JP6077955B2 - Poly (meth) acrylate viscosity index improver, and lubricating oil additive and lubricating oil composition containing the viscosity index improver - Google Patents

Description

  The present invention relates to a poly (meth) acrylate viscosity index improver, and a lubricating oil additive and a lubricating oil composition containing the viscosity index improver.

  Conventionally, in the field of lubricating oil, improvement of lubricating oil has been studied from the viewpoint of energy saving. In particular, in recent years, the trend of protecting the global environment has increased, and the demand for an energy saving improvement effect on lubricating oil has become even stronger.

  For example, in the case of a lubricating oil used for an internal combustion engine such as an automobile engine (also referred to as “lubricating oil for an internal combustion engine” or “engine oil”), as one means for improving fuel efficiency, a lubricating base oil is used. A method for increasing the viscosity index of a lubricating oil by adding a viscosity index improver is known. As for the viscosity index improver, the use of various viscosity index improvers has been proposed so far, but in particular, the use of poly (meth) acrylate-based viscosity index improvers has been proposed (for example, Patent Documents 1 to 3). 7).

JP 7-48421 A JP-A-7-62372 JP-A-6-145258 JP-A-3-100099 JP 2002-302687 A JP 2004-124080 A JP 2005-187736 A

  However, when the conventional poly (meth) acrylate viscosity index improver is used, there is room for improvement in terms of high shear viscosity in order to achieve practically sufficient fuel economy. In particular, 0W-20, which has a high demand for fuel economy, needs to maintain a high shear viscosity at 150 ° C. at a certain high level, while reducing the high shear viscosity at 100 ° C. On the other hand, with a conventional poly (meth) acrylate viscosity index improver, it is difficult to reduce the high shear viscosity at 100 ° C. while maintaining the high shear viscosity at 150 ° C.

  Recently, in addition to fuel saving, it is required to secure fluidity at low temperatures (especially extremely low temperatures). Furthermore, in addition to these, fuel consumption sustainability is also required. Since the shear stability of the viscosity index improver greatly influences the fuel efficiency, it is desirable that the viscosity index improver is excellent in shear stability. However, conventional poly (meth) acrylate-based viscosity index improvers do not necessarily satisfy all of fuel economy, low-temperature fluidity and shear stability.

  Therefore, the present invention can sufficiently reduce the high shear viscosity at 100 ° C. while maintaining a high shear viscosity at 150 ° C., and can sufficiently ensure low-temperature fluidity, and has high shear stability. It is an object of the present invention to provide a viscosity index improver exhibiting the above, a lubricating oil additive and a lubricating oil composition containing the viscosity index improver.

  As a result of intensive studies, the inventors of the present invention have a specific structure, and poly (meth) acrylate having a weight average molecular weight Mw and a ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn satisfying a specific condition. The system viscosity index improver can sufficiently reduce the high shear viscosity at 100 ° C. while maintaining the high shear viscosity at 150 ° C., and can secure low-temperature fluidity, and has high shear stability. As a result, the present invention has been completed.

［式（１）及び（２）中、Ｒ_１は水素又はメチル基を示し、Ｒ_２は下記一般式（３）で表される基を示し、Ｒ_３は直鎖又は炭素数５以下の分岐を有する炭素数１〜１８のアルキル基を示す。

式（３）中、ｍ及びｎは、ｍ≧５かつｎ≧４かつｍ＋ｎ≦３１を満たす整数である。］ That is, the present invention comprises a core part, a polymer chain containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), and one end of the polymer chain is a core part. Three or more arm portions bonded to each other, the weight average molecular weight Mw is 100,000 or more, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 1.6 or less. A poly (meth) acrylate viscosity index improver.

[In the formulas (1) and (2), R ₁ represents hydrogen or a methyl group, R ₂ represents a group represented by the following general formula (3), and R ₃ represents a straight chain or a branched chain having 5 or less carbon atoms. And an alkyl group having 1 to 18 carbon atoms.

In formula (3), m and n are integers that satisfy m ≧ 5, n ≧ 4, and m + n ≦ 31. ]

  Moreover, this invention provides the lubricating oil additive containing the said poly (meth) acrylate type viscosity index improver.

  The present invention also provides a lubricating oil composition comprising a lubricating base oil and the poly (meth) acrylate viscosity index improver.

