WO2024005185A1 - Composition d'additif pour huiles lubrifiantes et composition d'huile lubrifiante - Google Patents

Composition d'additif pour huiles lubrifiantes et composition d'huile lubrifiante Download PDF

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Publication number
WO2024005185A1
WO2024005185A1 PCT/JP2023/024357 JP2023024357W WO2024005185A1 WO 2024005185 A1 WO2024005185 A1 WO 2024005185A1 JP 2023024357 W JP2023024357 W JP 2023024357W WO 2024005185 A1 WO2024005185 A1 WO 2024005185A1
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group
copolymer
structural unit
lubricating oil
monomer
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PCT/JP2023/024357
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English (en)
Japanese (ja)
Inventor
幸生 吉田
将太 加藤
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出光興産株式会社
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Priority claimed from JP2022106709A external-priority patent/JP2024006117A/ja
Priority claimed from JP2022106711A external-priority patent/JP2024006118A/ja
Priority claimed from JP2022106706A external-priority patent/JP2024006116A/ja
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Publication of WO2024005185A1 publication Critical patent/WO2024005185A1/fr

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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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
    • C10M153/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a lubricating oil additive composition and a lubricating oil composition containing the lubricating oil additive composition.
  • Various lubricating oil additives are blended into lubricating oils for the purpose of imparting properties and performance necessary for lubricating oils, or supplementing and enhancing them.
  • One of the typical lubricating oil additives is a load-bearing additive that imparts wear resistance and extreme pressure properties to the lubricating oil.
  • load-bearing additives low-molecular-weight compounds containing sulfur and phosphorus, such as dithiophosphoric acid esters, are widely used (for example, see Patent Document 1).
  • low molecular weight compounds containing sulfur and phosphorus do not have sufficient wear resistance and extreme pressure properties, and there is room for further improvement. Furthermore, low molecular weight compounds containing sulfur and phosphorus have problems such as poor thermal stability and tend to generate sludge when used at high temperatures for long periods of time.
  • the present invention provides an additive composition for lubricating oil that is suitable as a load-bearing additive and has excellent wear resistance, extreme pressure properties, and thermal stability, and a lubricating oil containing the additive composition for lubricating oil.
  • An object of the present invention is to provide a composition.
  • the present inventors conducted extensive studies to solve the above problems. As a result, it was discovered that a poly(meth)acrylate copolymer that includes structural units derived from a plurality of specific monomers and satisfies specific requirements can solve the above problems, leading to the completion of the present invention.
  • the copolymer (X) has at least one of the following groups in the side chain.
  • [2] A method of using the lubricating oil additive composition according to [1] above as a load-bearing additive.
  • [3] A lubricating oil composition containing the lubricating oil additive composition according to [1] above and a lubricating oil base oil.
  • [4] A method for producing a lubricating oil composition, comprising a step of mixing the lubricating oil additive composition described in [1] above and a lubricating oil base oil.
  • an additive composition for lubricating oil that is suitable as a load-bearing additive and has excellent wear resistance, extreme pressure properties, and thermal stability, and a lubricating oil containing the additive composition for lubricating oil. It becomes possible to provide a composition.
  • the lubricating oil additive composition of the present embodiment contains a copolymer (X) that includes the following structural units (a) and (b) and satisfies the following requirements (1) to (3).
  • the copolymer (X) has at least one of the following groups in the side chain.
  • the present inventors conducted extensive studies in order to solve the above problems. As a result, a copolymer (X) containing the structural unit (a) derived from the above monomer (A) and the structural unit (b) derived from the above monomer (B) and satisfying the above requirements (1) to (3) The present inventors have discovered that the copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability, and that the copolymer (X) can be suitably used as an additive for lubricating oils (particularly as a load-bearing additive). Ta.
  • copolymer (X) has excellent wear resistance, extreme pressure properties, and thermal stability is that oil solubility (solubility in base oil (especially mineral oil)) is ensured by containing the above structural unit (a). "phosphorus and sulfur” or “sulfur” is This is presumed to be due to the introduction of a predetermined amount into the side chain. More specifically, in the lubricating oil composition, "phosphorus and sulfur” or “sulfur” introduced into the side chain is protected by the steric hindrance of the copolymer (X), thereby improving thermal stability.
  • the copolymer (X) is compressed and the "phosphorus and sulfur” or “sulfur” introduced into the side chain is exposed, so that the “phosphorus and sulfur” or “sulfur” is exposed. It is presumed that “sulfur” reacts with the metal, improving wear resistance and extreme pressure properties.
  • the monomer (A) used in this embodiment has a (meth)acryloyl group and an alkyl group having 8 to 20 carbon atoms.
  • the structural unit (a) derived from the monomer (A) mainly functions to exhibit oil solubility (solubility in mineral oil) in the copolymer (X).
  • the monomers (A) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain only one type of structural unit (a) derived from the monomer (A), or may contain two or more types.
  • the (meth)acryloyl group possessed by the monomer (A) functions as a polymerizable functional group, and may be either an acryloyl group or a methacryloyl group, but from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
  • the (meth)acryloyl group that monomer (A) has is preferably an acryloyl group.
  • the monomer (A) has an alkyl group having 8 to 20 carbon atoms.
  • the number of carbon atoms in the alkyl group is less than 8, and when the number of carbon atoms in the alkyl group is more than 20, it becomes difficult to ensure the oil solubility of the copolymer (X).
  • alkyl group having 8 to 20 carbon atoms examples include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and Examples include chain alkyl groups such as icosyl group. These may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
  • the monomer (A) contains an alkyl (meth)acrylate (A1) described below.
  • Alkyl (meth)acrylate (A1) is a monomer represented by the following general formula (a-1).
  • the alkyl (meth)acrylates (A1) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (a1) derived from the alkyl (meth)acrylate (A1), or may contain two or more types.
  • R a1 is a hydrogen atom or a methyl group. That is, the alkyl (meth)acrylate (A1) has an acryloyl group or a methacryloyl group as a polymerizable functional group. Monomers in which R a1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
  • R a1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the alkyl (meth)acrylate (A1) has an acryloyl group as a polymerizable functional group.
  • R a2 represents an alkyl group having 8 to 20 carbon atoms.
  • the alkyl group having 8 to 20 carbon atoms that can be selected as R a2 include those mentioned above as the alkyl group constituting the monomer (A). These may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 10 to 18, more preferably 10 to 16, and still more preferably 10 to 14. .
  • the content of the structural unit (a1) derived from the alkyl (meth)acrylate (A1) is preferably 50 mol% based on the total structural units of the structural unit (a) derived from the monomer (A). -100 mol%, more preferably 60 mol% - 100 mol%, even more preferably 70 mol% - 100 mol%, even more preferably 80 mol% - 100 mol%, even more preferably 90 mol% - 100 mol% It is.
  • the monomer (B) used in this embodiment has a (meth)acryloyl group and a polar group.
  • the structural unit (b) derived from the monomer (B) has a function of making the copolymer (X) a multi-point adsorption type copolymer, and is presumed to contribute to improving wear resistance.
  • monomer (B) may be used individually by 1 type, and may be used in combination of 2 or more types. Therefore, the copolymer (X) may contain only one type of structural unit (b) derived from the monomer (B), or may contain two or more types.
  • the (meth)acryloyl group possessed by the monomer (B) functions as a polymerizable functional group, and may be either an acryloyl group or a methacryloyl group, but from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
  • the (meth)acryloyl group that monomer (B) has is preferably an acryloyl group.
  • the monomer (B) has a polar group.
  • the polar group does not include a group containing at least one selected from phosphorus and sulfur.
