the content exceeds 2% by mass, the solubility after acid trapping is inferior, causing sludge generation, which is not preferable. On the other hand, the lower limit of the content of component (B) is 0.01% by mass, preferably 0.05% by mass, more preferably 0.1% by mass, based on the total amount of the composition. When the content of the component (B) is less than 0.01% by mass, the acid scavenging effect is insufficient, which is not preferable.
 本発明の難燃性油圧作動油組成物は、(C)成分として、硫黄含有リン酸エステル、酸性リン酸エステル、酸性リン酸エステルアミン塩、及び亜リン酸エステルよりなる群から選ばれる少なくとも1種類の摩耗防止剤を含有する。 The flame-retardant hydraulic fluid composition of the present invention has at least one selected from the group consisting of a sulfur-containing phosphate ester, an acidic phosphate ester, an acidic phosphate amine salt, and a phosphite ester as the component (C). Contains various types of antiwear agents.
 硫黄含有リン酸エステルとしては、具体的には、アルキル基が炭素数4~18であるトリアルキルフォスフォロチオネート、トリオレイルフォスフォロチオネート、トリフェニルフォスフォロチオネート、トリクレジルフォスフォロチオネート、トリキシレニルフォスフォロチオネート、クレジルジフェニルフォスフォロチオネート、キシレニルジフェニルフォスフォロチオネート、トリス(n-プロピルフェニル)フォスフォロチオネート、トリス(イソプロピルフェニル)フォスフォロチオネート、トリス(n-ブチルフェニル)フォスフォロチオネート、トリス(イソブチルフェニル)フォスフォロチオネート、トリス(s-ブチルフェニル)フォスフォロチオネート、トリス(t-ブチルフェニル)フォスフォロチオネート等が挙げられる。 Specific examples of the sulfur-containing phosphate ester include trialkyl phosphorothioate, trioleyl phosphorothioate, triphenyl phosphorothioate, tricresyl phosphorothioate having an alkyl group of 4 to 18 carbon atoms. , Trixylenyl phosphorothioate, cresyl diphenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phosphorothioate, tris (N-butylphenyl) phosphothionate, tris (isobutylphenyl) phosphothionate, tris (s-butylphenyl) phosphothionate, tris (t-butylphenyl) phosphothionate, etc. It is.
 酸性リン酸エステルの具体例としては、アルキル基が炭素数4~22であるアルキルアシッドフォスフェート及びジオレイルアシッドホスフェート、芳香族基酸性リン酸エステルである、ジフェニルアシッドフォスフェート、ジクレジルエステルアシッドフォスフェートなどが挙げられる。その中でも、芳香族を含まず、アルキル基の炭素数4~22であるジアルキルアシッドフォスフェートが好ましく、更に好ましくはアルキル基炭素数6~18であるジアルキルアシッドフォスフェートが好ましい。 Specific examples of acidic phosphate esters include alkyl acid phosphates and dioleyl acid phosphates having an alkyl group of 4 to 22 carbon atoms, diphenyl acid phosphates and dicresyl ester acid phosphates which are aromatic acid phosphate esters. Fate etc. are mentioned. Of these, dialkyl acid phosphates that do not contain aromatics and have an alkyl group with 4 to 22 carbon atoms are preferred, and dialkyl acid phosphates with an alkyl group with 6 to 18 carbon atoms are more preferred.
 酸性リン酸エステルアミン塩としては、具体的には、前記酸性リン酸エステルと、炭素数1~8のアルキル基を有するアミン、炭素数1~8のアルキル基を2個有するアミン、及び炭素数1~8のアルキル基を3個有するアミンから選ばれるアミンとの塩が挙げられる。 Specifically, the acid phosphate ester amine salt includes the acid phosphate ester, an amine having an alkyl group having 1 to 8 carbon atoms, an amine having two alkyl groups having 1 to 8 carbon atoms, and the number of carbon atoms. Examples thereof include salts with amines selected from amines having 3 alkyl groups of 1-8.
 亜リン酸エステルとしては、具体的には、炭素数4~12のアルキル基を2個有するジアルキルホスファイト、ジオレイルホスファイト、ジフェニルホスファイト、ジクレジルホスファイト、炭素数4~12のアルキル基を3個有するトリアルキルホスファイト、トリオレイルホスファイト、トリフェニルホスファイト、及びトリクレジルホスファイトなどが挙げられる。 Specific examples of the phosphite ester include dialkyl phosphites, dioleyl phosphites, diphenyl phosphites, dicresyl phosphites having 4 to 12 carbon atoms, and alkyl groups having 4 to 12 carbon atoms. And trialkyl phosphites, trioleyl phosphites, triphenyl phosphites, and tricresyl phosphites.
 本発明で用いる(C)成分としては、中でも合成エステル及び油脂中での効果が高いことから、硫黄含有リン酸エステル、酸性リン酸エステル、酸性リン酸エステルアミン塩が好ましく用いられる。 As the component (C) used in the present invention, sulfur-containing phosphate esters, acidic phosphate esters, and acidic phosphate ester amine salts are preferably used because of their high effects in synthetic esters and fats and oils.