  According to the present invention, while maintaining a high shear viscosity at 150 ° C., the high shear viscosity at 100 ° C. can be sufficiently reduced, and low temperature fluidity can be sufficiently ensured, and high shear stability. And a lubricating oil additive and a lubricating oil composition containing the viscosity index improver can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

［式（１）及び（２）中、Ｒ^１は水素又はメチル基を示し、Ｒ^２は下記一般式（３）で表される基を示し、Ｒ^３は直鎖又は炭素数５以下の分岐を有する炭素数１〜１８のアルキル基を示す。

式（３）中、ｍ及びｎは、ｍ≧５かつｎ≧４かつｍ＋ｎ≦３１を満たす整数である。］ [First Embodiment: Poly (meth) acrylate viscosity index improver]
The poly (meth) acrylate viscosity index improver according to the first embodiment is a polymerization including a core, a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2). And three or more arm portions made of chains. The poly (meth) acrylate viscosity index improver has a weight average molecular weight Mw (hereinafter, simply referred to as “Mw” in some cases) of 100,000 or more, and a weight average molecular weight Mw and a number average molecular weight Mn (hereinafter, depending on circumstances). The ratio Mw / Mn (hereinafter simply referred to as “Mw / Mn”) is 1.6 or less.

[In the formulas (1) and (2), R ¹ represents hydrogen or a methyl group, R ² represents a group represented by the following general formula (3), and R ³ represents a straight chain or a branched chain having 5 or less carbon atoms. And an alkyl group having 1 to 18 carbon atoms.

In formula (3), m and n are integers that satisfy m ≧ 5, n ≧ 4, and m + n ≦ 31. ]

R ¹ may be either hydrogen or a methyl group, but is preferably a methyl group.

R ² is preferably m from 5 to 16 and n from 4 to 15, more preferably m from 6 to 15, and n from 6 to 10, and m from 7 from the viewpoint of viscosity reduction. 10 to 10 and n is more preferably 6 to 9. When the structural unit represented by the general formula (1) contained in the polymer chain is 2 or more, R ¹ and R ² may be the same or different among the structural units.

  As described above, the polymer chain constituting the arm portion includes the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). The structural unit represented by the general formula (1) is preferably contained in an amount of 20 to 80% by weight, more preferably 20 to 70% by weight, based on the total amount of the structural units contained in the polymer chain, and more preferably 20 to 50%. More preferably, it is contained by mass%. In addition, the polymer chain preferably contains 20-80% by mass of the structural unit represented by the general formula (2) based on the total amount of the structural unit contained in the polymer chain, from the viewpoint of fuel economy. It is more preferable to contain 30-80 mass%, and it is still more preferable to contain 50-80 mass%. The polymer chain is a combination of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), and is based on the total amount of the structural units contained in the polymer chain. It is preferable to contain at least 80% by mass, more preferably at least 80% by mass, still more preferably at least 90% by mass, and most preferably at least 100% by mass.

When the structural unit represented by the general formula (2) contained in the polymer chain is 2 or more, R ¹ and R ³ may be the same or different among the structural units. When two or more structural units different in R ³ are included, from the viewpoint of the solubility of poly (meth) acrylate, the structural unit in which R ³ is a methyl group is based on the total amount of structural units contained in the polymer chain. 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 20 to 45% by mass. From the viewpoint of low-temperature fluidity, it is preferable that the structural unit in which R ³ is an alkyl group having 18 carbon atoms is contained in an amount of 5 to 50% by mass based on the total amount of structural units contained in the polymer chain. More preferably, it is contained in an amount of 45% by mass, and still more preferably 20-40% by mass.

  The polymer chain may contain only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may further contain other structural units. Good. Moreover, one end is couple | bonded with the core part among the terminals of a polymer chain, and there is no restriction | limiting in particular in the atom couple | bonded about the other end. Among such polymer chains, only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) are included, one end is bonded to the core portion, and the other end is A polymer chain bonded to a hydrogen atom, that is, a polymer chain represented by the following general formula (4) is preferable.

In formula (4), R ¹ represents hydrogen or a methyl group, and R ⁴ is a group represented by the above general formula (3), or a straight chain or a C 1-18 having a branch having 5 or less carbon atoms. An alkyl group is shown, and n is an integer selected so that Mw and Mw / Mn satisfy the above conditions. n is an integer of 400 to 2000, for example.

