WO2014196467A1 - 多機能潤滑剤組成物 - Google Patents
多機能潤滑剤組成物 Download PDFInfo
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- WO2014196467A1 WO2014196467A1 PCT/JP2014/064427 JP2014064427W WO2014196467A1 WO 2014196467 A1 WO2014196467 A1 WO 2014196467A1 JP 2014064427 W JP2014064427 W JP 2014064427W WO 2014196467 A1 WO2014196467 A1 WO 2014196467A1
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N O=P(Oc1ccccc1)(Oc1ccccc1)Oc1ccccc1 Chemical compound O=P(Oc1ccccc1)(Oc1ccccc1)Oc1ccccc1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/003—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
- C10M2223/0415—Triaryl phosphates used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/66—Hydrolytic stability
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- the present invention relates to a lubricant composition containing a multifunctional phosphate that can be used as a lubricating base oil or a lubricating additive.
- Lubricating oil is an oil used to reduce friction at the contact portion of a machine.
- base oil mineral oil, synthetic oil, animal and vegetable oil, or a mixed oil thereof is generally well known. .
- the base oil is properly used depending on the application, but when using lubricating oil in aircraft and advanced hydraulic systems, hydraulic oil with high flame resistance may be required.
- synthetic flame retardant working base oils based on compounds that are difficult to burn, water-containing flame retardant working base oils that contain water in the working base oil to increase flame retardancy, etc. are used. Is common.
- the synthetic system examples include phosphate ester compounds such as TCP (tricresyl phosphate) and TPP (triphenyl phosphate), and ester compounds of polyols and linear saturated fatty acids (Patent Document 1).
- the water-containing system includes a mixture system of water and glycol, a water-in-oil (W / O) emulsion system in which water droplets are dispersed in oil, an oil-in-water (O / W) emulsion system in which oil droplets are dispersed in water, and the like. (Patent Documents 2 and 3).
- phosphate ester compounds such as TCP (tricresyl phosphate) and TPP (triphenyl phosphate) are flame retardant, but are highly toxic and too low in viscosity to be used as a base oil. There are concerns that environmental impacts and restrictions on the use of oil are necessary. In addition, an ester compound of a polyol and a linear saturated fatty acid has low toxicity but has insufficient flame retardancy. On the other hand, when water-containing base oil is used, although it is low in toxicity and low in price, there is a problem that maintenance management is not easy, such as loss due to moisture evaporation, mold, corrosion due to bacteria, fungi, and the like. That is, the market is demanding a high-performance flame-retardant base oil that is safer and easier to use as a base oil than the conventional products.
- Patent Document 4 phosphate ester compounds such as TCP (tricresyl phosphate) and TPP (triphenyl phosphate) are used as lubricant bases. It is also well known that there is an effect of preventing wear as an additive for lubrication, not as oil (Patent Document 4). However, as described above, since these compounds are highly toxic, alternative compounds have been sought in the field of additives. In recent years, in response to this demand, a low toxicity phosphorus-based antiwear composition for lubricants has begun to be developed (Patent Document 5) and is attracting attention.
- TCP tricresyl phosphate
- TPP triphenyl phosphate
- the usefulness and novelty of this compound will be improved. It is very high and can be expected to play an active role in various technical fields. Therefore, in the market, the development of a compound that has not only one function but also multiple functions is highly desirable because it has advantages on both the supply side and the demand side in terms of efficiency and convenience. ing.
- the antiwear composition for phosphorus-based lubrication described in Patent Document 5 is an additive having low toxicity and good wear resistance. However, because of its high viscosity, it cannot be used as a base oil. Even when used as an additive, if the viscosity is high, the miscibility with the lubricating base oil may deteriorate, and it may be difficult to handle.
- the problem to be solved by the present invention is a base oil having a good viscosity with high safety and hydrolytic stability as compared with an existing flame retardant lubricating base oil, and Another object of the present invention is to provide a multifunctional lubricant composition exhibiting high antiwear performance as a lubricating additive.
- the present invention relates to a phosphorus compound (B) represented by the following general formula (2) in an amount of 26 to 43 with respect to 100 parts by mass of the phosphorus compound (A) represented by the following general formula (1). It contains 0 to 1.3 parts by mass of a phosphorus compound (C) represented by the following general formula (3), and 0 to 1.3 parts by mass in total of triphenyl phosphate and tricresyl phosphate. It is the multifunctional lubricant composition characterized.
- R 1 represents a hydrocarbon group having 1 to 10 carbon atoms
- R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 3 and R 4 are each independently a hydrogen atom. Or a methyl group, provided that when R 1 is a methyl group, R 2 is not a hydrogen atom.
- R 5 and R 7 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 9 represents a hydrogen atom or a methyl group, provided that when R 5 is a methyl group, R 6 is not a hydrogen atom, and when R 7 is a methyl group, R 8 is a hydrogen atom. Must not.
- R 10 , R 12 and R 14 each independently represents a hydrocarbon group having 1 to 10 carbon atoms
- R 11 , R 13 and R 15 each independently represents a hydrogen atom or a methyl group.
- R 10 is a methyl group
- R 11 is not a hydrogen atom
- R 12 is a methyl group
- R 13 is not a hydrogen atom
- R 14 is a methyl group
- R 15 does not become a hydrogen atom.
- the effect of the present invention is a base oil having a high safety and hydrolytic stability and a good viscosity as compared with existing flame retardant lubricating base oils, and also as a lubricating additive.
- Another object of the present invention is to provide a multifunctional lubricant composition exhibiting high wear prevention performance.
- the multifunctional lubricant composition of the present invention is a phosphorus compound (B) represented by the following general formula (2) with respect to 100 parts by mass of the phosphorus compound (A) represented by the following general formula (1). 26 to 43 parts by mass, phosphorus compound (C) represented by the following general formula (3) 0 to 1.3 parts by mass, triphenyl phosphate and tricresyl phosphate in total 0 to 1.3 parts by mass It is a multifunctional lubricant composition characterized by containing.
- R 1 represents a hydrocarbon group having 1 to 10 carbon atoms
- R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 3 and R 4 are each independently a hydrogen atom. Or a methyl group, provided that when R 1 is a methyl group, R 2 is not a hydrogen atom.
- R 5 and R 7 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 9 represents a hydrogen atom or a methyl group, provided that when R 5 is a methyl group, R 6 is not a hydrogen atom, and when R 7 is a methyl group, R 8 is a hydrogen atom. Must not.
- R 10 , R 12 and R 14 each independently represents a hydrocarbon group having 1 to 10 carbon atoms
- R 11 , R 13 and R 15 each independently represents a hydrogen atom or a methyl group.