  • the polar group preferably includes a nitrogen atom-containing group such as an amide group, a primary amino group, a secondary amino group, a tertiary amino group, a nitrile group, a urea group, and a urethane group; a hydroxyl group; a carboxyl group, etc. .
  • the monomer (B) contains a polar group-containing (meth)acrylate (B1) described below.
  • the polar group-containing (meth)acrylate (B1) includes a monomer having a (meth)acryloyl group and a nitrogen atom-containing group, a monomer having a (meth)acryloyl group and a hydroxyl group, and a monomer having a (meth)acryloyl group and a carboxyl group.
  • One or more types selected from the group consisting of monomers having Therefore, the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1) may contain one type alone, or may contain two or more types.
  • monomers having a (meth)acryloyl group and a nitrogen atom-containing group include amide group-containing acrylic monomers, primary amino group-containing acrylic monomers, Examples include secondary amino group-containing acrylic monomers, tertiary amino group-containing acrylic monomers, nitrile group-containing acrylic monomers, urea group-containing acrylic monomers, urethane group-containing acrylic monomers, and the like.
  • amide group-containing acrylic monomers include (meth)acrylamide; N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, and monoalkylamino(meth)acrylamide such as N-isobutyl(meth)acrylamide; N-methylaminoethyl(meth)acrylamide, N-ethylaminoethyl(meth)acrylamide, N-isopropylamino-n-butyl(meth)acrylamide , N-butylamino-n-butyl (meth)acrylamide, and N-isobutylamino-n-butyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide; Dialkylamino(meth)acrylamides such as N,N-diethyl(meth)acrylamide, N,N-diisopropyl(
  • acrylic monomer containing a primary amino group examples include aminoalkyl (meth)acrylate having an alkyl group having 2 to 6 carbon atoms, such as aminoethyl (meth)acrylate.
  • acrylic monomer containing a secondary amino group examples include monoalkylaminoalkyl (meth)acrylates such as tert-butylaminoethyl (meth)acrylate and methylaminoethyl (meth)acrylate.
  • acrylic monomer containing a tertiary amino group examples include dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
  • Examples of the nitrile group-containing acrylic monomer include (meth)acrylonitrile.
  • Examples of the urea group-containing acrylic monomer include 2-isocyanatoethyl (meth)acrylate.
  • Examples of the urethane group-containing acrylic monomer include monofunctional urethane acrylate.
  • - Monomer having a (meth)acryloyl group and a hydroxyl group examples include hydroxyl group-containing acrylic monomers.
  • examples of hydroxyl group-containing acrylic monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2- or 3-hydroxypropyl (meth)acrylate; N,N-dihydroxymethyl (meth)acrylamide; , N,N-dihydroxypropyl (meth)acrylamide, N,N-di-2-hydroxybutyl (meth)acrylamide, and other mono- or dihydroxyalkyl-substituted (meth)acrylamides.
  • Examples of the monomer having a (meth)acryloyl group and a carboxyl group include carboxyl group-containing acrylic monomers.
  • Examples of the carboxyl group-containing acrylic monomer include (meth)acrylic acid; carboxyalkyl (meth)acrylates such as carboxyethyl (meth)acrylate.
  • ⁇ Preferred acrylic monomer Among the above acrylic monomers, dialkylaminoalkyl (meth)acrylamide, hydroxyalkyl (meth)acrylate, and carboxyalkyl (meth)acrylate are selected from among the above-mentioned acrylic monomers, from the viewpoint of easily improving the effects of the present invention. One or more selected types are preferred.
  • the number of carbon atoms in the alkyl groups of these monomers is preferably 1 to 6, more preferably 1 to 4, each independently.
  • the content of the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1) is preferably 50% based on the total structural unit (b) derived from the monomer (B).
  • mol% to 100 mol% more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%. It is mole%.
  • the polar group-containing (meth)acrylate (B1) includes a hydroxyl group-containing (meth)acrylate (B11) from the viewpoint of making it easier to improve the effects of the present invention.
  • the hydroxyl group-containing (meth)acrylate (B11) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11), or may contain two or more types.
  • R b1 is a hydrogen atom or a methyl group. That is, the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group or a methacryloyl group as a polymerizable functional group.
  • Monomers in which R b1 is a substituent other than a hydrogen atom or a methyl group are difficult to obtain, and since these monomers have low reactivity, it is also difficult to polymerize them.
  • R b1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the hydroxyl group-containing (meth)acrylate (B11) has an acryloyl group as a polymerizable functional group.
  • R b2 represents an alkylene group having 2 to 4 carbon atoms.
  • the number of carbon atoms in the alkylene group is 1, the polarity becomes high and the oil solubility decreases.
  • the number of carbon atoms in the alkylene group is 5 or more, the oil solubility increases too much and the adsorption to metals decreases.
  • the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
  • m1 represents an integer from 1 to 10.
  • m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different.
  • the bonding mode between the moieties represented by -(OR b2 ) m1 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
  • the hydroxyl group-containing (meth)acrylate (B11) becomes a carboxylic acid, resulting in decreased oil solubility.
  • m1 is an integer of 11 or more, the polarity becomes high due to the influence of the -(OR b2 )- moiety, and the oil solubility decreases.
  • m1 is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2, and even more preferably 1.
  • the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is based on all the structural units of the structural unit (b1) derived from the polar group-containing (meth)acrylate (B1). and, preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably It is 90 mol% to 100 mol%.
  • the content of the structural unit (b11) derived from the hydroxyl group-containing (meth)acrylate (B11) is preferably 50 mol based on the total structural unit (b) derived from the monomer (B). % to 100 mol%, more preferably 60 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, even more preferably 80 mol% to 100 mol%, even more preferably 90 mol% to 100 mol%. %.
  • requirement (1) is defined as follows.
  • the copolymer (X) has at least one of the following groups in the side chain. Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
  • the sulfur-containing group copolymer (X) does not have any of the above groups in the side chain, sufficient wear resistance and extreme pressure properties cannot be ensured.
  • phosphorus and sulfur are elements that cause a decrease in thermal stability, they are elements that are generally not introduced from the viewpoint of ensuring thermal stability.
  • the structural unit (a) derived from the monomer (A) and the monomer (B ) By introducing the above group into the side chain of the copolymer (X) in which the structural unit (b) derived from It has been found that the copolymer (X) as a whole has excellent thermal stability, as well as excellent abrasion resistance and extreme pressure properties.
  • the above-mentioned group included in the side chain of the copolymer (X) includes at least one of the following groups. Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.)
  • examples of the phosphorus- and sulfur-containing group include a thiophosphoric acid group, thiophosphoryl, and the like.
  • examples of the phosphorus-containing group include a phosphonic acid group, a phosphorous acid group, a phosphinic acid group, a phosphorous acid group, and a phosphorous group.
  • examples include acid groups, pyrophosphate groups, and ester groups thereof.
  • the sulfur-containing group (a group having sulfur in one group and not having phosphorus) includes, for example, a mercapto group; an acetylthio group; a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
  • thioester groups such as; dithioester groups; alkylthio groups such as methylthio and ethylthio groups; arylthio groups such as phenylthio, methylphenylthio, and naphthylthio groups; thioacyl groups; thioether groups; thiocyanate ester groups; isothiocyanate ester groups ; Sulfone ester groups such as methyl sulfonate group, ethyl sulfonate group, and phenyl sulfonate group; Sulfonamide groups such as phenylsulfonamide group, N-methylsulfonamide group, and N-methyl-p-toluenesulfonamide group ; thiocarboxyl group; dithiocarboxyl group; sulfo group; sulfonyl group; sulfinyl group; sulfenyl group.
  • requirement (2) is defined as follows.
  • the copolymer (X) contains a phosphorus atom the phosphorus atom content (P) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X). , it becomes easy to ensure sufficient wear resistance and extreme pressure properties.