 本発明の難燃性油圧作動油組成物における(C)成分の含有量の上限値は、組成物全量基準で5質量%であり、好ましくは2質量%、より好ましくは1.5質量%である。含有量が5質量%を超える場合、熱安定性に劣り、スラッジ発生の原因となるので好ましくない。一方、(C)成分の含有量の下限値は、組成物全量基準で0.001質量%であり、好ましくは0.005質量%、より好ましくは0.01質量%である。(C)成分の含有量が0.001質量%に満たない場合は、耐摩耗性及び耐焼き付き性が不足するので好ましくない。 The upper limit of the content of the component (C) in the flame-retardant hydraulic fluid composition of the present invention is 5% by mass, preferably 2% by mass, more preferably 1.5% by mass based on the total amount of the composition. is there. When the content exceeds 5% by mass, the thermal stability is inferior and sludge is generated, which is not preferable. On the other hand, the lower limit of the content of the component (C) is 0.001% by mass, preferably 0.005% by mass, more preferably 0.01% by mass based on the total amount of the composition. When the content of the component (C) is less than 0.001% by mass, the wear resistance and seizure resistance are insufficient, which is not preferable.
 本発明の難燃性油圧作動油組成物は、さらにアミン系酸化防止剤及び/又はフェノール系酸化防止剤を含有することが好ましい。酸化防止剤を併用することでより高い酸化防止性とスラッジ抑制性を付加することができる。酸化防止剤としては、潤滑油の酸化防止剤として用いられる任意のアミン系化合物、フェノール系が使用可能であり、特に限定されるのもではない。 The flame retardant hydraulic fluid composition of the present invention preferably further contains an amine-based antioxidant and / or a phenol-based antioxidant. By using an antioxidant in combination, higher antioxidant properties and sludge suppression properties can be added. As the antioxidant, any amine compound or phenol used as an antioxidant for lubricating oil can be used, and it is not particularly limited.
 代表的なアミン系酸化防止剤としては、以下の式(4)で示すフェニル-α-ナフチルアミン類、あるいは式(5)で示すp,p’-ジアルキル化ジフェニルアミンが挙げられる。 Representative amine antioxidants include phenyl-α-naphthylamines represented by the following formula (4) or p, p'-dialkylated diphenylamine represented by the following formula (5).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
 一般式(4)において、R13は水素原子又は炭素数1~16のアルキル基を示す。
 一般式(5)において、R14及びR15は、それぞれ個別に、炭素数1~16のアルキル基を示す。
In the general formula (4), R 13 represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.
In the general formula (5), R 14 and R 15 each independently represents an alkyl group having 1 to 16 carbon atoms.
 一般式(4)で表される化合物の中でもR13がアルキル基である場合は、より優れたスラッジ生成抑制効果が得られることから、R13は、炭素数8~16の分枝アルキル基が好ましく、さらに炭素数3又は4のオレフィンのオリゴマーから誘導される炭素数8~16の分枝アルキル基がより好ましい。炭素数3又は4のオレフィンとしては、具体的にはプロピレン、1-ブテン、2-ブテン及びイソブチレンが挙げられるが、より優れたスラッジ生成抑制効果を得るためには、プロピレン又はイソブチレンが好ましい。更に優れたスラッジ生成抑制効果を得るためには、R13は、イソブチレンの2量体から誘導される分枝オクチル基、プロピレンの3量体から誘導される分枝ノニル基、イソブチレンの3量体から誘導される分枝ドデシル基、プロピレンの4量体から誘導される分枝ドデシル基またはプロピレンの5量体から誘導される分枝ペンタデシル基がさらに好ましく、イソブチレンの2量体から誘導される分枝オクチル基、イソブチレンの3量体から誘導される分枝ドデシル基又はプロピレンの4量体から誘導される分枝ドデシル基がより好ましく、分岐ドデシル基が最も好ましい。 Among the compounds represented by the general formula (4), when R 13 is an alkyl group, a more excellent sludge generation suppressing effect can be obtained. Therefore, R 13 is a branched alkyl group having 8 to 16 carbon atoms. Further, a branched alkyl group having 8 to 16 carbon atoms derived from an oligomer of an olefin having 3 or 4 carbon atoms is more preferable. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene and isobutylene, but propylene or isobutylene is preferable in order to obtain a more excellent sludge formation suppressing effect. In order to obtain a further excellent sludge production inhibitory effect, R 13 represents a branched octyl group derived from an isobutylene dimer, a branched nonyl group derived from a propylene trimer, and an isobutylene trimer. A branched dodecyl group derived from a propylene tetramer, a branched dodecyl group derived from a propylene tetramer, or a branched pentadecyl group derived from a propylene pentamer is more preferred, and a branch derived from a dimer of isobutylene. A branched dodecyl group derived from a branched octyl group, a trimer of isobutylene or a branched dodecyl group derived from a tetramer of propylene is more preferred, and a branched dodecyl group is most preferred.
 一般式(5)で表されるp,p’-ジアルキルジフェニルアミンのR14及びR15は、より優れたスラッジ生成抑制効果を得るために、それぞれ個別に、炭素数3~16の分枝アルキル基が好ましく、さらに炭素数3又は4のオレフィン、又はそのオリゴマーから誘導される炭素数3~16の分枝アルキル基がより好ましい。上記炭素数3又は4のオレフィンとしては、具体的にはプロピレン、1-ブテン、2-ブテンおよびイソブチレン等が挙げられるが、より優れたスラッジ生成抑制効果を得るためにプロピレン又はイソブチレンが好ましい。
 さらに、R14又はR15は、より優れた酸化防止効果を得るために、イソブチレンから誘導されるtert-ブチル基、イソブチレンの2量体から誘導される分枝オクチル基が最も好ましい。
R 14 and R 15 of p, p′-dialkyldiphenylamine represented by the general formula (5) are each independently a branched alkyl group having 3 to 16 carbon atoms in order to obtain a more excellent sludge generation inhibiting effect. Further, a branched alkyl group having 3 to 16 carbon atoms derived from an olefin having 3 or 4 carbon atoms or an oligomer thereof is more preferable. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene, and isobutylene, but propylene or isobutylene is preferable in order to obtain a more excellent sludge generation suppressing effect.