- R 10 is a methyl group
- R 11 is not a hydrogen atom
- R 12 is a methyl group
- R 13 is not a hydrogen atom
- R 14 is a methyl group
- R 15 does not become a hydrogen atom.
- R 1 represents a hydrocarbon group having 1 to 10 carbon atoms
- R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- R 1 is a methyl group
- R 2 is not a hydrogen atom.
- Examples of the hydrocarbon group having 1 to 10 carbon atoms that R 1 and R 2 can take include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t -Butyl group, n-pentyl group, branched pentyl group, secondary pentyl group, tertiary pentyl group, n-hexyl group, branched hexyl group, secondary hexyl group, tertiary hexyl group, n-heptyl group Branched heptyl group, secondary heptyl group, tertiary heptyl group, n-octyl group, 2-ethylhexyl group, branched octyl group, secondary octyl group, tertiary octyl group, n
- Cyclopentyl group methylcyclopentyl group, ethylcyclopentyl group, propylcyclopentyl group, butylcyclopentyl Group, pentylcyclopentyl group, cyclohexyl group, methylcyclohexyl Xyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, cycloheptyl, methylcycloheptyl, ethylcycloheptyl, propylcycloheptyl, cyclopentenyl, methylcyclopentenyl, ethylcyclopentenyl, propylcyclo Pentenyl group, butylcyclopentenyl group, pentylcyclopentenyl group, cyclohexenyl group, methylcyclohexenyl group, ethylcyclohexenyl group, propylcyclohexeny
- a hydrocarbon group of R 1 is 2 to 8 carbon atoms, R 2 ⁇ , compound is preferably R 4 are all hydrogen atoms, R 1 is para to the marked with a carbon number of 2 to 8 aliphatic hydrocarbon More preferably, R 2 to R 4 are all hydrogen atoms, R 1 is an aliphatic hydrocarbon group having 2 to 5 carbon atoms attached to the para position, and R 2 to R 4 are all hydrogen atoms.
- a certain compound is more preferable, and a compound in which R 1 is a t-butyl group attached to the para position and R 2 to R 4 are all hydrogen atoms is most preferable.
- the “para-position” is a position relative to the position where the oxygen atom bonded to the phosphorus atom of the phosphorus compound (A) is bonded to the benzene ring.
- R 5 and R 7 each independently represent a hydrocarbon group having 1 to 10 carbon atoms
- R 6 and R 8 each independently represent a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms. Represents a group. However, when R 5 is a methyl group, R 6 does not become a hydrogen atom, and when R 7 is a methyl group, R 8 does not become a hydrogen atom.
- Examples of the hydrocarbon group having 1 to 10 carbon atoms that R 5 to R 8 can take include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t -Butyl group, n-pentyl group, branched pentyl group, secondary pentyl group, tertiary pentyl group, n-hexyl group, branched hexyl group, secondary hexyl group, tertiary hexyl group, n-heptyl group Branched heptyl group, secondary heptyl group, tertiary heptyl group, n-octyl group, 2-ethylhexyl group, branched octyl group, secondary octyl group, tertiary octyl group, n
- R 5 and R 7 are a hydrocarbon group having 2 to 8 carbon atoms, preferably a compound R 6, R 8 and R 9 are all hydrogen atoms, R 5 and R 7 are attached to the para position More preferably, it is an aliphatic hydrocarbon group having 2 to 8 carbon atoms, and R 6 , R 8 and R 9 are all hydrogen atoms, and an aliphatic hydrocarbon group having 2 to 5 carbon atoms in which R 5 and R 7 are para-positioned. More preferred are hydrocarbon groups in which R 6 , R 8 and R 9 are all hydrogen atoms, R 5 and R 7 are t-butyl groups attached to the para position, and R 6 , R 8 and R 9 are Most preferred are compounds that are all hydrogen atoms.
- the “para-position” is a position relative to the position where the oxygen atom bonded to the phosphorus atom of the phosphorus compound (B) is bonded to the benzene ring.
- R 10 , R 12 and R 14 each independently represent a hydrocarbon group having 1 to 10 carbon atoms
- R 11 , R 13 and R 15 are each independently a hydrogen atom or methyl Represents a group.
- R 10 is a methyl group
- R 11 is not a hydrogen atom
- R 12 is a methyl group
- R 13 is not a hydrogen atom
- R 14 is a methyl group
- 15 does not become a hydrogen atom.
- Examples of the hydrocarbon group having 1 to 10 carbon atoms that R 10 , R 12 and R 14 can take include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and s-butyl.
- a hydrocarbon group of R 10, R 12 and R 14 are 2 to 8 carbon atoms, compounds R 11, R 13 and R 15 are all hydrogen atoms are preferred, R 10, R 12 and R 14 A compound having 2 to 8 carbon atoms in the para position, wherein R 11 , R 13 and R 15 are all hydrogen atoms, more preferably R 10 , R 12 and R 14 are in the para position. Further preferred is a compound having 2 to 5 carbon atoms and an aliphatic hydrocarbon group in which R 11 , R 13 and R 15 are all hydrogen atoms, and t-butyl wherein R 10 , R 12 and R 14 are attached to the para position. Most preferred are compounds in which R 11 , R 13 and R 15 are all hydrogen atoms.
- the “para-position” is a position relative to the position at which the oxygen atom bonded to the phosphorus atom of the phosphorus compound (C) is bonded to the benzene ring.
- R 1 , R 5 , R 7 , R 10 , R 12 and R 14 are preferably the same group.
- R 1 , R 5 , R 7 , R 10 , R 12 and R 14 are each a hydrocarbon group having 2 to 8 carbon atoms attached to the para position
- R 2 to R 4 , R 6 , R 14 More preferred is a compound in which all of R 8 , R 9 , R 11 , R 13 and R 15 are hydrogen atoms, and R 2 , R 5 , R 7 , R 10 , R 12 and R 14 have 2 carbon atoms attached to the para position.
- R 2 to R 4 , R 6 , R 8 , R 9 , R 11 , R 13 and R 15 are all hydrogen atoms, and are R 1 , R 5 , R 7. , R 10 , R 12 and R 14 are t-butyl groups attached to the para position, and R 2 to R 4 , R 6 , R 8 , R 9 , R 11 , R 13 and R 15 are all hydrogen atoms. Compounds are most preferred.
- the product of the present invention includes a phosphorus compound (A) represented by the general formula (1), a phosphorus compound (B) represented by the general formula (2), a phosphorus compound (C) represented by the general formula (3), It is a mixture composed of triphenyl phosphate and tricresyl phosphate, and is a multifunctional lubricant composition that can be used as a lubricating base oil and can also be used as a lubricating additive.