  The weight average molecular weight Mw per arm part is appropriately selected so that the Mw of the poly (meth) acrylate viscosity index improver satisfies the above conditions, but is preferably 10,000 or more, and 15,000. More preferably, it is more preferably 18,000 or more.

  The number average molecular weight Mn per arm is appropriately selected so that the Mw / Mn of the poly (meth) acrylate viscosity index improver satisfies the above-mentioned conditions, but is preferably 8,000 or more. Is more preferably 15,000 or more, and further preferably 15,000 or more.

  The weight average molecular weight Mw of the poly (meth) acrylate viscosity index improver is 100,000 or more, preferably 125,000 or more, more preferably 150,000 or more from the viewpoint of fuel saving performance. Preferably, it is more preferably 175,000 or more. The upper limit of Mw is not particularly limited, but Mw is, for example, 500,000 or less.

  The number average molecular weight Mn of the poly (meth) acrylate viscosity index improver is appropriately selected so that Mw / Mn satisfies the above conditions. From the viewpoint of fuel saving performance, Mn is preferably 75,000 or more, more preferably 94,000 or more, and further preferably 110,000 or more. Although the upper limit of Mn is not particularly limited, Mn is, for example, 300,000 or less.

  Mw / Mn of the poly (meth) acrylate viscosity index improver is 1.6 or less, but from the viewpoint of fuel saving characteristics, it is preferably 1.5 or less, more preferably 1.4 or less. Preferably, it is 1.2 or less. Further, Mw / Mn is preferably 1.00 or more, more preferably 1.01 or more, and further preferably 1.02 or more, from the viewpoint of fuel saving characteristics.

  In the present invention, “weight average molecular weight Mw”, “number average molecular weight Mn” and “ratio Mw / Mn of weight average molecular weight Mw and number average molecular weight Mn” are Mw, Mn and Mw obtained by GPC analysis. / Mn (polystyrene (standard sample) conversion value). Mw / Mn of the poly (meth) acrylate viscosity index improver and Mw and Mn per arm part can be measured, for example, as follows.

  Tetrahydrofuran is used as a solvent and diluted to prepare a solution with a sample concentration of 2% by mass. The sample solution is analyzed using a GPC apparatus (Waters Alliance 2695). The analysis is carried out using a column having a solvent flow rate of 1 ml / min, an analyzable molecular weight of 10,000 to 256,000, and a refractive index as a detector. The relationship between the column retention time and the molecular weight is determined using a polystyrene standard with a clear molecular weight, a calibration curve is separately prepared, and the molecular weight is determined from the obtained retention time. The molecular weight of the arm (Mw and Mn) can be calculated by dividing the obtained molecular weight (Mw and Mn) by the number of functional groups of the initiator.

  The core portion is derived from a compound having three or more functional groups that react with the carbon-carbon double bond of the acryloyl group. Examples of the compound having three or more functional groups that react with the carbon-carbon double bond of the acryloyl group include 1,1,1-tris (2-bromoisobutyloxymethylene) ethane, pentaerythritol tetrakis (2-bromoiso). Butyrate) and dipentaerythritol hexakis (2-bromoisobutyrate).

  The number of arm portions of the poly (meth) acrylate viscosity index improver corresponds to the number of the functional groups. From the viewpoint of shear stability, the number of arm portions, that is, the number of functional groups is preferably 2 to 12, more preferably 2 to 8, and still more preferably 3 to 6.

  Although it does not restrict | limit especially as a manufacturing method of the poly (meth) acrylate type viscosity index improver which concerns on this embodiment, For example, a polymerization catalyst is added to the mixed solution containing an alkyl (meth) acrylate, an initiator, and a solvent, and alkyl ( A method of polymerizing (meth) acrylate is mentioned.

  As the alkyl (meth) acrylate, an alkyl (meth) acrylate represented by the following general formula (5) and an alkyl (meth) acrylate represented by the following general formula (6) can be used.

In formulas (5) and (6), R ¹ represents hydrogen or a methyl group, R ² represents a group represented by the general formula (3), and R ³ represents a straight chain or a branch having 5 or less carbon atoms. The C1-C18 alkyl group which has is shown.

R ¹ is preferably a methyl group. R ² is preferably m of 5 to 16 and n of 4 to 15, more preferably m of 6 to 15, and n of 6 to 10, m of 7 to 10, and n of 6 to 6. What is 9 is still more preferable.