Further, R 14 or R 15 is most preferably a tert-butyl group derived from isobutylene or a branched octyl group derived from a dimer of isobutylene in order to obtain a better antioxidant effect.
 一般式(5)で表されるp,p’-ジアルキルジフェニルアミンは市販のものを用いても良くまた合成物を用いても良い。合成物は、一般式(4)で表されるフェニル-α-ナフチルアミンと同様に、炭素数1~16のハロゲン化アルキル化合物とジフェニルアミン、あるいは炭素数2~16のオレフィン又は炭素数2~16のオレフィン又はこれらのオリゴマーとジフェニルアミンとをフリーデル・クラフツ触媒を用いて反応させることにより、容易に合成することができるが、いずれの合成方法であっても良い。 As the p, p'-dialkyldiphenylamine represented by the general formula (5), a commercially available product or a synthesized product may be used. Similar to the phenyl-α-naphthylamine represented by the general formula (4), the synthesized product is a halogenated alkyl compound having 1 to 16 carbon atoms and diphenylamine, or an olefin having 2 to 16 carbon atoms or an alkyl having 2 to 16 carbon atoms. Although it can be easily synthesized by reacting an olefin or an oligomer thereof with diphenylamine using a Friedel-Crafts catalyst, any synthesis method may be used.
 アミン系酸化防止剤の含有量の上限値は、組成物全量基準で2質量%が好ましく、より好ましくは1.5質量%、さらに好ましくは1質量%である。含有量が2質量%を超える場合、スラッジ発生の原因となるので好ましくない。一方、アミン系酸化防止剤の含有量の下限値は、組成物全量基準で、0.001質量%が好ましく、より好ましくは0.05質量%、さらに好ましくは0.1質量%である。酸化防止剤の含有量が0.001質量%に満たない場合は、酸化防止効果が不足するので好ましくない。 The upper limit of the content of the amine-based antioxidant is preferably 2% by mass based on the total amount of the composition, more preferably 1.5% by mass, and even more preferably 1% by mass. If the content exceeds 2% by mass, sludge is generated, which is not preferable. On the other hand, the lower limit of the content of the amine antioxidant is preferably 0.001% by mass, more preferably 0.05% by mass, and still more preferably 0.1% by mass based on the total amount of the composition. When the content of the antioxidant is less than 0.001% by mass, the antioxidant effect is insufficient, which is not preferable.
 フェノール系酸化防止剤としては、潤滑油の酸化防止剤として用いられる任意のアルキルフェノール系化合物が使用可能であり、特に限定されるのもではないが、例えば、下記の一般式(6)又は一般式(7)で表される化合物の中から選ばれる1種または2種以上のアルキルフェノール化合物が好ましいものとして挙げられる。 As the phenolic antioxidant, any alkylphenolic compound used as an antioxidant for lubricating oils can be used, and is not particularly limited. For example, the following general formula (6) or general formula One or more alkylphenol compounds selected from the compounds represented by (7) are preferred.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
 上記(6)式中、R16は炭素数1~4のアルキル基を示し、R17は水素原子又は炭素数1~4のアルキル基を示し、R18は水素原子、炭素数1~4のアルキル基、下記の一般式(i)で表される基又は下記の一般式(ii)で表される基を示す。 In the above formula (6), R 16 represents an alkyl group having 1 to 4 carbon atoms, R 17 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 18 represents a hydrogen atom, and has 1 to 4 carbon atoms. An alkyl group, a group represented by the following general formula (i) or a group represented by the following general formula (ii) is shown.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
 上記式(i)中、R19は炭素数1~6のアルキレン基、R20は炭素数1~24のアルキル基又はアルケニル基を示す。
 上記式(ii)中、R21は炭素数1~6のアルキレン基を示し、R22は炭素数1~4のアルキル基を示し、R23は水素原子又は炭素数1~4のアルキル基を示し、nは0または1の整数を示す。
In the above formula (i), R 19 represents an alkylene group having 1 to 6 carbon atoms, and R 20 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms.
In the above formula (ii), R 21 represents an alkylene group having 1 to 6 carbon atoms, R 22 represents an alkyl group having 1 to 4 carbon atoms, and R 23 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. N represents an integer of 0 or 1.
Figure JPOXMLDOC01-appb-C000011
 上記(7)式中、R24及びR28は、それぞれ個別に、炭素数1~4のアルキル基を示し、R25及びR29は、それぞれ個別に、水素原子又は炭素数1~4のアルキル基を示し、R26及びR27は、それぞれ個別に、炭素数1~6のアルキレン基を示し、Yは炭素数1~18のアルキレン基又は下記の一般式(iii)で表される基を示す。
   -R30-S-R31- (iii)
 上記式(iii)中、R30及びR31は、それぞれ個別に、炭素数1~6のアルキレン基を示す。
Figure JPOXMLDOC01-appb-C000011
In the above formula (7), R 24 and R 28 each independently represent an alkyl group having 1 to 4 carbon atoms, and R 25 and R 29 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 26 and R 27 each independently represents an alkylene group having 1 to 6 carbon atoms, and Y represents an alkylene group having 1 to 18 carbon atoms or a group represented by the following general formula (iii): Show.