- the multifunctional lubricant composition of the present invention is used as a lubricating base oil, it is preferably used as a flame retardant lubricating base oil because of its good heat resistance.
- an additive for lubrication when used as an additive for lubrication, it is preferably used as an antiwear agent (antiwear agent) for lubrication because of its excellent wear resistance. Further, since the hydrolysis stability is good, it can also be used for lubricating base oil applications and lubricating additive applications where there is a high possibility of water contamination.
- the product of the present invention has a phosphorus compound (A), phosphorus compound (B), phosphorus compound (C), triphenyl phosphate and tricresyl phosphate mixing ratio of 100 parts by mass of the phosphorus compound (A).
- (B) is 26 to 43 parts by mass
- phosphorus compound (C) is 0 to 1.3 parts by mass
- triphenyl phosphate and tricresyl phosphate are 0 to 1.3 parts by mass in total.
- the solubility in oil deteriorates, so that it may be difficult to use as a lubricating additive.
- the viscosity becomes too high and it may be very difficult to use as a flame retardant lubricating base oil.
- the phosphorus compound (C) when the amount exceeds 1.3 parts by mass, the viscosity may be increased more than the phosphorus compound (B).
- triphenyl phosphate and tricresyl phosphate these compounds themselves are highly toxic.
- PRTR Law Act on Understanding the Release of Specific Chemical Substances into the Environment and Promotion of Improvement of Management
- Class 1 Since it is designated as a designated chemical substance, the total of both is preferably 0 to 1.0 part by mass, more preferably 0 to 0.5 part by mass, and most preferably not contained. If it exceeds 1.3 parts by mass, it may interfere with the conservation of the natural environment.
- the hydrolyzability of the multifunctional lubricant composition of this invention may go up.
- the production method of the multifunctional lubricant composition of the present invention is not particularly limited, and there is no problem as long as it is produced by a known production method.
- the phosphorus compound (A) 26 to 43 parts by mass of the phosphorus compound (B), 0 to 1.3 parts by mass of the phosphorus compound (C), total of triphenyl phosphate and tricresyl phosphate
- the composition containing 0 to 1.3 parts by mass is synthesized in one step by adjusting the charging ratio of the raw materials, and only the phosphorus compound (A) contains only the phosphorus compound (B ) Only, the phosphor compound (C) alone is produced individually, and there is no problem even if it is a composition obtained by blending it.
- An example of obtaining the multifunctional lubricant composition of the present invention is the following method.
- a phenol compound (one or more) having one substituent and / or a cresol compound having one substituent (1 or more) in the presence of an appropriate catalyst and a nitrogen atmosphere in diphenyl chlorophosphate and / or dicresyl chlorophosphate (1
- the phosphorus compound (A) represented by the general formula (1) is obtained by reacting the species.
- phenol compound (one or more) having one substituent and / or cresol having one substituent in the presence of a suitable catalyst and nitrogen atmosphere in phenyl dichlorophosphate and / or cresyl dichlorophosphate The compound (one or more) is reacted to obtain the phosphorus compound (B) represented by the general formula (2).
- the phosphorus oxychloride is reacted with a phenol compound (one or more) having one substituent and / or a cresol compound (one or more) having one substituent in the presence of a suitable catalyst and in a nitrogen atmosphere.
- C represented by the general formula (3).
- reaction system may be depressurized after the reaction, and may be depressurized continuously, intermittently or temporarily during the reaction.
- 100 parts by mass of the obtained phosphorus compound (A) 26 to 43 parts by mass of the phosphorus compound (B) and 0 to 1.3 parts by mass of the phosphorus compound (C) are blended.
- the multifunctional lubricating material composition of the invention is obtained.
- a phenol compound (one or more) having one substituent and / or a cresol compound (one or more) having one substituent is added to phosphorus oxychloride in the presence of a suitable catalyst and in a nitrogen atmosphere. Then, phenol and / or cresol are added in the same system and reacted to obtain the multifunctional lubricant composition of the present invention. At this time, the phenol compound and / or the cresol compound is added in a total amount of 1.1 mol to 1.3 mol, preferably 1.18 mol to 1.28 mol, per mol of phosphorus oxychloride.
- phenol and / or cresol are added in a total amount of 1.7 mol to 1.9 mol, preferably 1.72 mol to 1.82 mol, per mol of phosphorus oxychloride.
- phenols having one substituent and / or one or more kinds of cresols having one substituent may be added to phosphorus oxychloride all at once. May be divided and added.
- hydrochloric acid and the like present in the reaction system under reduced pressure.
- the reaction system may be depressurized after the reaction, and may be depressurized continuously, intermittently or temporarily during the reaction.
- the “phenol compound having one substituent” corresponds to R 1 , R 5 , R 7 , R 10 , R 12 and R 14 among the compounds of the general formulas (1) to (3).
- the “cresol compound having one substituent” means a substituent corresponding to R 1 , R 5 , R 7 , R 10 , R 12 and R 14 among the compounds of the general formulas (1) to (3).
- a compound having a group, wherein R 2 , R 6 , R 8 , R 11 , R 13 and R 15 are methyl groups.
- Examples of the compound corresponding to the phenol compound include alkylphenols such as ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, pentylphenol, hexylphenol, heptylphenol, n-octylphenol, 2-ethylhexylphenol and the like.
- Alkenylphenols such as ethenylphenol, propenylphenol, butenylphenol, pentenylphenol, hexenylphenol, heptenylphenol, octenylphenol; phenylphenol, tolylphenol, xylylphenol, cumenylphenol, mesitylphenol, benzylphenol Phenol having a group having an aromatic ring such as phenethylphenol; cyclopentylphenol Lumpur, alkyl cyclopentyl phenols, cyclohexyl phenols, phenol and the like having a group having a cyclic ring such as an alkyl cyclohexyl phenols.
- alkylphenol and alkenylphenol are preferable, and alkylphenol is most preferable.
- the alkyl group of the alkylphenol is usually an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 2 to 5 carbon atoms, more preferably a t-butyl group, and a para-position relative to the hydroxyl group of phenol. Most preferred is a t-butyl group.
- Examples of the compound corresponding to the cresol compound include ethyl cresol, n-propyl cresol, isopropyl cresol, n-butyl cresol, t-butyl cresol, pentyl cresol, hexyl resole, heptyl cresol, n-octyl cresol, 2- Alkyl cresols such as ethylhexylresole; alkenyl cresols such as ethenyl cresol, propenyl cresol, butenyl cresol, pentenyl cresol, hexenyl cresol, heptenyl cresol, octenyl cresol; phenyl cresol, tolyl cresol, xylyl cresol, cumenyl cresol, Cresol having a group having an aromatic ring such as mesityl cresol, benzyl cresol, phenethyl cresol; Le cresol, alkyl cyclopentyl
- alkyl cresol and alkenyl cresol are preferable, and alkyl cresol is most preferable.