  As the alkyl (meth) acrylate, as described above, the alkyl (meth) acrylate represented by the general formula (5) and the alkyl (meth) acrylate represented by the general formula (6) can be used. The content of the alkyl (meth) acrylate represented by the general formula (5) is preferably 20 to 80% by mass and more preferably 20 to 70% by mass based on the total amount of the alkyl (meth) acrylate. Preferably, it is 20-50 mass%. Moreover, it is preferable that content of the alkyl (meth) acrylate represented by the said General formula (5) is 20-80 mass% on the basis of the alkyl (meth) acrylate whole quantity basis, and is 30-80 mass%. Is more preferable, and it is still more preferable that it is 50-80 mass%.

As the alkyl (meth) acrylate represented by the general formula (6), one kind of the alkyl (meth) acrylate represented by the general formula (6) may be used alone, or two or more kinds may be mixed and used. However, it is preferable to use a mixture of two or more. When using 2 or more types mixedly, it is preferable that content of methyl (meth) acrylate whose R < ² > is a methyl group is 5-50 mass% on the basis of alkyl (meth) acrylate whole quantity, More preferably, it is 20 mass%, and it is still more preferable that it is 20-45 mass%. The content of ^{R 2} is alkyl (meth) acrylate is an alkyl group of 18 carbon atoms, an alkyl (meth) acrylate total amount of preferably 5 to 50 wt%, 10 to 45 wt% It is more preferable, and it is still more preferable that it is 20-40 mass%.

  As the initiator, one derived from a compound having three or more functional groups that react with the carbon-carbon double bond of the acryloyl group can be used. For example, 1,1,1-tris (2-bromoisobutyloxy Methylene) ethane, pentaerythritol tetrakis (2-bromoisobutyrate), dipentaerythritol hexakis (2-bromoisobutyrate) can be used.

  As the solvent, for example, highly refined mineral oil, anisole, and toluene can be used. As a preferred solvent, highly refined mineral oil can be exemplified.

  Examples of the polymerization catalyst include copper (II) bromide, tris (2-pyridylmethyl) amine, azobisisobutyronitrile, tin (II) 2-ethylhexanoate, and tris [2- (dimethylamino) ethyl]. Amines can be used. Preferred examples of the polymerization catalyst include copper (II) bromide, tris (2-pyridylmethyl) amine, azobisisobutyronitrile, and tin (II) 2-ethylhexanoate. You may use these polymerization catalysts individually by 1 type or in mixture of 2 or more types.

  The reaction temperature at the time of polymerizing the alkyl (meth) acrylate can be appropriately selected. As preferable reaction temperature, 60-100 degreeC can be illustrated. By setting the reaction temperature within the above range, the Mw / Mn of the resulting poly (meth) acrylate viscosity index improver tends to be 1.6 or less. For example, when the reaction temperature is 60 to 80 ° C., Mw / Mn tends to be 1.0 to 1.2, and when the reaction temperature is 80 to 90 ° C., Mw / Mn is 1.2 to 1.4. When the reaction temperature is 90 to 100 ° C., Mw / Mn tends to be 1.4 to 1.6.

  The reaction time depends on the reaction conditions such as the raw material alkyl (meth) acrylate, polymerization reagent, solvent and initiator, reaction temperature, and the like, and the desired poly (meth) acrylate Mw and Mw / Mn. It can be selected as appropriate. Examples of preferable reaction time include 8 to 16 hours.

  The polymerization of the alkyl (meth) acrylate is preferably performed in a nitrogen atmosphere.

[Second Embodiment: Lubricating Oil Additive]
The lubricating oil additive according to the second embodiment of the present invention comprises a core, a structural unit represented by the general formula (1), and a polymer chain including the structural unit represented by the general formula (2). And an arm part in which one end of the polymer chain is bonded to the core part, the weight average molecular weight Mw is 100,000 or more, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is A poly (meth) acrylate viscosity index improver that is 1.6 or less is contained. The poly (meth) acrylate-based viscosity index improver in the present embodiment is the same as the viscosity index improver in the first embodiment, and a duplicate description is omitted here.

  The lubricating oil additive may consist only of the above poly (meth) acrylate viscosity index improver, or a mixture of the viscosity index improver and other additives (ie, additive composition). It may be. When the lubricating oil additive is a mixture of the viscosity index improver and other additives, the mixing ratio is not particularly limited and can be appropriately selected according to the application.