-R 30 -S-R 31 - ( iii)
In the above formula (iii), R 30 and R 31 each independently represents an alkylene group having 1 to 6 carbon atoms.
 一般式(6)において、R16は炭素数1~4のアルキル基を示す。中でも耐スラッジ性により優れる点からtert-ブチル基が好ましい。また、R17は水素原子又は炭素数1~4のアルキル基を示す。中でも、耐スラッジ性により優れる点から水素原子、メチル基又はtert-ブチル基が好ましい。また、R18は水素原子、炭素数1~4のアルキル基、上記式(i)で表される基又は上記式(ii)で表される基を示す。R18が示す炭素数1~4のアルキル基としては、中でも耐スラッジ性により優れる点からメチル基又はエチル基であるのが好ましい。 In the general formula (6), R 16 represents an alkyl group having 1 to 4 carbon atoms. Of these, a tert-butyl group is preferred because it is more excellent in sludge resistance. R 17 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Among these, a hydrogen atom, a methyl group, or a tert-butyl group is preferable because it is more excellent in sludge resistance. R 18 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a group represented by the above formula (i), or a group represented by the above formula (ii). The alkyl group having 1 to 4 carbon atoms represented by R 18 is preferably a methyl group or an ethyl group from the viewpoint of superior sludge resistance.
 一般式(6)で表される化合物としては、上述の通り各種化合物が含まれるが、これらの中で好ましいものを例示すれば、R18が炭素数1~4のアルキル基である場合の化合物として、2,6-ジ-tert-ブチル-p-クレゾール、2,6-ジ-tert-ブチル-4-エチルフェノール等;R18が式(i)で表される基である場合の化合物として、(3-メチル-5-tert-ブチル-4-ヒドロキシフェニル)酢酸n-ヘキシル、(3-メチル-5-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸イソヘキシル、(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)酢酸n-ヘプチル、(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸2-エチルヘキシル、(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸イソドデシル等;R18が式(ii)で表される基である場合の化合物として、ビス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)、ビス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)メタン、等;及びこれらの混合物等が挙げられる。 The compound represented by the general formula (6) includes various compounds as described above. Preferred examples of these compounds include compounds in which R 18 is an alkyl group having 1 to 4 carbon atoms. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, etc .; as a compound when R 18 is a group represented by formula (i) N-hexyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, isohexyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, (3,5-di-tert -Butyl-4-hydroxyphenyl) acetic acid n-heptyl, (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid 2-ethylhexyl, (3,5-di-tert) Butyl-4-hydroxyphenyl) isododecyl propionic acid; a compound where R 18 is a group represented by the formula (ii), bis (3,5-di -tert- butyl-4-hydroxyphenyl) bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, and the like; and mixtures thereof.
 また、一般式(7)において、Yは炭素数1~18のアルキレン基または上記式(iii)で表される基を示す。Yが示す炭素数1~18のアルキレン基としては、直鎖状でも分枝状でも良い。原料入手の容易さ等から、炭素数1~6のアルキレン基がより好ましく、エチレン基(ジメチレン基)、トリメチレン基、直鎖ブチレン基(テトラメチレン基)、直鎖ペンチレン基(ペンタメチレン基)、直鎖ヘキシレン基(ヘキサメチレン基)等の炭素数2~6の直鎖アルキレン基が特に好ましい。 In the general formula (7), Y represents an alkylene group having 1 to 18 carbon atoms or a group represented by the above formula (iii). The alkylene group having 1 to 18 carbon atoms represented by Y may be linear or branched. An alkylene group having 1 to 6 carbon atoms is more preferable from the viewpoint of easy availability of raw materials, and includes an ethylene group (dimethylene group), a trimethylene group, a linear butylene group (tetramethylene group), a linear pentylene group (pentamethylene group), A straight-chain alkylene group having 2 to 6 carbon atoms such as a straight-chain hexylene group (hexamethylene group) is particularly preferred.
 フェノール系酸化防止剤の含有量の上限値は、組成物全量基準で5質量%が好ましく、より好ましくは2質量%、さらに好ましくは1.5質量%である。含有量が5質量%を超える場合、スラッジ発生の原因となるので好ましくない。一方、フェノール系系酸化防止剤の含有量の下限値は、組成物全量基準で、0.01質量%が好ましく、より好ましくは0.05質量%、さらに好ましくは0.1質量%である。酸化防止剤の含有量が0.01質量%に満たない場合は、酸化防止効果が不足するので好ましくない。 The upper limit of the content of the phenolic antioxidant is preferably 5% by mass, more preferably 2% by mass, and even more preferably 1.5% by mass based on the total amount of the composition. When the content exceeds 5% by mass, sludge is generated, which is not preferable. On the other hand, the lower limit of the content of the phenolic antioxidant is preferably 0.01% by mass, more preferably 0.05% by mass, and still more preferably 0.1% by mass based on the total amount of the composition. When the content of the antioxidant is less than 0.01% by mass, the antioxidant effect is insufficient, which is not preferable.