- the alkyl group of the alkyl cresol is usually an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 2 to 5 carbon atoms, more preferably a t-butyl group, and a para-position relative to the hydroxyl group of cresol. The t-butyl group located is most preferred.
- the multifunctional lubricant composition of the present invention may be obtained by using the above-described method 1 or by using the method 2. However, since it can be obtained easily and in a short time, the method 2 is preferred. preferable.
- the viscosity range required for the base oil is preferably in the range of 30 to 55 mm 2 / s at a kinematic viscosity of 40 ° C. If it is less than 30 mm 2 / s, it may not function as a lubricating base oil, and oil film breakage (because the oil film becomes thinner) may easily occur when the oil temperature rises. On the other hand, if it exceeds 55 mm 2 / s, the viscosity of the base oil may be too high to be used.
- the base oil is used in a large amount, if the viscosity is too high, the handling is poor and the container In some cases, the process of removing from the container becomes difficult (a treatment such as heating must be performed if necessary). In addition, loss (amount remaining in the container) may be increased compared to a low-viscosity base oil, and handling may be more difficult in cold regions than in regions with a warm climate. Furthermore, a large mechanical force is required for stirring, and it may take more time and labor (heating treatment, etc.) and time than necessary when dissolving other additives. Since the possibility of biting is increased, the contact area with air is increased by the influence of the bubbles, and deterioration may be promoted in some cases.
- the effect of the present invention may be used in combination with other base oils.
- mineral base oils chemically synthesized bases may be used. These are selected from oils and animal and plant base oils, and these various base oils may be used alone or in combination of two or more.
- the multifunctional lubricant composition of the present invention When used as a base oil for flame retardant lubrication, a known lubricating additive is appropriately used depending on the purpose of use as long as the effects of the present invention are not impaired. It is possible.
- an antiwear agent other than the multifunctional lubricant composition of the present invention extreme pressure agent, friction modifier, metallic detergent, ashless dispersant, antioxidant Agents, friction reducers, viscosity index improvers, pour point depressants, rust inhibitors, corrosion inhibitors, load-carrying additives, antifoaming agents, metal deactivators, emulsifiers, antiemulsifiers, and fungicides It is preferable to contain 0.001 to 40 parts by mass of one or more kinds of compounds.
- the multifunctional lubricant composition of the present invention When used as a flame retardant lubricating base oil, the multifunctional lubricant composition of the present invention also exhibits an antiwear effect as a lubricating additive, but other antiwear agents may be used in combination.
- the antiwear or extreme pressure agent other than the multifunctional lubricant composition of the present invention include, for example, sulfurized fats and oils, olefin polysulfides, sulfurized olefins, dibenzyl sulfide, ethyl-3-[[bis (1-methylethoxy) phos Finothioil] thio] propionate, tris-[(2 or 4) -isoalkylphenol] thiophosphate, 3- (di-isobutoxy-thiophosphorylsulfanyl) -2-methyl-propionic acid, triphenylphosphothionate, ⁇ -Dithiophosphorylated propionic acid, methylene bis (dibutyl
- R 16 to R 19 each independently represents a primary alkyl group, secondary alkyl group or aryl group having 1 to 20 carbon atoms).
- R 16 to R 19 each independently represent a hydrocarbon group having 1 to 20 carbon atoms.
- examples of such groups include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl.
- Alkyl group secondary propyl group, secondary butyl group, secondary pentyl group, secondary hexyl group, secondary heptyl group, secondary octyl group, secondary nonyl group, secondary decyl group, secondary undecyl group, secondary Dodecyl group, secondary tridecyl group, secondary tetradecyl group, secondary pentadecyl group, secondary hexadecyl group, secondary heptadecyl group, secondary octadecyl group, 2 Secondary alkyl groups such as secondary nonadecyl group and secondary icosyl group; tertiary butyl group, tertiary pentyl group, tertiary hexyl group, tertiary heptyl group, tertiary octyl group, tertiary nonyl group, tertiary decyl group, Tertiary undecyl group, tert
- Examples of the friction modifier include higher alcohols such as oleyl alcohol, stearyl alcohol and lauryl alcohol; fatty acids such as oleic acid, stearic acid and lauric acid; glyceryl oleate, glyceryl stearate, glyceryl laurate, alkyl glyceryl ester , Alkenyl glyceryl ester, alkynyl glyceryl ester, ethylene glycol oleate, ethylene glycol stearate, ethylene glycol laurate, propylene glycol oleate, propylene glycol stearate and propylene glycol laurate; oleyl Amides, stearyl amides, lauryl amides, alkyl amides, alkenyl amides and alkyls Amides such as nylamide; oleylamine, stearylamine, laurylamine, alkylamine, alkenylamine, alkyny
- metal detergents include sulfonates such as calcium, magnesium and barium, phenates, salicylates, phosphates, and overbased salts thereof.
- overbased salts are preferred, and among the overbased salts, those having a TBN (total basic number) of 10 to 500 mgKOH / g are more preferred.
- a preferable blending amount of these metallic detergents is 0.5 to 10% by mass, more preferably 1 to 8% by mass with respect to the base oil.
- any ashless dispersant used in lubricating oils can be used without particular limitation.
- a linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms may be used as a molecule.
- Specific examples include succinimide, succinic amide, succinic ester, succinic ester-amide, benzylamine, polyamine, polysuccinimide, and Mannich base, and derivatives thereof include boron compounds.
- examples thereof include boron compounds such as acids and borates, phosphorus compounds such as thiophosphoric acid and thiophosphate, organic acids and hydroxypolyoxyalkylene carbonate.
- the solubility of the compound in the lubricating base oil may be reduced.
- the alkyl group or alkenyl group has a carbon number of more than 400, the lubricating oil composition
- the low temperature fluidity of the product may deteriorate.
- a preferable blending amount of these ashless dispersants is 0.5 to 10% by mass, more preferably 1 to 8% by mass with respect to the base oil.
- antioxidants examples include 2,6-di-tert-butylphenol (hereinafter, tert-butyl is abbreviated as t-butyl), 2,6-di-tert-butyl-4-methylphenol, 2, 6-di-t-butyl-4 -ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-bis ( 2,6-di-tert-butylphenol), 4,4′-bis (2- methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis (2,6-di-t -Butylphenol), 2,2'-methylenebis (4-
- Examples of the friction reducing agent include sulfurized oxymolybdenum dithiocarbamate represented by the following general formula (5), sulfurized oxymolybdenum dithiophosphate represented by the general formula (6), and dialkylamine represented by the general formula (7). And an organic molybdenum compound such as a reaction product of a compound having a pentavalent or hexavalent molybdenum atom.