  • the phosphorus atom content (P) in the copolymer (X) is 2.0% by mass or less based on the total amount of the copolymer (X), the oil solubility of the copolymer (X) is It can be easily secured.
  • the phosphorus atom content (P) in the copolymer (X) is preferably 0.02 The amount is preferably from 0.04% to 1.00% by weight, and even more preferably from 0.04% to 0.50% by weight.
  • the phosphorus atom content (P) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricating oil base oil), and then calculating the amount of phosphorus in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
  • an organic solvent for example, lubricating oil base oil
  • requirement (3) is defined as follows.
  • the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
  • the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X)
  • the sulfur atom content (S) in the copolymer (X) is preferably 0, based on the total amount of the copolymer (X).
  • the content is .02% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.04% by mass.
  • the sulfur atom content (S) in the copolymer (X) is Based on the total amount, it is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, even more preferably 1.00% by mass or less, even more preferably 0.50% by mass or less.
  • the upper and lower limits of these numerical ranges can be arbitrarily combined.
  • the sulfur atom content (S) of the copolymer (X) is determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (for example, lubricant base oil), and then calculating the amount of sulfur in the organic solvent by JPI- It can be calculated based on the results measured in accordance with 5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
  • an organic solvent for example, lubricant base oil
  • the method for preparing the copolymer (X) that satisfies requirements (1) to (3) is not particularly limited, but preferably includes the following Preparation Examples 1 to 4, and more preferably the following Preparation Examples 1 to 2 are listed.
  • a copolymer (X) that satisfies the above requirement (1) can be prepared by polymerizing a monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group together with monomers (A) and (B). . At that time, by adjusting the input amount of monomer (C), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
  • a copolymer (X) satisfying the above requirement (1) can be prepared by polymerizing a monomer (D1) having a polymerizable functional group and a sulfur-containing group together with monomers (A) and (B). At that time, by adjusting the input amount of the monomer (D1), a copolymer (X) that also satisfies the above requirement (3) can be prepared. In addition, in Preparation Example 3, since the copolymer (X) does not contain a phosphorus atom, it is not necessary to satisfy the above requirement (2).
  • a monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group, a monomer (D1) having a polymerizable functional group and a sulfur-containing group, and/or a monomer having a polymerizable functional group and a phosphorus-containing group By polymerizing (D2) together with monomers (A) and (B), a copolymer (X) that satisfies the above requirement (1) can be prepared. At that time, by adjusting the input amounts of monomer (C), monomer (D1), and monomer (D2), a copolymer (X) that also satisfies the above requirements (2) and (3) can be prepared.
  • the copolymer (X) further contains one or more structural units ( ⁇ ) containing the group specified in requirement (1).
  • the monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group which can be suitably applied to Preparation Examples 1 to 5 (preferably Preparation Examples 1 to 2), a polymerizable functional group and a sulfur-containing group, A monomer (D1) having the following and a monomer (D2) having a polymerizable functional group and a phosphorus-containing group will be exemplified.
  • the monomer (C) having a polymerizable functional group and a phosphorus- and sulfur-containing group includes a (meth)acryloyl group and a compound represented by the following general formula (1).
  • Preferred examples include compounds having a monovalent group containing phosphorus and sulfur.
  • the copolymer (X) contains the structural unit (c) derived from the monomer (C), phosphorus and sulfur-containing groups are introduced into the side chains of the copolymer (X), which improves wear resistance and polarity. It can improve pressure resistance.
  • the monomer (C) may be used alone or in combination of two or more. Therefore, the copolymer (X) may contain one type of structural unit (c) derived from the monomer (C), or may contain two or more types.
  • the monomer (C) has a (meth)acryloyl group as a polymerizable functional group.
  • the polymerizable functional group that the monomer (C) has is preferably an acryloyl group.
  • R 1 and R 2 are preferably each independently an alkyl group having 1 to 10 carbon atoms from the viewpoint of improving the effects of the present invention.
  • Examples of the alkyl group having 1 to 10 carbon atoms that can be selected as R 1 and R 2 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.
  • Examples include chain alkyl groups such as.
  • the chain alkyl group may be linear or branched. From the viewpoint of improving the effects of the present invention, the alkyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and even more preferably 3 carbon atoms.
  • the monomer (C) is preferably a compound represented by the following general formula (c-1).
  • R c1 is preferably a hydrogen atom or a methyl group.
  • R c1 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X).
  • R c2 is preferably an alkylene group having 2 to 4 carbon atoms.
  • the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
  • the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
  • the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
  • m2 is an integer from 0 to 10.
  • m2 is an integer of 2 or more, a plurality of R c2 may be the same or different.
  • the bonding mode between the moieties represented by -(OR c2 ) m2 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
  • m2 is an integer of 10 or less, oil solubility can be easily ensured.
  • m2 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
  • L 1 represents a linker.
  • Linkers that can be selected as L 1 include, for example, divalent aliphatic hydrocarbon groups having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, and butylene group; -O-; -OC(O) -;-O-C(O)-R C3 - (R C3 is an alkylene group having 2 to 4 carbon atoms), and the like.
  • -OC(O)-R C3 - is preferred as the linker that can be selected as L 1 .
  • L 1 may be a direct bond.
  • R 1 and R 2 are as explained in the above general formula (1), and the preferred ranges are also as explained in the above general formula (1).
  • ⁇ Monomer (D1) having a polymerizable functional group and a sulfur-containing group As the monomer (D1) having a polymerizable functional group and a sulfur-containing group (hereinafter also simply referred to as "monomer (D1)"), a compound represented by the following general formula (d1-1) is preferably mentioned.
  • the copolymer (X) contains the structural unit (d1) derived from the monomer (D1), a sulfur-containing group is introduced into the side chain of the copolymer (X). Therefore, wear resistance and extreme pressure properties can be improved.
  • the copolymer (X) further contains a structural unit (d2) derived from the monomer (D2). Thereby, the phosphorus-containing group is also introduced into the side chain of the copolymer (X), and the wear resistance and extreme pressure properties can be further improved.
  • the monomer (D1) may be used alone or in combination of two or more types. Therefore, the copolymer (X) may contain only one type of structural unit (d1) derived from the monomer (D1), or may contain two or more types.
  • R d11 is preferably a hydrogen atom or a methyl group.
  • R d11 is preferably a hydrogen atom. That is, it is preferable that the monomer (D1) has an acryloyl group as a polymerizable functional group.
  • R d12 represents an alkylene group having 2 to 4 carbon atoms.
  • the number of carbon atoms in the alkylene group is 2 or more, oil solubility is easily ensured.
  • the number of carbon atoms in the alkylene group is 4 or less, adsorption to metals is likely to be good.
  • the number of carbon atoms in the alkylene group is preferably 2 to 3, more preferably 2, from the viewpoint of easily ensuring appropriate oil solubility and appropriate adsorption to metal.
  • m3 is preferably an integer of 0 to 10, more preferably an integer of 1 to 10.
  • a plurality of R d12 may be the same or different.
  • the bonding mode between the moieties represented by -(OR d12 ) m3 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
  • m3 is an integer of 10 or less, oil solubility can be easily ensured.
  • m3 is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
  • R d13 is preferably an alkyl group having 4 to 20 carbon atoms.
  • the number of carbon atoms in the alkyl group is 4 or more, and when the number of carbon atoms in the alkyl group is 20 or less, the effects of the present invention are more likely to be exhibited.
  • alkyl group having 4 to 20 carbon atoms that can be selected as R d13 include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include chain alkyl groups such as a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group. These may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 6 to 18, more preferably 6 to 16, and even more preferably 6 to 14.