 本発明においては、上述したとおり、炭化水素油、合成エステル及び油脂からなる群より選ばれる少なくとも1種の基油に、(B)成分、(C)成分さらにはアミン系酸化防止剤及び/又はフェノール系酸化防止剤を配合することにより、酸化防止性能及び耐摩耗性に優れる難燃性油圧作動油が得られるが、その性能をさらに向上させる目的で、必要に応じて、さらにその他の酸化防止剤、さび止め剤、金属不活性化剤、摩耗防止剤、粘度指数向上剤、流動点降下剤、消泡剤、抗乳化剤、スティックスリップ防止剤、油性剤等に代表される各種添加剤を単独で、又は数種類組み合わせて含有させても良い。 In the present invention, as described above, at least one base oil selected from the group consisting of hydrocarbon oils, synthetic esters and fats and oils, (B) component, (C) component, and further an amine-based antioxidant and / or By adding a phenolic antioxidant, a flame-retardant hydraulic fluid with excellent antioxidant performance and wear resistance can be obtained. In order to further improve the performance, other antioxidants are added as necessary. Agent, rust inhibitor, metal deactivator, antiwear agent, viscosity index improver, pour point depressant, antifoaming agent, anti-emulsifier, stick-slip inhibitor, oily agent, etc. Or in combination of several kinds.
 さび止め剤としては、具体的には、アミノ酸誘導体、多価アルコールの部分エステル;ラノリン脂肪酸エステル、アルキルコハク酸エステル、アルケニルコハク酸エステル等のエステル類;ザルコシン;ソルビタン脂肪酸エステル等の多価アルコール部分エステル類;脂肪酸金属塩、ラノリン脂肪酸金属塩、酸化ワックス金属塩等の金属石けん類;カルシウムスルフォネート、バリウムスルフォネート等のスルフォネート類;酸化ワックス;アミン類;リン酸;リン酸塩等が例示できる。中でもアミノ酸誘導体は防錆効果が高いので好ましい。 Specific examples of rust inhibitors include amino acid derivatives, partial esters of polyhydric alcohols; esters such as lanolin fatty acid esters, alkyl succinic acid esters, and alkenyl succinic acid esters; sarcosine; polyhydric alcohol moieties such as sorbitan fatty acid esters. Esters; metal soaps such as fatty acid metal salts, lanolin fatty acid metal salts, and oxidized wax metal salts; sulfonates such as calcium sulfonate and barium sulfonate; oxidized wax; amines; phosphoric acid; It can be illustrated. Of these, amino acid derivatives are preferred because of their high rust prevention effect.
 上記のアミノ酸誘導体としては、下記一般式(8)で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000012
As said amino acid derivative, the compound shown by following General formula (8) is mentioned.
Figure JPOXMLDOC01-appb-C000012
 式(8)中、Aは、式(9)又は式(10)で示される基であり、Bは炭素数1~12のアルキル基又は式(11)で示される1価カルボン酸エステルの残基であり、R32は炭素数4~12のアルキル基であり、R33は、炭素数1~10のアルキル基である。
   R35O-CO-R34-     (9) 
   R37O-CO-R36-CO-  (10) 
   -C-CO-O-R38     (11)
(式(9)~(11)中、R34は炭素数1~12のアルキレン基であり、R36は炭素数1~10のアルキレン基であり、R35及びR37は、それぞれ水素原子又は炭素数1~10のアルキル基であり、R38は炭素数1~10のアルキル基である。)
In the formula (8), A is a group represented by the formula (9) or the formula (10), and B is an alkyl group having 1 to 12 carbon atoms or the residue of the monovalent carboxylic acid ester represented by the formula (11). R 32 is an alkyl group having 4 to 12 carbon atoms, and R 33 is an alkyl group having 1 to 10 carbon atoms.
R 35 O—CO—R 34 — (9)
R 37 O—CO—R 36 —CO— (10)
-C-CO-O-R 38 (11)
(In the formulas (9) to (11), R 34 is an alkylene group having 1 to 12 carbon atoms, R 36 is an alkylene group having 1 to 10 carbon atoms, and R 35 and R 37 are each a hydrogen atom or (It is an alkyl group having 1 to 10 carbon atoms, and R 38 is an alkyl group having 1 to 10 carbon atoms.)
 R32は炭素数4~12のアルキル基であり、好ましくは炭素数4~10、さらに好ましくは炭素数6~10のアルキル基である。また、R33及びR38は、それぞれ個別に、炭素数1~10のアルキル基であり、好ましくは炭素数1~8、さらに好ましくは炭素数1~6のアルキル基である。R37は水素又は炭素数1~10のアルキル基であり、好ましくは炭素数1~8のアルキル基であり、さらに好ましくは炭素数1~6のアルキル基である。 R 32 is an alkyl group having 4 to 12 carbon atoms, preferably an alkyl group having 4 to 10 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms. R 33 and R 38 are each independently an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. R 37 is hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
 本発明においては、これらのさび止め剤の中から任意に選ばれる1種類あるいは2種類以上の化合物を、任意の量で油圧作動油組成物に含有させることができるが、通常、その含有量は、油圧作動油組成物全量基準で0.001~2.0質量%が好ましく、より好ましくは0.01~1.5質量%、さらに好ましくは0.05~1質量%である。 In the present invention, one or two or more compounds arbitrarily selected from these rust inhibitors can be contained in the hydraulic fluid composition in any amount, but usually the content is The total amount of the hydraulic fluid composition is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.5% by mass, and still more preferably 0.05 to 1% by mass.