- R 20 to R 23 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X 1 to X 4 each represents a sulfur atom or an oxygen atom.
- R 24 to R 27 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X 5 to X 8 each represents a sulfur atom or an oxygen atom.
- R 28 and R 29 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, but they are not simultaneously hydrogen atoms.
- R 20 to R 23 each independently represents a hydrocarbon group having 1 to 20 carbon atoms.
- groups include a methyl group, an ethyl group, a propyl group, a butyl group, Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group (these The group may be linear or branched, and may be primary, secondary or tertiary.) Saturated aliphatic hydrocarbon group such as ethenyl group (vinyl group), propenyl group (allyl group), butenyl group, pentenyl Group
- Aliphatic hydrocarbon group phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, cinnamyl group, benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butylphenyl group Pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, styrenated phenyl group, p-cumylphenyl group, phenylphenyl group, benzylphenyl Group, ⁇ -naphthyl group, ⁇ - Aromatic hydrocarbon groups such as naphthyl group; cycl
- R 24 to R 27 in the general formula (6) and R 28 and R 29 in the general formula (7) are each independently of 1 to 20 carbon atoms, similarly to R 20 to R 23 in the general formula (5).
- a preferable blending amount of these friction reducing agents is 30 to 2000 ppm by mass, more preferably 50 to 1000 ppm by mass, based on the base oil.
- viscosity index improver examples include poly (C1-18) alkyl methacrylate, (C1-18) alkyl acrylate / (C1-18) alkyl methacrylate copolymer, and dimethylaminoethyl methacrylate / (C1-18) alkyl methacrylate.
- Polymer ethylene / (C1-18) alkyl methacrylate copolymer, polyisobutylene, polyalkylstyrene, ethylene / propylene copolymer, styrene / maleic ester copolymer, styrene / isoprene hydrogenated copolymer, olefin copolymer (OCP) and a star polymer.
- a dispersion-type or multifunctional viscosity index improver imparted with dispersion performance may be used.
- the weight average molecular weight is about 10,000 to 1,500,000, preferably about 20,000 to 500,000.
- a preferred blending amount of these viscosity index improvers is 0.1 to 20% by mass, more preferably 0.3 to 15% by mass with respect to the base oil.
- pour point depressant examples include polyalkyl methacrylate, polyalkyl acrylate, polyalkyl styrene, ethylene-vinyl acetate copolymer, and polyvinyl acetate.
- the weight average molecular weight is 1000 to 100,000, preferably 5000 to It is about 50,000.
- a preferable blending amount of these pour point depressants is 0.00 to 5 to 3% by mass, more preferably 0.01 to 2% by mass with respect to the base oil.
- Examples of the rust preventive include sodium nitrite, oxidized paraffin wax calcium salt, oxidized paraffin wax magnesium salt, beef tallow fatty acid alkali metal salt, alkaline earth metal salt, alkaline earth amine salt, alkenyl succinic acid, alkenyl succinic acid half Examples include esters (the molecular weight of the alkenyl group is about 100 to 300), sorbitan monoesters, nonylphenol ethoxylates, and lanolin fatty acid calcium salts.
- a preferable blending amount of these rust preventives is 0.01 to 3% by mass, more preferably 0.02 to 2% by mass with respect to the base oil.
- corrosion inhibitor and metal deactivator examples include 2-hydroxy-N- (1H-1,2, which is a triazole, tolyltriazole, benzotriazole, benzimidazole, benzothiazole, benzothiadiazole or a derivative of these compounds.
- antifoaming agents examples include polydimethyl silicone, dimethyl silicone oil, trifluoropropyl methyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy / propoxylate, fatty acid ethoxy / propoxylate, and sorbitan partial fatty acid ester. Is mentioned.
- a preferable blending amount of these antifoaming agents is 0.001 to 0.1% by mass, more preferably 0.001 to 0.01% by mass with respect to the base oil.
- the multifunctional lubricant composition of the present invention is used as a lubricating additive such as an antiwear agent
- a lubricating base oil other than the lubricating base oil of the present invention as the lubricating base oil.
- the blending amount of the lubricating additive of the present invention is preferably 0.01 to 6 parts by mass with respect to 100 parts by mass of the lubricating base oil. If the amount is less than 0.01 parts by mass, the active ingredient may be insufficient, and the effect as an antiwear agent may not be exhibited. If the amount is more than 6 parts by mass, the solubility in the base oil is reduced, and further, as an antiwear agent. The effect may not be seen. In order to be usable as an additive for lubrication, it is preferable that the solubility in the base oil is good. It is not preferable that insoluble components are observed.
- the multifunctional lubricant composition of the present invention When the multifunctional lubricant composition of the present invention is used as a lubricant additive such as an antiwear agent, other additives can be added as long as the effects of the present invention are not impaired.
- Other additives that can be used include antiwear agents other than the multifunctional lubricant composition of the present invention, extreme pressure agents, friction modifiers, metal detergents, ashless dispersants, antioxidants, friction reducers, viscosity Index improvers, pour point depressants, rust inhibitors, corrosion inhibitors, load-bearing additives, antifoaming agents, metal deactivators, emulsifiers, demulsifiers and fungicides are selected from these. It is preferable to contain 0.001 to 40 parts by mass of one or more compounds. These additives are the same as those listed above as other additives that can be used when the multifunctional lubricant composition of the present invention is used as a base oil for flame retardant lubrication.
- the base oil that can be used, and a mineral base is appropriately selected according to the purpose of use and conditions of use. Selected from oils, chemically synthesized base oils, animal and vegetable base oils, and mixed base oils thereof.
- the mineral base oil may be, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or by distillation under reduced pressure of residual oil of atmospheric distillation or Examples include refined oils obtained by refining them according to conventional methods, specifically solvent refined oils, hydrogenated refined oils, dewaxed oils, and clay-treated oils.
- Examples of the chemically synthesized base oil include poly- ⁇ -olefin, polyisobutylene (polybutene), diester, polyol ester, silicate ester, polyalkylene glycol, polyphenyl ether, silicone, fluorinated compound, and alkylbenzene.
- poly- ⁇ -olefin, polyisobutylene (polybutene), diester, polyol ester and the like can be used for general purposes.
- poly- ⁇ -olefin examples include 1-hexene, 1-octene, 1-octene, Nonene, 1-decene, 1-dodecene, 1-tetradecene, etc., which are polymerized or oligomerized, or those obtained by hydrogenating these, and diesters include, for example, glutaric acid, adipic acid, azelaic acid, sebacin Acid and dodecanedioic acid, etc.