  Other additives include viscosity index improvers other than the above poly (meth) acrylate viscosity index improvers, antioxidants, antiwear agents (or extreme pressure agents), corrosion inhibitors, rust inhibitors, viscosity indexes Examples thereof include additives such as improvers, pour point depressants, demulsifiers, metal deactivators, antifoaming agents, and ashless friction modifiers. These additives can be used individually by 1 type or in combination of 2 or more types.

  As the viscosity index improver other than the above poly (meth) acrylate viscosity index improver, poly (meth) acrylate viscosity index improver other than the above poly (meth) acrylate viscosity index improver, polyisobutene viscosity index Examples thereof include an improver, an ethylene-propylene copolymer viscosity index improver, and a styrene-butadiene hydrogenated copolymer viscosity index improver.

  Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as zinc, copper, and molybdenum.

  Examples of phenolic antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′. -Bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6) -Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl-6-silane) (Rohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6 -Di-tert-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethylphenol), 4,4'-thiobis (2-methyl-6- tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy) -5-tert-butylbenzyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 2,2'-thio -Diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tridecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, stearyl 3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octyl-3- (3-methyl-5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like. You may use these in mixture of 2 or more types.

  As the amine-based antioxidant, for example, known amine-based antioxidants generally used for lubricating oils such as aromatic amine compounds, alkyldiphenylamines, alkylnaphthylamines, phenyl-α-naphthylamines, alkylphenyl-α-naphthylamines, etc. Agents.

  Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.

  Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.

  Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.

Examples of antifoaming agents include silicone oils having a kinematic viscosity at 25 ° C. of 1,000 to 100,000 mm ² / s, alkenyl succinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, and methyl salicylates. o-Hydroxybenzyl alcohol and the like can be mentioned.

  As the ashless friction modifier, any compound usually used as an ashless friction modifier for lubricating oils can be used, for example, an alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly 6 to 30 carbon atoms. And ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols and aliphatic ethers having at least one linear alkyl group or linear alkenyl group in the molecule. Various ashless friction modifiers exemplified in International Publication No. 2005/037967 pamphlet such as nitrogen-containing compounds and acid-modified derivatives thereof described in JP-A-2009-286831 can also be used.

  Moreover, the lubricating oil additive according to this embodiment may further contain a solvent. As the solvent, highly refined mineral oil, solvent refined base oil, and synthetic oil can be used. Among these, it is preferable to use highly refined mineral oil. When the lubricating oil additive contains a solvent, the content of the solvent is preferably 5 to 75 mass%, more preferably 30 to 60 mass%, based on the total amount of the lubricating oil additive.

[Third Embodiment: Lubricating Oil Composition]
The lubricating oil composition according to the third embodiment comprises a lubricating base oil, a polymer chain containing a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and An arm part in which the polymer chain is bonded to the core part, the weight average molecular weight Mw is 100,000 or more, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 1.6. A poly (meth) acrylate viscosity index improver which is: Here, the lubricating oil composition according to the present embodiment includes a mode including the lubricating base oil and the lubricating oil additive according to the second embodiment. The poly (meth) acrylate-based viscosity index improver in the present embodiment is the same as the poly (meth) acrylate-based viscosity index improver in the first embodiment and the second embodiment, and is included in the lubricating oil composition. The other additives and solvents to be obtained are the same as the other additives and solvents in the second embodiment, and redundant description is omitted here.

  The lubricating base oil is not particularly limited, and a lubricating base oil used for ordinary lubricating oil can be used. Specifically, a mineral oil base oil, a synthetic oil base oil, or a mixture of two or more kinds of lubricant base oils selected from these can be used.

  Examples of mineral oil base oils include, for example, solvent oil removal, solvent extraction, hydrocracking, solvent removal of lubricating oil fractions obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil. Examples thereof include those refined by performing one or more treatments such as dewaxing and hydrorefining, or base oils produced by a method of isomerizing wax isomerized mineral oil or GTL wax (gas-tuly wax).

  Synthetic oil-based lubricating oils include, for example, polybutene or hydrides thereof; poly-α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl Diesters such as adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate; alkylnaphthalene And aromatic synthetic oils such as alkylbenzene or mixtures thereof.