  • ⁇ Monomer (D2) having a polymerizable functional group and a phosphorus-containing group As the monomer (D2) having a polymerizable functional group and a phosphorus-containing group (hereinafter also simply referred to as "monomer (D2)"), a compound represented by the following general formula (d2-1) is preferably mentioned.
  • the copolymer (X) contains the structural unit (d2) derived from the monomer (D2), a phosphorus-containing group is introduced into the side chain of the copolymer (X). Therefore, when the copolymer (X) further contains the structural unit (d1) derived from the monomer (D1), a sulfur-containing group is also introduced into the side chain of the copolymer (X), which improves wear resistance and polarity. Pressure properties can be improved.
  • the monomer (D2) may be used alone or in combination of two or more types. Therefore, the copolymer (X) may contain one type of structural unit (d2) derived from the monomer (D2), or may contain two or more types.
  • R d21 is preferably a hydrogen atom or a methyl group.
  • R d21 is preferably a hydrogen atom from the viewpoint of making it easier to adjust the molecular weight of the copolymer (X). That is, it is preferable that the monomer (D2) has an acryloyl group as a polymerizable functional group.
  • R d22 represents an ethylene group.
  • m4 is an integer from 1 to 6.
  • the plurality of R d2 may be the same or different.
  • the bonding mode between the moieties represented by -(OR d22 ) m4 may be random bonding or block bonding, but from the viewpoint of ease of polymerization, random bonding is preferable.
  • m4 is 1 to 6, it is easy to ensure oil solubility.
  • m4 is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.
  • n represents an integer of 1 or 2.
  • at least one of the plurality of R d23 represents a hydrogen atom.
  • R d23 is a hydrogen atom.
  • only one of the plurality of R d23 may be a hydrogen atom.
  • the other of the plurality of R d23 is a hydrocarbon group.
  • the hydrocarbon group is a methyl group or an ethyl group.
  • the lubricating oil additive composition of the present embodiment further satisfies the following requirement (4) from the viewpoint of improving the effects of the present invention.
  • - Requirement (4) When the copolymer (X) contains a phosphorus atom, the content ratio of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) [( S)/(P)] is 0.10 to 3.00 in mass ratio. From the viewpoint of making it easier to improve the effects of the present invention, the content ratio [(S)/(P)] is preferably 0.15 to 2.80, more preferably 0.15 to 2.60 in mass ratio. , more preferably 0.20 to 2.50.
  • the content ratio [(S)/(P)] is a mass ratio, It is preferably 0.50 to 3.00, more preferably 1.00 to 3.00, even more preferably 1.50 to 2.50.
  • the content ratio [(S)/(P)] is , in terms of mass ratio, is preferably 0.10 to 2.00, more preferably 0.10 to 1.00, even more preferably 0.20 to 0.80.
  • the copolymer (X) contains the above structural units (a) and (b), furthermore, the structural unit (c) derived from the monomer (C), the structural unit (d1) derived from the monomer (D1), and the monomer (D2).
  • structural units derived from other monomers may be contained within a range that does not impede the effects of the present invention.
  • the other monomers include functional group-containing monomers other than monomers (A), (B), (C), (D1), and (D2).
  • the copolymer (X) is derived from a functional group-containing monomer other than monomers (A), (B), (C), (D1), and (D2).
  • the content of the structural units is preferably less than 50% by mass, more preferably less than 40% by mass, even more preferably less than 30% by mass, even more preferably less than 20% by mass, even more preferably 10% by mass, based on all the structural units. Less than % by mass.
  • the copolymer (X) contains a total of monomers (A), monomers (B), and structural units derived from monomers (constituent units ( ⁇ )) used to satisfy requirements (1) to (3).
  • the amount is based on all the constituent units of the copolymer (X), preferably 70% by mass to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more Preferably it is 95% by mass to 100% by mass.
  • the content of the structural unit (a) in the copolymer (X) is preferably 50 mass based on the total amount of the copolymer (X) from the viewpoint of ensuring oil solubility and improving the effects of the present invention. % or more, more preferably 60% to 95% by weight, still more preferably 70% to 90% by weight.
  • the content of the structural unit (b) in the copolymer (X) is preferably 1% by mass or more, more preferably 3% by mass, based on the total amount of the copolymer (X).
  • the amount is preferably 6% to 25% by weight, preferably 6% to 25% by weight.
  • the content of the structural unit (c) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
  • the content of the structural unit (d1) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. Based on the total amount of , it is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.8% by mass to 3.0% by mass.
  • the content of the structural unit (d2) in the copolymer (X) is determined from the viewpoint of improving the effect of the present invention. It is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, even more preferably 0.8% by mass to 3.0% by mass, based on the total amount of.
  • the copolymer (X) of this embodiment has a content ratio of the structural unit (a) and the structural unit (b) [(a)/( b)] is preferably in a molar ratio of 50/50 to 90/10, more preferably 55/45 to 85/15.
  • the mass average molecular weight (Mw) of the copolymer (X) of this embodiment is preferably 5,000 to 100,000, more preferably 5,000 to 100,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. ,000 to 70,000, more preferably 5,000 to 50,000.
  • the mass average molecular weight (Mw) of the copolymer (X) is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 40,000, from the viewpoint of ensuring oil solubility and improving the effects of the present invention. It is.
  • the mass average molecular weight (Mw) of the copolymer (X) is preferably 5 from the viewpoint of ensuring oil solubility and improving the effect of the present invention. ,000 to 100,000, more preferably 5,000 to 70,000, even more preferably 5,000 to 50,000.
  • the molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably is 3.4 or less.
  • the molecular weight distribution (Mw/Mn) of the copolymer (X) of this embodiment may be 1.01 or more, 1.3 or more, or 1.5 or more. good.
  • the molecular weight distribution (Mw/Mn ) is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, from the viewpoint of making it easier to exhibit the effects of the present invention.
  • the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
  • the molecular weight distribution (Mw/Mn) of the copolymer (X) is preferably 4.0 or less in order to more easily improve the effects of the present invention. , more preferably 3.6 or less, still more preferably 3.4 or less.
  • the molecular weight distribution (Mw/Mn) of the copolymer (X) in this case may be 1.01 or more, 1.3 or more, or 1.5 or more. .
  • the mass average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) are values measured or calculated by the method described in the Examples described later.
  • the polymerization mode of the copolymer (X) of this embodiment is not particularly limited, and may be any of block copolymerization, random copolymerization, and block/random copolymerization. Among these, random copolymerization is preferred from the viewpoint of ease of polymerization reaction.
  • the method for producing an additive composition for lubricating oil includes a step (S) of producing a copolymer (X) by polymerizing monomers in one of the following combinations.
  • Monomer (A), monomer (B), and monomer (C) (2) Monomer (A), monomer (B), monomer (D1), and monomer (D2) (3) Monomer (A), monomer (B), and monomer (D1) (4) Monomer (A), monomer (B), monomer (C), and monomer (D1) and/or monomer (D2)
  • the method for producing the copolymer (X) is not particularly limited, and the copolymer (X) is produced by applying any known method. Examples of such methods include emulsion polymerization, suspension polymerization, and solution polymerization.
  • the method for producing the copolymer (X) (polymerization method) is based on a lubricating oil base. It is preferable to employ a solution polymerization method in which a solvent soluble in oil is used as a solvent.
  • the content ratio of each structural unit in the copolymer (X) usually corresponds to the ratio (feeding ratio) of each monomer constituting the copolymer (X). Therefore, the blending ratio of each of the above monomers is appropriately determined in consideration of the content ratio of each of the above structural units in the copolymer (X).