- diesters examples include dibasic acids and diesters of alcohols such as 2-ethylhexanol, octanol, decanol, dodecanol and tridecanol.
- polyol esters examples include neopentyl glycol, trimethylol ethane, trimethylol propane, pentaerythritol, dipenta
- esters of polyols such as erythritol and tripentaerythritol with fatty acids such as caproic acid, caprylic acid, lauric acid, capric acid, myristic acid, palmitic acid, stearic acid and oleic acid.
- Animal and plant base oils include, for example, castor oil, olive oil, cacao butter, sesame oil, rice bran oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, cottonseed oil And vegetable oils such as coconut oil, animal fats such as beef tallow, pork tallow, milk fat, fish oil and whale oil.
- castor oil olive oil, cacao butter, sesame oil, rice bran oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, cottonseed oil
- vegetable oils such as coconut oil, animal fats such as beef tallow, pork tallow, milk fat, fish oil and whale oil.
- Toxicity data including triphenyl phosphate and tricresyl phosphate is shown in Table 1 below.
- Hime Daka Acute Toxicity 96h-LC 50 mg / L is based on the “List of Ecological Effects Test Results (March 2010 Edition, Ministry of the Environment)” as a reference
- the value of Rainbow Trout Acute Toxicity 96 h-LC 50 mg / L is "International Common Chemical Information Data Base” and "US Environmental Protection Agency High Production Chemical Information System” are used as references.
- the tri-tert-butylphenyl system (mixture) in Table 1 represents a mixture of tri-tert-butylphenyl phosphate, di-tert-butylphenyl phosphate and mono-tert-butylphenyl phosphate. It is unknown. However, although the mixing ratio is different, tri-tert-butylphenyl phosphate is the phosphorus compound (C) in the multifunctional lubricant composition of the present invention, and di-tert-butylphenyl phosphate is The phosphorus compound (B) in the multifunctional lubricant composition, and mono-tert-butylphenyl phosphate is the phosphorus compound (A) in the multifunctional lubricant composition of the present invention.
- the multifunctional lubricant composition is expected to exhibit the same toxicity as the tri-tert-butylphenyl system (mixture) in Table 1 above. Therefore, the multifunctional lubricant composition of the present invention is less toxic and safer than phosphorus compounds such as triphenyl phosphate and tricresyl phosphate.
- Example 1 Synthesis method of compound II
- a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, a suction pipe for decompression, and a stirrer 153.3 g (1.0 mol) of phosphorus oxychloride and 166.9 g of p-tert-butylphenol (1. 1 mol) was added, and magnesium chloride as a catalyst was further added to 0.3 g of the system.
- the temperature in the system was raised to 130 ° C. with stirring and a normal pressure reaction was carried out for 2 hours. Thereafter, the pressure in the system was reduced to 3.0 ⁇ 10 3 Pa and the pressure was reduced for 2 hours. Reaction was performed.
- compositions of compounds I to VII after synthesis are shown in Table 2.
- Comparative Example 1 4 parts by mass of phosphorus compound (B) with respect to 100 parts by mass of phosphorus compound (A)
- Example 1 27 parts by mass of phosphorus compound (B) with respect to 100 parts by mass of phosphorus compound (A).
- Example 2 30 mass parts of phosphorus compounds (B) with respect to 100 mass parts of phosphorus compounds (A).
- Example 3 36 mass parts of phosphorus compounds (B) with respect to 100 mass parts of phosphorus compounds (A).
- Example 4 38 mass parts of phosphorus compounds (B) with respect to 100 mass parts of phosphorus compounds (A).
- Example 5 41 parts by mass of phosphorus compound (B) with respect to 100 parts by mass of phosphorus compound (A) 0.7 part by mass of phosphorus compound (C).
- Comparative Example 2 132 parts by mass of phosphorus compound (B) and 5 parts by mass of phosphorus compound (C) with respect to 100 parts by mass of phosphorus compound (A).
- Viscosity data Table 3 shows the results of kinematic viscosity measurement of the above compounds I to VII at 40 ° C.
- the viscosity measuring instrument used was a stinger visometer “SVM 3000” manufactured by Anton Paar.
- the multifunctional lubricant composition of the present invention satisfies an appropriate viscosity range (40 ° C. kinematic viscosity 30 to 55 mm 2 / s) required when used as a lubricating base oil, and may be used as an additive. It can be said that the viscosity is easy to handle.
- Comparative Example 2 has a high viscosity due to the influence of the phosphorus compounds (B) and (C), is not suitable for use as a lubricating base oil, and may be difficult to handle even when used as an additive. is there.
- the base oil used is a mineral oil having a kinematic viscosity of 19.5 mm 2 / s at 40 ° C. and a viscosity index of 123.
- ⁇ Evaluation method> The sample after the solubility test is completely dissolved, ⁇ if it is colorless and transparent, ⁇ if it is cloudy, ⁇ if it is turbid, sediment, or insoluble component, and test What was previously insoluble was evaluated as x.
- the multifunctional lubricant composition of the present invention exhibits good solubility and can be used as a lubricant additive.
- Comparative Example 1 shows white turbidity due to insoluble components and is not suitable for use as a lubricating additive.
- the wear resistance of the multifunctional lubricant composition of the present invention was evaluated.
- the compounds I to VII used as the lubricating base oil were tested, and further, the solutions II to VII using the compounds II to VII as the lubricating additives were tested (compound I was converted into the base oil by the solubility test described above). Because of its poor solubility, the wear resistance as an additive was not evaluated). Solutions II to VII using compounds II to VII as additives were further diluted with base oil, and adjusted so that compounds II to VII would be 0.1 wt% with respect to the base oil, and evaluated.
- the base oil used is a mineral oil having a kinematic viscosity of 19.5 mm 2 / s at 40 ° C.
- the test was conducted using a SRV tester (manufacturer name Optimol, model type 3) under the following conditions by the point contact method (Ball on Disk), and the size of the wear scar on the Ball after the test was evaluated. .
- Test conditions ⁇ Load 200 N ⁇ Amplitude 4.0 mm ⁇ Frequency 20 Hz ⁇ Temperature 80 °C ⁇ Time 60 min Evaluation method ⁇ : Wear scar diameter 0.40 to 0.55 mm ⁇ : Wear scar diameter 0.56 to 0.70 mm ⁇ : Wear scar diameter 0.71 to 0.85 mm ⁇ : Wear scar diameter 0.86 to 1.00 mm
- Tables 5 and 6 show the evaluation results of wear resistance.
- the multifunctional lubricant composition of the present invention exhibits very good wear resistance when used as a lubricating additive, and can also exhibit wear resistance when used as a lubricating base oil. all right.