The kinematic viscosity of the lubricating base oil at 100 ° C. is preferably 2.5 to 10.0 mm ² / s, more preferably 3.0 to 8.0 mm ² / s, still more preferably 3.5 to 6.0 mm ^2. / S. The viscosity index of the lubricating base oil is preferably 90 to 165, more preferably 100 to 155, and still more preferably 120 to 150.

  The saturated content of the lubricating base oil by chromatographic analysis is preferably 80% or more, more preferably, in order to facilitate the effects of additives such as the poly (meth) acrylate viscosity index improver according to the first embodiment. 85% or more, more preferably 90% or more, and most preferably 95% or more.

  The content of the poly (meth) acrylate viscosity index improver according to the first embodiment is preferably 0.1 to 20.0 mass%, more preferably 0.5 to 15 based on the total amount of the lubricating oil composition. It is 0.0 mass%, More preferably, it is 1.0-10.0 mass%. When the content is equal to or higher than the lower limit value, it is easy to obtain a sufficient addition effect. On the other hand, when the content is equal to or lower than the upper limit value, shear stability is increased and fuel consumption sustainability is improved.

The kinematic viscosity at 100 ° C. of the lubricating oil composition is preferably 3.0 to 16.3 mm ² / s, more preferably 3.5 to 12.5 mm ² / s, still more preferably 4.0 to 9.3 mm ^2. / S. When the kinematic viscosity at 100 ° C. is not less than the above lower limit value, it becomes easy to ensure lubricity, while when the kinematic viscosity at 100 ° C. is not more than the above upper limit value, fuel economy is further improved. The kinematic viscosity at 100 ° C. in the present invention means the kinematic viscosity at 100 ° C. defined in JIS K-2283-1993.

  The viscosity index of the lubricating oil composition is preferably 150 to 250, more preferably 160 to 240, and still more preferably 170 to 230. When the viscosity index is equal to or higher than the lower limit, fuel economy can be further improved while maintaining the HTHS viscosity, and the low temperature viscosity is easily lowered. On the other hand, when the viscosity index is less than or equal to the above upper limit, low temperature fluidity, solubility of additives, and compatibility with sealing materials can be ensured. In addition, the viscosity index in this invention means the viscosity index prescribed | regulated to JISK2283-1993.

  The HTHS viscosity at 150 ° C. of the lubricating oil composition is preferably 1.7 mPa · s or more, more preferably 2.0 mPa · s or more, still more preferably 2.3 mPa · s or more, and most preferably 2.6 mPa · s or more. It is. When the HTHS viscosity at 150 ° C. is equal to or higher than the lower limit, evaporation of the lubricating oil composition can be suppressed, and lubricity can be ensured. Moreover, the HTHS viscosity at 100 ° C. of the lubricating oil composition is preferably 5.2 mPa · s or less, more preferably 5.1 mPa · s or less, and further preferably 5.0 mPa · s or less. When the HTHS viscosity at 100 ° C. is not more than the above upper limit value, higher fuel economy can be obtained. In the present invention, the HTHS viscosity at 150 ° C. or 100 ° C. means a high temperature high shear viscosity at 150 ° C. or 100 ° C. as defined in ASTM D-4683.

  The MRV viscosity at −40 ° C. of the lubricating oil composition is preferably 60,000 mPa · s or less, more preferably 40,000 mPa · s or less, and still more preferably 30,000 mPa · s or less. When the MRV viscosity at −40 ° C. is not more than the above upper limit value, the pumping characteristics at low temperature are excellent. In the present invention, the MRV viscosity at −40 ° C. means the MRV viscosity at −40 ° C. defined by ASTM D-4684.

  The shear stability of the lubricating oil composition is evaluated by, for example, the viscosity reduction rate. The viscosity reduction rate of the lubricating oil composition is preferably 5.2% or less, more preferably 5.1% or less, and still more preferably 5.0% or less. When the viscosity reduction rate is less than or equal to the above upper limit, fuel economy is excellent. The viscosity reduction rate referred to in the present invention means the viscosity reduction rate in the ultrasonic shear test. Specifically, in accordance with JASO M347-95 (automatic transmission oil shear stability test method), only the sample volume is used. It means the rate of decrease in thickening due to the viscosity index improver when evaluated under increased conditions.