  • solvents used in the solution polymerization method include alcohols such as methanol, ethanol, propanol, 2-propanol, and butanol; hydrocarbons such as benzene, toluene, xylene, and hexane; ethyl acetate, butyl acetate, and isobutyl acetate.
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ethers such as methoxybutanol, ethoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dioxane; Mineral oil; Poly- ⁇ - Examples include synthetic oils such as olefins, ethylene- ⁇ -olefin copolymers, alkylbenzenes, alkylnaphthalenes, polyphenyl ethers, alkyl-substituted diphenyl ethers, polyol esters, dibasic acid esters, hindered esters, monoesters, and GTL base oils. These may be used alone or in combination of two or more.
  • initiators used in the solution polymerization method include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis- (N,N-dimethyleneisobutyramidine) dihydrochloride, azo initiators such as 1,1'-azobis(cyclohexyl-1-carbonitrile); hydrogen peroxide; benzoyl peroxide, t-butyl hydroperoxide, Organic peroxides such as cumene hydroperoxide, methyl ethyl ketone peroxide, and perbenzoic acid; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; hydrogen peroxide-Fe 2+ redox initiators; other existing radicals Examples include initiators.
  • the molecular weight of the copolymer (X) is controlled by a known method.
  • the molecular weight of the copolymer (X) can be controlled by the reaction temperature, reaction time, amount of initiator, amount of each monomer charged, type of solvent, use of chain transfer agent, etc.
  • the additive composition for lubricating oil of the present embodiment has a content of copolymer (X) that can be added to Preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, based on the total amount of the agent composition. Preferably it is 95% by mass or more. Considering the purity of copolymer (X), the content of copolymer (X) is usually less than 99% by mass based on the total amount of the lubricating oil additive composition.
  • the lubricating oil additive composition of this embodiment may be diluted with a diluting solvent from the viewpoint of solubility with the lubricating base oil and ease of handling.
  • the content of the copolymer (X) in the additive composition for lubricating oil means the content based on the total amount of active ingredients in the additive composition for lubricating oil, excluding the dilution solvent.
  • the lubricating oil additive composition of this embodiment has excellent wear resistance, extreme pressure properties, and thermal stability. Therefore, it is useful as a load-bearing additive. Therefore, in this embodiment, a method of using the lubricating oil additive composition as a load-bearing additive is provided.
  • the lubricating oil composition of this embodiment contains a lubricating oil additive composition containing the copolymer (X) and a lubricating oil base oil.
  • the content of the lubricating oil additive composition is determined such that the content of the resin component of the copolymer (X) is the same as the total amount of the lubricating oil composition, from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well. Based on the standard, it is preferably adjusted to 0.3% by mass to 10% by mass, more preferably 0.6% by mass to 8.0% by mass, and even more preferably 1.0% by mass to 6.0% by mass. Ru.
  • the content of the lubricating oil additive composition is determined from the viewpoint of exhibiting the additive effect of the lubricating oil additive composition well, and the amount of sulfur derived from the copolymer (X) is determined by the total amount of the lubricating oil composition. Based on the standard, it is preferably 10 mass ppm to 300 mass ppm, more preferably 20 mass ppm to 200 mass ppm, and still more preferably 30 mass ppm to 150 mass ppm.
  • the amount of phosphorus derived from the copolymer (X) is Based on the total amount of the composition, preferably 5 ppm to 150 ppm by weight, more preferably 10 ppm to 100 ppm by weight, and still more preferably 15 ppm to 75 ppm by weight.
  • lubricating base oil any general base oil used in lubricating oil compositions can be used without particular limitation. Specifically, for example, one or more types selected from the group consisting of mineral oil and synthetic oil may be mentioned.
  • the kinematic viscosity at 100° C. of the lubricating base oil is preferably in the range of 1 mm 2 /s to 50 mm 2 /s, more preferably in the range of 2 mm 2 /s to 30 mm 2 /s, and more preferably 3 mm 2 /s. More preferably, the speed is in the range of ⁇ 20 mm 2 /s.
  • the viscosity index of the lubricating base oil is preferably 80 or more, more preferably 90 or more, and even more preferably 100 or more.
  • the kinematic viscosity and viscosity index of the lubricating base oil are values measured or calculated according to JIS K2283:2000.
  • lubricant base oils include, for example, distillate oil obtained by atmospheric distillation and/or vacuum distillation of paraffinic crude oil, intermediate crude oil, or naphthenic crude oil; refined oil obtained by refining the distillate oil according to a conventional method; oil; etc.
  • Examples of the purification method for obtaining refined oil include solvent dewaxing treatment, hydroisomerization treatment, hydrofinishing treatment, clay treatment, and the like.
  • Examples of synthetic oils include hydrocarbon oils, aromatic oils, ester oils, and ether oils.
  • GTL Gas To Liquids obtained by isomerizing wax (GTL wax, Gas To Liquids WAX) produced from natural gas by the Fischer-Tropsch method or the like may be used.
  • the lubricating oil composition of the present embodiment contains an antioxidant, an oily agent, a detergent dispersant, a viscosity index improver, a rust preventive agent, and a metal deactivator within a range that does not inhibit the effects of the above-mentioned lubricating oil additive composition.
  • Other additives such as antifoaming agents and antifoaming agents may also be included. These may be used alone or in combination of two or more.
  • a drug package is also provided.
  • antioxidants As the antioxidant, amine antioxidants, phenolic antioxidants, etc. used in conventional lubricating oil compositions can be used. These antioxidants may be used alone or in combination of two or more.
  • amine antioxidants include monoalkyldiphenylamine compounds such as monooctyldiphenylamine and monononyldiphenylamine; 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, , 4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; dialkyldiphenylamine compounds such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; Poly
  • phenolic antioxidants include monophenolic compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; 4,4' -methylenebis(2,6-di-tert-butylphenol) and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) and other bisphenol compounds.
  • the content of the antioxidant may be the minimum amount necessary to maintain the oxidative stability of the lubricating oil composition. Specifically, for example, it is preferably 0.01 to 1% by mass based on the total amount of the lubricating oil composition.
  • oily agent examples include aliphatic alcohols; fatty acid compounds such as fatty acids and fatty acid metal salts; ester compounds such as polyol esters, sorbitan esters, and glycerides; and amine compounds such as aliphatic amines.
  • the content of the oily agent is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
  • Detergent-dispersing agents include metal sulfonates, metal salicylates, metal phenates, succinimides, and the like.
  • the content of the detergent dispersant is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
  • Viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, olefin copolymer (e.g., ethylene-propylene copolymer, etc.), dispersed olefin copolymer, styrene copolymer (e.g., styrene-diene hydrogenated copolymers, etc.).
  • the content of the viscosity index improver is preferably 0.3 to 5% by mass, based on the total amount of the lubricating oil composition.
  • rust preventive agent examples include metal sulfonates, succinic acid esters, and alkanolamines such as alkylamines and monoisopropanolamines.
  • the content of the rust inhibitor is usually 0.01 to 5% by mass, preferably 0.03 to 3% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the effect of addition.
  • metal deactivator examples include benzotriazole and thiadiazole. From the viewpoint of the effect of addition, the preferred content of the metal deactivator is usually 0.01 to 5% by mass, preferably 0.01 to 1% by mass, based on the total amount of the lubricating oil composition.
  • antifoaming agent examples include methyl silicone oil, fluorosilicone oil, and polyacrylate.
  • the content of the antifoaming agent is usually 0.0005 to 0.01% by mass based on the total amount of the lubricating oil composition from the viewpoint of the effect of addition.
  • the 100°C kinematic viscosity of the lubricating oil composition of the present embodiment is preferably 1.0 mm 2 /s to 50 mm 2 /s, more preferably 2.0 mm 2 / s to 30 mm 2 /s, even more preferably 3.0 mm. 2 /s to 20 mm 2 /s.