 金属不活性化剤としては、具体的には、ベンゾトリアゾール系、チアジアゾール系、イミダゾール系化合物等が例示できる。本発明においては、これらの金属不活性化剤の中から任意に選ばれる1種類あるいは2種類以上の化合物を、任意の量で含有させることができるが、通常、その含有量は、油圧作動油組成物全量基準で0.001~1質量%であるのが望ましい。 Specific examples of the metal deactivator include benzotriazole, thiadiazole, and imidazole compounds. In the present invention, one kind or two or more kinds of compounds arbitrarily selected from these metal deactivators can be contained in any amount, but the content thereof is usually hydraulic oil. The content is desirably 0.001 to 1% by mass based on the total amount of the composition.
 粘度指数向上剤としては、具体的には、各種メタクリル酸エステルから選ばれる1種又は2種以上のモノマーの共重合体若しくはその水素化物、エチレン-α-オレフィン共重合体(α-オレフィンとしてはプロピレン、1-ブテン、1-ペンテン等が例示できる。)若しくはその水素化物、ポリイソブチレン若しくはその水添物、スチレン-ジエン共重合体の水素化物及びポリアルキルスチレン等の非分散型粘度指数向上剤等が例示できる。本発明においては、これらの粘度指数向上剤の中から任意に選ばれる1種類あるいは2種類以上の化合物を、任意の量で含有させることができるが、通常、その含有量は、油圧作動油組成物全量基準で0.01~10質量%であるのが望ましい。 Specific examples of the viscosity index improver include a copolymer of one or more monomers selected from various methacrylic esters or a hydride thereof, an ethylene-α-olefin copolymer (as an α-olefin). Non-dispersed viscosity index improvers such as propylene, 1-butene, 1-pentene, etc.) or hydrides thereof, polyisobutylene or hydrogenated products thereof, hydrides of styrene-diene copolymers, and polyalkylstyrenes Etc. can be illustrated. In the present invention, one or two or more compounds arbitrarily selected from these viscosity index improvers can be contained in any amount, but the content is usually determined by the hydraulic fluid composition. It is desirable that the content is 0.01 to 10% by mass based on the total amount of the product.
 流動点降下剤としては、具体的には、各種アクリル酸エステルやメタクリル酸エステルから選ばれる1種又は2種以上のモノマーの共重合体若しくはその水添物等が例示できる。本発明においては、これらの流動点降下剤の中から任意に選ばれる1種類あるいは2種類以上の化合物を、任意の量で含有させることができるが、通常、その含有量は、油圧作動油組成物全量基準で0.01~5質量%であるのが望ましい。  Specific examples of the pour point depressant include copolymers of one or more monomers selected from various acrylic esters and methacrylic esters or hydrogenated products thereof. In the present invention, one or two or more compounds arbitrarily selected from these pour point depressants can be contained in any amount, but the content is usually determined by the hydraulic fluid composition. It is desirable that the content is 0.01 to 5% by mass based on the total amount of the product. *
 消泡剤としては、具体的には、ジメチルシリコーン、フルオロシリコーン等のシリコーン類が例示できる。本発明においては、これらの消泡剤の中から任意に選ばれる1種類あるいは2種類以上の化合物を、任意の量で含有させることができるが、通常、その含有量は、油圧作動油組成物全量基準で0.001~0.05質量%であるのが望ましい。
 抗乳化剤としては、例えば、ポリオキシアルキレングリコール,ポリオキシアルキレンアルキルエーテル,ポリオキシアルキレンアルキルアミド,ポリオキシアルキレン脂肪酸エステル等が挙げられる。
 スティックスリップ防止剤としては、具体的には、多価アルコールエステル(完全エステル、部分エステル)などが挙げられる。
 油性剤としては、具体的には脂肪酸、エステル、アルコール等が挙げられる。通常、その含有量は、油圧作動油組成物全量基準で0.01~0.5質量%であるのが望ましい。
Specific examples of the antifoaming agent include silicones such as dimethyl silicone and fluorosilicone. In the present invention, one kind or two or more kinds of compounds arbitrarily selected from these antifoaming agents can be contained in any amount, but the content thereof is usually a hydraulic fluid composition. It is desirable that the content is 0.001 to 0.05% by mass based on the total amount.
Examples of the demulsifier include polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamide, polyoxyalkylene fatty acid ester and the like.
Specific examples of the stick-slip preventing agent include polyhydric alcohol esters (complete esters and partial esters).
Specific examples of the oily agent include fatty acids, esters, alcohols and the like. Usually, the content is desirably 0.01 to 0.5% by mass based on the total amount of the hydraulic fluid composition.
 以下、本発明の内容を実施例及び比較例により更に具体的に説明するが、本発明はこれらの内容に何ら限定されるものではない。 Hereinafter, the contents of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these contents.
(実施例1~17、比較例1~3)
 表1~表4に示すように、基油および添加剤を配合して油圧作動油組成物を調製した。実施例及び比較例で用いた基油および添加剤は以下のとおりである。
(Examples 1 to 17, Comparative Examples 1 to 3)
As shown in Tables 1 to 4, hydraulic oil compositions were prepared by blending base oil and additives. The base oils and additives used in the examples and comparative examples are as follows.