- Example 3 The hydrolyzability of the multifunctional lubricant composition of the present invention (Example 3) was investigated. ⁇ Test method> 1 mass% of water is added to the phosphorus compound and stored in a constant temperature bath at 60 ° C. The hydrolyzability was evaluated by measuring the acid value for each elapsed day. The results are shown in FIG. As can be seen from FIG. 1, TPP has high hydrolyzability, and the multifunctional lubricant composition of the present invention (Example 3) has low hydrolyzability compared to this.
- the composition of the present invention is a multifunctional lubricant composition that can be used as a lubricating base oil or a lubricating additive. Combining performance such as flame retardancy and abrasion resistance, low toxicity and high hydrolysis stability, it is environmentally friendly and safe. In the future, it is expected to be used as an alternative compound for triphenyl phosphate and tricresyl phosphate in the lubrication industry and a wide variety of other industries.
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Abstract
Description
本発明の多機能潤滑剤組成物は、下記の一般式(1)で表されるリン化合物(A)100質量部に対して、下記の一般式(2)で表されるリン化合物(B)を26~43質量部、下記の一般式(3)で表されるリン化合物(C)を0~1.3質量部、トリフェニルホスフェート及びトリクレジルホスフェートを合計で0~1.3質量部含有することを特徴とする多機能潤滑剤組成物である。
なお、上記「パラ位」とは、リン化合物(A)のリン原子に結合する酸素原子がベンゼン環へ結合する位置に対する位置である。
なお、上記「パラ位」とは、リン化合物(B)のリン原子に結合する酸素原子がベンゼン環へ結合する位置に対する位置である。
なお、上記「パラ位」とは、リン化合物(C)のリン原子に結合する酸素原子がベンゼン環へ結合する位置に対する位置である。
< 方法1 >
まず、クロロリン酸ジフェニル及び/又はクロロリン酸ジクレジルに、適切な触媒存在下かつ窒素雰囲気下で、1つの置換基を有するフェノール化合物(1種以上)及び/又は1つの置換基を有するクレゾール化合物(1種以上)を反応させ、一般式(1)で表されるリン化合物(A)を得る。次に、ジクロロリン酸フェニル及び/又はジクロロリン酸クレジルに、適切な触媒存在下かつ窒素雰囲気下で、1つの置換基を有するフェノール化合物(1種以上)及び/又は1つの置換基を有するクレゾール化合物(1種以上)を反応させ、一般式(2)で表されるリン化合物(B)を得る。続いて、オキシ塩化リンに、適切な触媒存在下かつ窒素雰囲気下で、1つの置換基を有するフェノール化合物(1種以上)及び/又は1つの置換基を有するクレゾール化合物(1種以上)を反応させ、一般式(3)で表されるリン化合物(C)を得る。上記反応では、それぞれ、反応系中に存在する塩酸等を減圧して除去することが好ましい。反応後に反応系を減圧してもよく、反応中に、連続的に、断続的にもしくは一時的に減圧してもよい。最後に、得られたリン化合物(A)100質量部に対して、リン化合物(B)を26~43質量部、リン化合物(C)を0~1.3質量部含有するよう配合し、本発明の多機能潤滑材料組成物を得る。
まず、オキシ塩化リンに、適切な触媒の存在下かつ窒素雰囲気下で、1つの置換基を有するフェノール化合物(1種以上)及び/又は1つの置換基を有するクレゾール化合物(1種以上)を加え、反応させ、その後、同一系内に、フェノール及び/又はクレゾールを加え、反応させ、本発明の多機能潤滑剤組成物を得る。
この時、オキシ塩化リン1モルに対して、該フェノール化合物及び/又は該クレゾール化合物を総量で、1.1モル~1.3モル、好ましくは1.18モル~1.28モル添加する。また、フェノール及び/又はクレゾールは、総量で、オキシ塩化リン1モルに対して、1.7モル~1.9モル、好ましくは1.72モル~1.82モル添加する。ここで、1種以上の1つの置換基を有するフェノール及び/又は1種以上の1つの置換基を有するクレゾールを反応に使用する場合は、一括してオキシ塩化リンに加えてもよく、反応状況を考慮して分割して加えてもよい。また、反応系中に存在する塩酸等を減圧して除去することが好ましい。反応後に反応系を減圧してもよく、反応中に、連続的に、断続的にもしくは一時的に減圧してもよい。
また、本発明の多機能潤滑剤組成物は上記記載した方法1を用いて得ても、方法2を用いて得てもよいが、簡便かつ短時間で得られることから方法2で得る方が好ましい。
トリフェニルホスフェート及びトリクレジルホスフェートを含めた毒性データを下記表1に示す。ここで、ヒメダカ急性毒性96h-LC50mg/Lの値は「生態影響試験結果一覧(平成22年3月版、環境省)」を参考文献として使用し、ニジマス急性毒性96h-LC50mg/Lの値は「国際共通化学情報データベース(International Uniform Chemical Information Data Base)」、「アメリカ合衆国環境保護庁高生産化学物質情報システム」を参考文献として使用している。
よって、本発明の多機能潤滑剤組成物は、トリフェニルホスフェート及びトリクレジルホスフェート等のリン化合物に比べて、毒性が低く、安全である。
温度計、窒素導入管、減圧用の吸入管及び攪拌機を付した容量1000mlの4つ口フラスコに、オキシ塩化リン153.3g(1.0モル)及びp-tert-ブチルフェノール166.9g(1.1モル)を入れ、更に触媒として塩化マグネシウムを0.3g系内に添加した。窒素置換後、攪拌しながら系内の温度を130℃まで昇温し、2時間の常圧反応を行い、その後、系内の圧力を3.0×103Paまで減圧して2時間の減圧反応を行った。常圧に戻し、系内にフェノール180.6g(1.9モル)を添加し、更に130℃で5時間反応した。その後、系内の圧力を3.0×103Paまで減圧し3時間の減圧反応を行い、常圧に戻した後、水洗及び水洗後の水層の除去を行った。最後に、温度120℃、圧力3.0×103Paで2時間減圧脱水を行い、化合物IIを得た。