  • the viscosity index of the lubricating oil composition of this embodiment is preferably 90 or more, more preferably 100 or more, and still more preferably 110 or more.
  • the kinematic viscosity and viscosity index of the lubricating oil composition are values measured or calculated according to JIS K2283:2000.
  • the lubricating oil composition (new oil) of the present embodiment has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.53 mm or less, and still more preferably 0. It is 52 mm or less.
  • the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.53 mm or less, even more preferably 0.52 mm or less.
  • the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less.
  • the lubricating oil composition of this embodiment (the oil after the ISOT test) has a wear scar diameter of preferably 0.55 mm or less, more preferably 0.50 mm or less, and even more preferably is 0.45 mm or less.
  • the wear scar diameter is preferably 0. It is 55 mm or less, more preferably 0.50 mm or less, even more preferably 0.45 mm or less.
  • the wear scar diameter is preferably 0.55 mm or less, more preferably 0.50 mm or less, still more preferably 0.45 mm or less, even more preferably is 0.43 mm or less.
  • the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
  • the lubricating oil composition (new oil) of the present embodiment has a maximum non-seizure load (LNL) of preferably 392N or more, more preferably 490N, as determined by the shell four-ball test load resistance (EP) test described in the Examples below. That's all. Further, the fusion load (WL) according to the same test is preferably 1236N or more.
  • the maximum non-seizure load (LNL) is Preferably it is 392N or more, more preferably 490N or more.
  • the fusion load (WL) is preferably 1236N or more.
  • the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more.
  • the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
  • the lubricating oil composition (oil after ISOT test) of the present embodiment preferably has a maximum non-seizure load (LNL) of 490 N or more as determined by the shell four-ball test load resistance (EP) test described in the Examples below.
  • the fusion load (WL) according to the same test is preferably 1236N or more, more preferably 1569N or more.
  • the maximum non-seizure load (LNL) is Preferably it is 490N or more.
  • the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more.
  • the copolymer (X) contained in the lubricating oil composition contains the structural unit (a), the structural unit (b), and the structural unit (d1), or the structural unit (a), the structural unit (b ), structural unit (d1), and structural unit (d2)
  • the maximum non-seizure load (LNL) is preferably 392N or more, more preferably 490N or more, and still more preferably 618N or more.
  • the fusion load (WL) is preferably 1236N or more, more preferably 1569N or more, and still more preferably 1961N or more.
  • the oil after the ISOT test means the oil after forced deterioration by the ISOT test performed by the method described in the Examples.
  • the lubricating oil composition of the present embodiment preferably generates less than 10 mg/100 mL of sludge after the ISOT test described in Examples described below.
  • the amount of sludge generated is preferably 10 mg/ It is less than 100 mL, more preferably less than 7.0 mg/100 mL, even more preferably less than 5.0 mg/100 mL.
  • the amount of sludge generated is preferably less than 10 mg/100 mL.
  • the method for producing the lubricating oil composition of this embodiment is not particularly limited.
  • the method for producing a lubricating oil composition of the present embodiment includes a step of mixing the lubricating oil additive composition and a lubricating oil base oil.
  • a method that includes a step of blending the lubricating oil additive composition with the lubricating oil base oil can be mentioned.
  • the other additives mentioned above may also be added at the same time.
  • each component may be blended in the form of a solution (dispersion) by adding diluting oil or the like. After blending each component, it is preferable to stir and disperse uniformly by a known method.
  • the lubricating oil composition of this embodiment contains the copolymer (X), it has excellent wear resistance, extreme pressure properties, and thermal stability. Therefore, the lubricating oil composition of this embodiment is, for example, gear oil (manual transmission oil, differential oil, etc.), automatic transmission oil (automatic transmission oil, etc.), continuously variable transmission oil (belt CVT oil, toroidal CVT oil, etc.) Drive system oils such as power steering oils, shock absorber oils, and electric motor oils; Oils for internal combustion engines (engines) such as gasoline engines, diesel engines, and gas engines; Hydraulic oils; Turbine oils; Compressor oils ; Fluid bearing oil; Rolling bearing oil; Refrigerating machine oil, etc., as a lubricating oil composition that can be suitably used for various purposes, and is filled into equipment used in each of these applications to lubricate between the various parts of the equipment. It can be suitably used.
  • gear oil manual transmission oil, differential oil, etc.
  • automatic transmission oil automatic transmission oil, etc.
  • continuously variable transmission oil belt CVT
  • the lubricating method using the lubricating oil composition of the present embodiment is a method of filling the lubricating oil composition into equipment used in each of the above-mentioned applications and lubricating between each part of each of the equipment. can be mentioned.
  • the lubricating oil additive composition of this embodiment can also be used by being mixed into a grease composition. That is, in this embodiment, it is also possible to provide a grease composition containing the above lubricating oil additive composition, a thickener, and a lubricating oil base oil.
  • [1] to [15] are provided.
  • the copolymer (X) has at least one of the following groups in the side chain. Phosphorus- and sulfur-containing group Phosphorus-containing group and sulfur-containing group (However, the phosphorus-containing group is a sulfur-free group, and the sulfur-containing group is a phosphorus-free group.) Said sulfur-containing group/requirement (2): When said copolymer (X) contains a phosphorus atom, the phosphorus atom content (P) in said copolymer (X) is Based on the total amount, it is 0.01% by mass to 2.00% by mass.
  • the sulfur atom content (S) in the copolymer (X) is 0.01% by mass or more based on the total amount of the copolymer (X).
  • the structural unit ( ⁇ ) is a structural unit (c) derived from the monomer (C) having a polymerizable functional group and the phosphorus- and sulfur-containing group. agent composition.
  • the structural unit ( ⁇ ) is a structural unit (d1) derived from the monomer (D1) having a polymerizable functional group and the sulfur-containing group, and a monomer (D2) derived from the monomer (D2) having a polymerizable functional group and the phosphorus-containing group.
  • the content ratio [(S)/(P)] of the sulfur atom content (S) and the phosphorus atom content (P) in the copolymer (X) is 0 by mass ratio. .10 to 3.00.
  • the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1).
  • R a1 represents a hydrogen atom or a methyl group.
  • R a2 represents an alkyl group having 8 to 20 carbon atoms.
  • R b1 is a hydrogen atom or a methyl group.
  • R b2 represents an alkylene group having 2 to 4 carbon atoms.
  • m1 represents an integer from 1 to 10.
  • R d11 is a hydrogen atom or a methyl group.
  • R d12 represents an alkylene group having 2 to 4 carbon atoms.
  • m3 represents an integer from 1 to 10.
  • R d13 represents an alkyl group having 4 to 20 carbon atoms.
  • the monomer (D1) is a compound represented by the following general formula (d1-1),
  • R d11 is a hydrogen atom or a methyl group.
  • R d12 represents an alkylene group having 2 to 4 carbon atoms.
  • m3 represents an integer from 1 to 10.
  • R d12 When m3 is an integer of 2 or more, a plurality of R d12 may be the same or different.
  • R d13 represents an alkyl group having 4 to 20 carbon atoms.
  • R d21 is a hydrogen atom or a methyl group.
  • R d22 represents an ethylene group.
  • m4 represents an integer from 1 to 6. When m4 is an integer of 2 or more, a plurality of R d22 may be the same or different.
  • n represents an integer of 1 or 2.
  • the structural unit (a) includes a structural unit (a1) derived from a monomer (A1) represented by the following general formula (a-1).
  • the lubricating oil additive composition described in . [In the above general formula (a-1), R a1 represents a hydrogen atom or a methyl group. R a2 represents an alkyl group having 8 to 20 carbon atoms.