<(A)成分(基油)>
 A1:トリメチルロールプロパンのオレイン酸エステル(40℃における動粘度47.2mm/s、粘度指数190)
 A2:高オレイン酸含有菜種油(40℃における動粘度35mm/s、粘度指数190、エステルを構成する全脂肪酸に占めるオレイン酸の比率75モル%,エステルを構成する全脂肪酸に占める不飽和脂肪酸比率90モル%)
 A3:ポリα-オレフィンオリゴマー(40℃における動粘度44.5mm/s、粘度指数145)
<(A) component (base oil)>
A1: Trioleic propane oleate (kinematic viscosity at 40 ° C. 47.2 mm 2 / s, viscosity index 190)
A2: High oleic acid-containing rapeseed oil (kinematic viscosity at 40 ° C. 35 mm 2 / s, viscosity index 190, ratio of oleic acid to all fatty acids constituting the ester, 75 mol%, unsaturated fatty acid ratio to all fatty acids constituting the ester 90 mol%)
A3: Poly α-olefin oligomer (kinematic viscosity at 40 ° C. 44.5 mm 2 / s, viscosity index 145)
<(B)成分(酸捕捉剤)>
 B1:下式で示されるビス(2,6-ジ-tert-ブチルフェニル)カルボジイミド
Figure JPOXMLDOC01-appb-C000013
 (R及びRは水素、R,R,R及びRはtert-ブチル基である。)
 B2:1,2-エポキシテトラデカン
<(B) component (acid scavenger)>
B1: Bis (2,6-di-tert-butylphenyl) carbodiimide represented by the following formula
Figure JPOXMLDOC01-appb-C000013
(R 3 and R 8 are hydrogen, and R 4 , R 5 , R 6 and R 7 are tert-butyl groups.)
B2: 1,2-epoxytetradecane
<成分(C)(摩耗防止剤)>
 C1:トリフェニルチオフォスフェート
 C2:2-エチルヘキシルアシッドフォスフェート
 C3:トリクレジルホスフェート
<Component (C) (Antiwear Agent)>
C1: triphenylthiophosphate C2: 2-ethylhexyl acid phosphate C3: tricresyl phosphate
<酸化防止剤>
 D1:N-p-イソドデシルフェニル-α-ナフチルアミン
 D2:p,p’-ジオクチルジフェニルアミン
 D3:ビス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)メタン
<Antioxidant>
D1: Np-isododecylphenyl-α-naphthylamine D2: p, p′-dioctyldiphenylamine D3: Bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane
<防錆剤>
 E1:下式で示されるアミノ酸誘導体化合物。
Figure JPOXMLDOC01-appb-C000014
 (ここで、Rはオクチル基、Rはブチル基、Rはブチレン基を示す。)
 E2:ソルビタンモノオレエート
<Rust preventive>
E1: Amino acid derivative compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000014
(Here, R 1 represents an octyl group, R 2 represents a butyl group, and R 3 represents a butylene group.)
E2: Sorbitan monooleate
<その他の添加剤>
 F1:Nメチルベンゾトリアゾール
 F2:ポリメタクリレート(分子量5万)
<Other additives>
F1: N methylbenzotriazole F2: Polymethacrylate (molecular weight 50,000)
 調製した油圧作動油組成物について、引火点、RPVOT試験、四球試験、FZGギヤ試験、V104Cベーンポンプ試験、防錆試験および行った。その結果を表1~表4に示す。なお、各性状、試験等は以下に拠った。 The prepared hydraulic fluid composition was subjected to a flash point, an RPVOT test, a four-ball test, an FZG gear test, a V104C vane pump test, a rust prevention test, and the like. The results are shown in Tables 1 to 4. In addition, each property, a test, etc. were based on the following.
[引火点]
 JIS K 2265「原油及び石油製品-引火点試験方法」に準拠した。
[Flash point]
Conforms to JIS K 2265 "Crude oil and petroleum products-Flash point test method".
[RPVOT試験]
 JIS K 2514に規定する「回転ボンベ式酸化安定度方法」で、試料油50g、銅のコイル状触媒、水10mlを入れたふた付き試験容器を、圧力計を備えたボンベの中に入れ、酸素を620kPaに圧入し、150℃の恒温槽に入れる。ボンベを30℃の角度に保持しながら毎分100回転で回転させ、圧力が最高になった時点から、175kPaの圧力低下をするまでの時間で評価する。
[RPVOT test]
A test vessel with a lid containing 50 g of sample oil, a copper coiled catalyst, and 10 ml of water is placed in a cylinder equipped with a pressure gauge according to the “Rotating cylinder oxidation stability method” defined in JIS K 2514. Is pressed into 620 kPa and placed in a constant temperature bath at 150 ° C. The cylinder is rotated at 100 revolutions per minute while maintaining an angle of 30 ° C., and the time from when the pressure reaches the maximum to when the pressure is reduced to 175 kPa is evaluated.
[四球試験]
 ASTM D 2783-88に規定する潤滑油の極圧性能測定用標準試験方法(四球法){Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids (Four- Ball Method)}に準拠し、回転数1200rpm、荷重294N,油温室温、試験時間30分の条件で試験を実施し、3個の固定球の摩耗痕径(mm)の平均値を測定する。
[Four ball test]
Rotation speed in accordance with Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids (Four-Ball Method) stipulated in ASTM D 2783-88 The test is performed under the conditions of 1200 rpm, load 294 N, oil temperature room temperature, test time 30 minutes, and the average value of the wear scar diameter (mm) of the three fixed balls is measured.