次に、上記合成方法と同様の方法にて、実施例2~5を行い、化合物III~VIを得た。
温度計、窒素導入管、減圧用の吸入管及び攪拌機を付した容量1000mlの4つ口フラスコに、オキシ塩化リン153.3g(1.0モル)及びp-tert-ブチルフェノール151.7g(1.0モル)を入れ、更に触媒として塩化マグネシウムを0.3g系内に添加した。窒素置換後、攪拌しながら系内の温度を130℃まで昇温して2時間反応を行った。その後、系内にフェノール190.1g(2.0モル)を添加し、更に130℃で5時間反応した。その後、系内の圧力を3.0×103Paまで減圧し3時間の減圧反応を行い、常圧に戻した後、水洗及び水洗後の水層の除去を行い、更に温度120℃、圧力3.0×103Paで2時間減圧脱水を行い、化合物Iを得た。
次に、上記合成方法と同様の方法にて、比較例2を行い、化合物VIIを得た。
実施例1:リン化合物(A)100質量部に対してリン化合物(B)27質量部。
実施例2:リン化合物(A)100質量部に対してリン化合物(B)30質量部。
実施例3:リン化合物(A)100質量部に対してリン化合物(B)36質量部。
実施例4:リン化合物(A)100質量部に対してリン化合物(B)38質量部。
実施例5:リン化合物(A)100質量部に対してリン化合物(B)41質量部 リン化合物(C)0.7質量部。
比較例2:リン化合物(A)100質量部に対してリン化合物(B)132質量
部、リン化合物(C)5質量部。
上記化合物I~VIIの40℃での動粘度測定結果を表3に示す。用いた粘度測定機器は、Anton Paar社製のstabinger viscometer 「SVM 3000」である。
化合物I~VIIを潤滑用添加剤として使用する場合、基油への溶解性が良好であることが必須となる。そこで、基油への溶解性試験を実施したので、その結果を表4に示す。試験方法は以下の通りである。
< 試験方法 >
化合物I~VIIを基油100質量部に対して6質量部添加し、溶液I~VIIを調整した。各溶液I~VIIは、50℃で1時間加熱攪拌し、化合物I~VIIを基油に溶解させた。その後数時間室温放置し、25℃の恒温槽にて一週間静置した。使用した基油は、40℃の動粘度19.5mm2/s、粘度指数123の鉱物油である。
< 評価方法 >
溶解性試験終了後のサンプルが、完全に溶解しており、無色透明なものを◎、曇りが出てきたものを○、濁り・沈降物・不溶成分が出てきたものを△、試験を行う以前に不溶であったものを×として評価した。
本発明の多機能潤滑剤組成物について、耐摩耗性の評価を行った。潤滑用基油として使用した化合物I~VII原体、さらに、化合物II~VIIを潤滑用添加剤として使用した溶液II~VIIについて試験を実施した(化合物Iは前述した溶解性試験により基油への溶解性が悪いことから、添加剤としての耐摩耗性の評価は行わなかった)。
化合物II~VIIを添加剤として使用した溶液II~VIIは、更に基油で薄め、化合物II~VIIが基油に対して0.1wt%となるように調整し、評価を行った。使用した基油は、溶解性試験同様、40℃の動粘度19.5mm2/s、粘度指数123の鉱物油である。
試験は、SRV試験機(メーカー名 Optimol、型式 type3)を用い、以下条件で、点接触法(Ball on Disk)にて試験を行い、試験後のBallについた摩耗痕の大きさについて、評価した。
・ 荷重 200 N
・ 振幅 4.0 mm
・ 周波数 20 Hz
・ 温度 80 ℃
・ 時間 60 min
評価方法
◎ : 摩耗痕径 0.40 ~ 0.55 mm
○ : 摩耗痕径 0.56 ~ 0.70 mm
△ : 摩耗痕径 0.71 ~ 0.85 mm
× : 摩耗痕径 0.86 ~ 1.00 mm
本発明の多機能潤滑剤組成物(実施例3)の加水分解性について調査した。
< 試験方法 >
リン化合物に1mass%の水を添加し、60℃の恒温槽で保存。経過日数毎の酸価を測定することでその加水分解性を評価した。結果を図1に示す。
図1からわかるように、TPPは加水分解性が高く、これに比べ、本発明の多機能潤滑剤組成物(実施例3)は加水分解性が低いことがわかる。
Claims (8)
- 下記の一般式(1)で表されるリン化合物(A)100質量部に対して、下記の一般式(2)で表されるリン化合物(B)を26~43質量部、下記の一般式(3)で表されるリン化合物(C)を0~1.3質量部、トリフェニルホスフェート及びトリクレジルホスフェートを合計で0~1.3質量部含有する、多機能潤滑剤組成物。
- 一般式(1)で表される化合物(A)中のR1はパラ位の炭素数2~5の炭化水素基を表し、R2~R4は水素原子を表し、一般式(2)で表される化合物(B)中のR5及びR7はパラ位の炭素数2~5の炭化水素基を表し、R6、R8及びR9は水素原子を表し、一般式(3)で表される化合物(C)中のR10、R12及びR14はパラ位の炭素数2~5の炭化水素基を表し、R11、R13及びR15が水素原子を表す、請求項1に記載の多機能潤滑剤組成物。
- 前記R1、R5、R7、R10、R12及びR14が、t-ブチル基である、請求項2に記載の多機能潤滑剤組成物。
- 請求項1~3のいずれか一項に記載の多機能潤滑剤組成物からなる潤滑基油以外の潤滑基油100質量部に対して、請求項1~3のいずれか一項に記載の多機能潤滑剤組成物を0.01~6質量部含有する、潤滑油組成物。
- 更に、摩耗防止剤、極圧剤、摩擦調整剤、金属系清浄剤、無灰分散剤、酸化防止剤、摩擦低減剤、粘度指数向上剤、流動点降下剤、防錆剤、腐食防止剤、金属不活性化剤及び消泡剤から選択される1種又は2種以上の化合物を、前記潤滑基油100質量部に対して0.001~40質量部含有する、請求項4に記載の潤滑油組成物。
- 前記多機能潤滑剤組成物からなる潤滑基油以外の潤滑基油が、鉱物基油、化学合成基油、動植物基油またはこれらの混合基油から選択される、請求項3~5のいずれか一項に記載の潤滑油組成物。
- 請求項1又は2に記載の多機能潤滑剤組成物からなる潤滑基油。
- 請求項7に記載の潤滑基油100質量部に対して、摩耗防止剤、極圧剤、摩擦調整剤、金属系清浄剤、無灰分散剤、酸化防止剤、摩擦低減剤、粘度指数向上剤、流動点降下剤、防錆剤、腐食防止剤、金属不活性化剤及び消泡剤から選択される1種又は2種以上の化合物を0.001~40質量部含有する、潤滑油組成物。
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WO2023167036A1 (ja) * | 2022-03-02 | 2023-09-07 | Eneos株式会社 | 潤滑油用添加剤、潤滑油組成物及び作動流体組成物 |
JP7465768B2 (ja) | 2020-09-09 | 2024-04-11 | シチズン時計株式会社 | 難燃性工業油組成物 |
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