  • the structural unit (b) includes a structural unit (b11) derived from a monomer (B11) represented by the following general formula (b-1).
  • R b1 is a hydrogen atom or a methyl group.
  • R b2 represents an alkylene group having 2 to 4 carbon atoms.
  • m1 represents an integer from 1 to 10. When m1 is an integer of 2 or more, a plurality of R b2 's may be the same or different.
  • [17] The lubricating oil additive composition according to any one of [1] to [16] above, which is used as a load-bearing additive. [18] A method of using the lubricating oil additive composition according to any one of [1] to [17] above as a load-bearing additive. [19] A lubricating oil composition containing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil. [20] A method for producing a lubricating oil composition, comprising the step of mixing the lubricating oil additive composition according to any one of [1] to [17] above and a lubricating oil base oil.
  • the sulfur content and phosphorus content of the copolymer (X) are determined by dissolving a predetermined amount of the copolymer (X) in an organic solvent (lubricating oil base oil). Calculated based on the results of measuring the sulfur and phosphorus amounts in accordance with JPI-5S-38-03 and the amount of copolymer (X) dissolved in the organic solvent.
  • Examples A1 to A6, Examples B1 to B7, Comparative Example 1 The lubricant base oil and lubricant additive composition shown below were thoroughly mixed in the amounts (mass%) shown in Tables 3 and 4, and Examples A1 to A6, Examples B1 to B7, and Comparative The lubricating oil compositions of Example 1 were each prepared. Details of the lubricant base oil and lubricant additive composition used in Examples A1 to A6, Examples B1 to B7, and Comparative Example 1 are as shown below.
  • - Copolymer (X)-A1 Produced by the method described in Production Example A1.
  • - Copolymer (X)-A2 Produced by the method described in Production Example A2.
  • - Copolymer (X)-A3 Produced by the method described in Production Example A3.
  • - Copolymer (X)-A4 Produced by the method described in Production Example A4.
  • - Copolymer (X)-A5 Produced by the method described in Production Example A5.
  • - Copolymer (X)-A6 Produced by the method described in Production Example A6.
  • - Copolymer (X)-B1 Produced by the method described in Production Example B1.
  • - Copolymer (X)-B2 Produced by the method described in Production Example B2.
  • - Copolymer (X)-B3 Produced by the method described in Production Example B3.
  • - Copolymer (X)-B4 Produced by the method described in Production Example B4.
  • - Copolymer (X)-B5 Produced by the method described in Production Example B5.
  • - Copolymer (X)-B6 Produced by the method described in Production Example B6.
  • - Copolymer (X)-B7 Produced by the method described in Production Example B7.
  • SPM1 A compound represented by the following structural formula was used.
  • R c1 is a hydrogen atom
  • R c2 is an ethylene group (an alkylene group having 2 carbon atoms)
  • m2 1
  • L 1 is -O-C(O)-R c3 -
  • R c3 is a propylene group (alkylene group having 3 carbon atoms)
  • R 1 and R 2 are isobutyl groups (alkyl group having 4 carbon atoms). It is a certain compound.
  • the sulfur content is 15.0% by mass
  • the phosphorus content is 7.3% by mass.
  • SPM3 A compound represented by the following structural formula was used.
  • R c1 is a hydrogen atom
  • R c2 is an ethylene group (an alkylene group having 2 carbon atoms)
  • m2 1
  • L 1 is -O-C(O)-R c3 -
  • R c3 is an ethylene group (alkylene group having 2 carbon atoms)
  • R 1 and R 2 are ethylene groups (alkyl group having 2 carbon atoms); It is a certain compound.
  • the sulfur content is 18.0% by mass, and the phosphorus content is 8.7% by mass. It was used as monomer (C).
  • IRGALUBE353 is a compound represented by the following structural formula.
  • copolymer (X)-A1 was diluted with mineral oil so that the content of copolymer (X)-A1 was 50% by mass, and mixed into lubricating base oil.
  • Copolymer (X)-A2) was obtained by carrying out the same operation as in Production Example A1 except that 0.44 g (1.1 mmol) of SPM2 was charged instead of SPM1.
  • the mass average molecular weight (Mw) of copolymer (X)-A2 was 19,700, and the molecular weight distribution (Mw/Mn) was 2.0. Further, the phosphorus content of copolymer (X)-A2 was 760 mass ppm, and the sulfur content was 1700 mass ppm.
  • Copolymer (X)-A2 was diluted with mineral oil so that the content of copolymer (X)-A2 was 50% by mass, and mixed into lubricating base oil.
  • Copolymer (X)-A5 was obtained by carrying out the same operation as in Production Example A2 except that 22.0 g of 2-propanol was added as a solvent.
  • the mass average molecular weight (Mw) of copolymer (X)-A5 was 34,200, and the molecular weight distribution (Mw/Mn) was 2.3. Further, the phosphorus content of copolymer (X)-A5 was 800 mass ppm, and the sulfur content was 1700 mass ppm.
  • Copolymer (X)-A5 was diluted with mineral oil so that the content of copolymer (X)-A5 was 50% by mass, and mixed into lubricating base oil.
  • Poly(meth)acrylate copolymer (X)-A6 is diluted with mineral oil so that the content of poly(meth)acrylate copolymer (X)-A6 is 50% by mass, and then mixed with lubricating oil. Mixed with base oil.
  • composition of copolymer (X)-A1 to copolymer (X)-A6, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-A1 to copolymer (X)-A6 , and molecular weight distribution (Mw/Mn) are shown in Table 1.
  • Mw/Mn molecular weight distribution
  • copolymer (X)-B1 was diluted with mineral oil so that the content of copolymer (X)-B1 was 50% by mass, and mixed into lubricating base oil.
  • Copolymer (X)-B2) was obtained by carrying out the same operation as in Production Example B1 except that 0.46 g (1.9 mmol) of OTA was charged instead of DTA.
  • the mass average molecular weight (Mw) of copolymer (X)-B2 was 18,200, and the molecular weight distribution (Mw/Mn) was 1.9. Further, the phosphorus content of copolymer (X)-B2 was 3000 mass ppm, and the sulfur content was 1060 mass ppm.
  • Copolymer (X)-B2 was diluted with mineral oil so that the content of copolymer (X)-B2 was 50% by mass, and mixed into lubricating base oil.
  • Copolymer (X)-B3) was obtained by carrying out the same operation as in Production Example B1 except that 23.8 g of 2-propanol was charged as a solvent.
  • the mass average molecular weight (Mw) of copolymer (X)-B3 was 46,400, and the molecular weight distribution (Mw/Mn) was 3.2. Further, the phosphorus content of copolymer (X)-B3 was 2,800 mass ppm, and the sulfur content was 1,040 mass ppm.
  • Copolymer (X)-B3 was diluted with mineral oil so that the content of copolymer (X)-B3 was 50% by mass, and mixed into lubricating base oil.
  • Copolymer (X)-B5) was obtained by carrying out the same operation as in Production Example B2 except that 23.8 g of 2-propanol was charged as a solvent.
  • the mass average molecular weight (Mw) of copolymer (X)-B5 was 48,000, and the molecular weight distribution (Mw/Mn) was 3.3. Further, the phosphorus content of copolymer (X)-B5 was 2,800 mass ppm, and the sulfur content was 1,220 mass ppm.
  • Copolymer (X)-B5 was diluted with mineral oil so that the content of copolymer (X)-B5 was 50% by mass, and mixed into lubricating base oil.
  • copolymer (X)-B6 was diluted with mineral oil so that the content of copolymer (X)-B6 was 50% by mass, and mixed into lubricating base oil.