[FZGギヤ試験]
 ASTM D 5182に規定されたギヤ試験。1500回転(回転数1500rpm)、試験開始油温90℃で試験を開始し、各ステージで規定された重量でギヤに荷重をかけ、15分間運転する。ギヤが焼きつく荷重のステージで油の耐焼き付性の評価を行う。ギヤが焼きついた荷重のステージを不合格とする。
[FZG gear test]
Gear test as defined in ASTM D 5182. The test is started at 1500 rpm (rotation speed 1500 rpm) and the test start oil temperature is 90 ° C., the gear is loaded with the weight specified in each stage, and is operated for 15 minutes. The seizure resistance of the oil is evaluated on a stage where the gear is burned. A stage with a load with a burned out gear is rejected.
[ベーンポンプ試験(V104C試験)]
 ASTM D 2882に規定されたベーンポンプ試験を実施し、試験前後のベーンとリングの重量を計測し、摩耗量を測定した。試験時間は100時間とした。
[Vane pump test (V104C test)]
A vane pump test defined in ASTM D 2882 was conducted, the weight of the vane and the ring before and after the test was measured, and the amount of wear was measured. The test time was 100 hours.
[防錆試験]
 JIS K 2510に規定された、みがき棒鋼用一般鋼材を用いた防錆試験。使用する水により、蒸留水と人工海水の2種類の試験方法があるが、今回はより厳しい人工海水で試験を実施した。試験時間は24時間、試験油温波60℃である。
[Rust prevention test]
Rust prevention test using general steel materials for polished steel bars specified in JIS K 2510. There are two types of test methods, distilled water and artificial seawater, depending on the water used, but this time the test was conducted with more severe artificial seawater. The test time is 24 hours and the test oil temperature wave is 60 ° C.
[酸価]
 JIS K 2501に規定された、一定量の試料中に含まれ酸性成分を中和するのに必要な水酸化カリウムの滴定量で規定される。つまり1(KOH/mg)は、1mg中に含まれる、KOH溶液で測定できる酸性成分の量を示す。
[Acid value]
This is defined by the titration amount of potassium hydroxide required for neutralizing acidic components contained in a certain amount of sample as defined in JIS K 2501. That is, 1 (KOH / mg) indicates the amount of acidic component contained in 1 mg that can be measured with a KOH solution.
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000002
 
Figure JPOXMLDOC01-appb-T000002
 
Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000004
 
Figure JPOXMLDOC01-appb-T000004
 
 本発明により、長寿命性、スラッジ抑制性能、耐摩耗性、耐焼き付き性に優れ、特に加水分解しにくく長期間使用可能な難燃性油圧作動油組成物が提供される。 The present invention provides a flame-retardant hydraulic fluid composition that is excellent in long life, sludge suppression performance, abrasion resistance, and seizure resistance, and is particularly resistant to hydrolysis and usable for a long period of time.

Claims (3)

  1.  (A)炭化水素油、合成エステル及び油脂から選ばれる少なくとも1種の基油、(B)エポキシ化合物及び/又は下記一般式(1)で示されるカルボジイミド化合物を組成物全量基準で合計で0.01~2質量%、および(C)硫黄含有リン酸エステル、酸性リン酸エステル、酸性リン酸エステルアミン塩及び亜リン酸エステルから選ばれる少なくとも1種類の摩耗防止剤を組成物全量基準で0.001~5質量%、を含有することを特徴とする難燃性油圧作動油組成物。
    Figure JPOXMLDOC01-appb-C000015
    (式(1)中、RおよびRは、炭素数4~26のアルキル基、(アルキル)フェニル基、アラルキル基、または(アルキル)シクロアルキル基を示し、それぞれ同一でも異なっていてもよい。)
    (A) At least one base oil selected from hydrocarbon oils, synthetic esters and fats and oils, (B) an epoxy compound and / or a carbodiimide compound represented by the following general formula (1) in a total amount of 0. 01 to 2% by mass, and (C) at least one antiwear agent selected from sulfur-containing phosphate ester, acidic phosphate ester, acidic phosphate ester amine salt and phosphite ester, based on the total amount of the composition. A flame-retardant hydraulic fluid composition characterized by containing 001 to 5% by mass.
    Figure JPOXMLDOC01-appb-C000015
    (In the formula (1), R 1 and R 2 represent an alkyl group having 4 to 26 carbon atoms, an (alkyl) phenyl group, an aralkyl group, or an (alkyl) cycloalkyl group, which may be the same or different. .)
  2.  一般式(1)で示されるカルボジイミド化合物が、下記の一般式(2)で示される化合物であることを特徴とする請求項1に記載の難燃性油圧作動油組成物。
    Figure JPOXMLDOC01-appb-C000016
    (式(2)中、R~Rは、水素もしくは炭素数1~8のアルキル基を示し、それぞれ同一でも異なっていてもよい。)
    The flame retardant hydraulic fluid composition according to claim 1, wherein the carbodiimide compound represented by the general formula (1) is a compound represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-C000016
    (In formula (2), R 3 to R 8 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and may be the same or different.)
  3.  アミン系酸化防止剤及び/又はフェノール系酸化防止剤を組成物全量基準で0.01~5質量%含有することを特徴とする請求項1または2に記載の難燃性油圧作動油組成物。 The flame-retardant hydraulic fluid composition according to claim 1 or 2, comprising 0.01 to 5% by mass of an amine-based antioxidant and / or a phenol-based antioxidant based on the total amount of the composition.
PCT/JP2009/004519 2008-12-01 2009-09-11 Flame retardant hydraulic oil composition WO2010064347A1 (en)

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