  • composition of copolymer (X)-B1 to copolymer (X)-B7, sulfur content and phosphorus content, mass average molecular weight (Mw) of copolymer (X)-B1 to copolymer (X)-B7 , and the molecular weight distribution (Mw/Mn) are shown in Table 2.
  • Mw mass average molecular weight
  • ⁇ Shell wear test> The wear resistance of the lubricating oil composition was determined using a shell abrasion tester in accordance with ASTM D 4172, setting the test conditions to be a load of 30 kg, a rotation speed of 1,200 rpm, a temperature of 80°C, and a test time of 30 minutes. was evaluated. The results were expressed as the wear scar diameter (mm) of the test hard ball. In this test, wear resistance was judged to be good if the wear scar diameter was 0.55 mm or less.
  • ⁇ ISOT test> A copper piece and an iron piece were added as catalysts to the test oil (lubricating oil composition), and an ISOT test in accordance with JIS K 2514-1:2013 was conducted to forcefully degrade the test oil.
  • the test temperature (oil temperature) was 150°C.
  • the amount of sludge (mg/100 mL) was measured for the test oil 24 hours after the start of the ISOT test in accordance with JIS B 9931. And, if the amount of sludge was less than 10 mg/100 mL, it was determined that the thermal stability was good.
  • the above-mentioned shell wear test and shell four-ball test load resistance (EP) test were conducted on the test oil 24 hours after the start of the ISOT test. As with the new oil, it was determined that the wear resistance was good if the wear scar diameter was 0.55 mm or less. Furthermore, if the maximum non-seizure load (LNL) was 392N or more and the fusion load (WL) was 1236N or more, it was determined that the extreme pressure property was good.
  • LNL maximum non-seizure load
  • WL fusion load
  • the lubricating oil composition containing Copolymer (X)-B5, Copolymer (X)-B6, or Copolymer (X)-B7 has excellent wear resistance, extreme pressure properties, and thermal stability.
  • the wear resistance and extreme pressure properties are excellent.
  • the results shown in Comparative Example 1 show that a lubricating oil composition containing a low molecular weight sulfur- and phosphorus-containing compound has insufficient wear resistance and extreme pressure properties, and is clearly inferior in thermal stability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne une composition d'additif pour huiles lubrifiantes comprenant un copolymère (X) qui comprend les motifs constitutifs (a) et (b) suivants et satisfait les exigences (1) à (3) suivantes. Motif constitutif (a) : Un motif constitutif dérivé d'un monomère (A) ayant un groupe (méth)acryloyle et un groupe alkyle en C8-C20. Motif constitutif (b) : Un motif constitutif dérivé d'un monomère (B) ayant un groupe (méth)acryloyle et un groupe polaire. Exigence (1) : Le copolymère (X) a une ou plusieurs chaînes latérales comprenant au moins l'un quelconque des éléments suivants : un groupe contenant du phosphore et du soufre ; un groupe contenant du phosphore et un groupe contenant du soufre (le groupe contenant du phosphore est un groupe exempt de soufre et le groupe contenant du soufre est un groupe exempt de phosphore.) ; et le groupe contenant du soufre. Exigence (2) : Lorsque le copolymère (X) contient des atomes de phosphore, la teneur en atomes de phosphore (P) dans le copolymère (X) est de 0,01 à 2,00 % en masse par rapport à l'ensemble du copolymère (X). Exigence (3) : La teneur en atomes de soufre (S) dans le copolymère (X) est de 0,01 à 2,00 % en masse par rapport à l'ensemble du copolymère (X).
PCT/JP2023/024357 2022-06-30 2023-06-30 Composition d'additif pour huiles lubrifiantes et composition d'huile lubrifiante WO2024005185A1 (fr)

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JP2022-106709 2022-06-30
JP2022-106711 2022-06-30
JP2022106709A JP2024006117A (ja) 2022-06-30 2022-06-30 潤滑油用添加剤組成物及び潤滑油組成物
JP2022-106706 2022-06-30
JP2022106711A JP2024006118A (ja) 2022-06-30 2022-06-30 潤滑油用添加剤組成物及び潤滑油組成物
JP2022106706A JP2024006116A (ja) 2022-06-30 2022-06-30 潤滑油用添加剤組成物及び潤滑油組成物

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JPH0641160A (ja) * 1992-06-02 1994-02-15 Ciba Geigy Ag 潤滑剤添加剤としてのビスチオ燐酸誘導体
JPH06505276A (ja) * 1990-11-01 1994-06-16 モービル・オイル・コーポレーション アクリレートとメタクリレートのポリマーのジメルカプト誘導体をベースとした耐摩耗性／耐酸化性の添加剤とそのアミン反応生成物
JPH06172774A (ja) * 1990-06-18 1994-06-21 Tonen Corp 作動・潤滑・流体継手用組成物
JP2009149874A (ja) * 2007-11-30 2009-07-09 Sanyo Chem Ind Ltd 粘度指数向上剤及び潤滑油組成物
JP2016065221A (ja) * 2014-09-16 2016-04-28 三洋化成工業株式会社 粘度指数向上剤組成物及び潤滑油組成物
JP2016074657A (ja) * 2014-10-08 2016-05-12 アフトン・ケミカル・コーポレーションＡｆｔｏｎ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ リン含有化合物及びその使用
JP2016169368A (ja) * 2015-03-12 2016-09-23 三洋化成工業株式会社 潤滑油組成物
JP2017106016A (ja) * 2015-12-09 2017-06-15 株式会社日本触媒 粘度指数向上剤並びに潤滑油組成物
KR20180112211A (ko) * 2017-03-31 2018-10-12 한국화학연구원 디카르복실산 유도체 및 이를 포함하는 내마모제 및 윤활유 조성물
JP2020026519A (ja) * 2018-08-09 2020-02-20 三洋化成工業株式会社 粘度指数向上剤及び潤滑油組成物
JP7061242B1 (ja) * 2020-12-28 2022-04-27 出光興産株式会社 潤滑油用添加剤組成物及び潤滑油組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06172774A (ja) * 1990-06-18 1994-06-21 Tonen Corp 作動・潤滑・流体継手用組成物
JPH06505276A (ja) * 1990-11-01 1994-06-16 モービル・オイル・コーポレーション アクリレートとメタクリレートのポリマーのジメルカプト誘導体をベースとした耐摩耗性／耐酸化性の添加剤とそのアミン反応生成物
JPH0641160A (ja) * 1992-06-02 1994-02-15 Ciba Geigy Ag 潤滑剤添加剤としてのビスチオ燐酸誘導体
JP2009149874A (ja) * 2007-11-30 2009-07-09 Sanyo Chem Ind Ltd 粘度指数向上剤及び潤滑油組成物
JP2016065221A (ja) * 2014-09-16 2016-04-28 三洋化成工業株式会社 粘度指数向上剤組成物及び潤滑油組成物
JP2016074657A (ja) * 2014-10-08 2016-05-12 アフトン・ケミカル・コーポレーションＡｆｔｏｎ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ リン含有化合物及びその使用
JP2016169368A (ja) * 2015-03-12 2016-09-23 三洋化成工業株式会社 潤滑油組成物
JP2017106016A (ja) * 2015-12-09 2017-06-15 株式会社日本触媒 粘度指数向上剤並びに潤滑油組成物
KR20180112211A (ko) * 2017-03-31 2018-10-12 한국화학연구원 디카르복실산 유도체 및 이를 포함하는 내마모제 및 윤활유 조성물
JP2020026519A (ja) * 2018-08-09 2020-02-20 三洋化成工業株式会社 粘度指数向上剤及び潤滑油組成物
JP7061242B1 (ja) * 2020-12-28 2022-04-27 出光興産株式会社 潤滑油用添加剤組成物及び潤滑油組成物

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