  More specifically, after adjusting the output with the standard oil A defined in the ASTM test method, a shear test was performed under the conditions of an amplitude of 28 μm, a vibration frequency of 10 KHz, an irradiation time of 10 minutes, and a sample volume of 50 mL. It means the permanent shear stability index PSSI (Permanent Shear Stability Index) calculated based on the measured kinematic viscosity. PSSI is calculated by increasing the viscosity (V1) of the viscosity index improver at 100 ° C. measured before the shear test and increasing the viscosity index improver at 100 ° C. measured after the shear test. Based on the viscosity (V2), it is calculated by ((V1−V2) / V1 × 100) (%).

  The viscosity index improver according to the first embodiment described above, the lubricating oil additive according to the second embodiment, and the lubricating oil composition according to the third embodiment include a lubricating oil for an internal combustion engine, a drive system lubricating oil, and the like. Although it can be used in a wide range of fields, it is particularly useful in the field of lubricating oils for internal combustion engines. In this case, the fuel of the internal combustion engine may be either gasoline or diesel fuel.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to a following example at all.

[Example 1]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 1”).

A 300 ml 5-neck separable flask equipped with a vertical metal stirring blade (with vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen and a sample inlet was charged with methyl methacrylate (R ^{1 in} formula (6) and Compound in which R ² is both a methyl group (hereinafter referred to as “C1-MA”) 24 g, 2-octyldodecyl methacrylate (R ¹ in formula (5) is methyl group, R ² is 9 in formula (3)) N = 6, hereinafter referred to as “A2”) 18 g, stearyl methacrylate (in formula (6), R ¹ is a methyl group, R ² is a stearyl group (linear alkyl group having 18 carbon atoms)) A certain compound, hereinafter referred to as “C18-MA”) 18 g, 1,1,1-tris (2-bromoisobutyroxymethyl) ethane (hereinafter referred to as “X”) which is a trifunctional initiator as an initiator. .) .061G, and highly refined mineral oil as a solvent (100 ° C. kinematic ^viscosity: 4.2mm 2 / s) 117g were added, and a homogeneous solution under stirring. This solution was cooled to 0 ° C. in an ice bath, and vacuum degassing / nitrogen purging of the reaction system was performed 5 times using a diaphragm pump. Further, from a sample inlet under a nitrogen flow, a complex solution in which 0.004 g of copper (II) bromide and 0.005 g of tris (2-pyridylmethyl) amine as a polymerization catalyst were dissolved in 2.0 g of anisole, and azobisiso After adding 0.056 g of butyronitrile (AIBN), polymerization was carried out by stirring for 12 hours at a solution temperature of 70 ° C. in a nitrogen atmosphere, and a poly (meth) acrylate viscosity index having three arm parts A solution containing an improver was obtained.

  About the obtained poly (meth) acrylate type viscosity index improver, the weight average molecular weight Mw and the number average molecular weight Mn were measured by GPC analysis. As a result, the weight average molecular weight Mw was 241,000, the number average molecular weight Mn was 165,000, and Mw / Mn was 1.46. The procedure of GPC analysis is as follows.

  Tetrahydrofuran was used as a solvent and diluted to prepare a solution having a sample concentration of 2% by mass. The sample solution was analyzed using a GPC apparatus (Waters Alliance 2695). The analysis was carried out using a column with a solvent flow rate of 1 ml / min and an analyzable molecular weight of 10,000 to 256,000 and using the refractive index as a detector. The relationship between the column retention time and the molecular weight was determined using a polystyrene standard with a clear molecular weight, a calibration curve was prepared separately, and the molecular weight was determined from the obtained retention time.

[Example 7]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 2”).

A 300 ml 5-neck separable flask equipped with a vertical metal stirring blade (with vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen, and a sample inlet, 24 g of methyl methacrylate (C1-MA), 2-octyl 18 g of dodecyl methacrylate (A2), 18 g of stearyl methacrylate (C18-MA), 0.061 g of 1,1,1-tris (2-bromoisobutyroxymethyl) ethane (X) which is a trifunctional initiator as an initiator, and 117 g of highly refined mineral oil (kinematic viscosity at 100 ° C .: 4.2 mm ² / s) was added as a solvent, and a uniform solution was obtained under stirring. This solution was cooled to 0 ° C. in an ice bath, and vacuum degassing / nitrogen purging of the reaction system was performed 5 times using a diaphragm pump. Furthermore, a complex solution prepared by dissolving 0.004 g of copper (II) bromide and 0.005 g of tris (2-pyridylmethyl) amine as a polymerization catalyst in 2.0 g of anisole from a sample introduction port under a nitrogen flow, and 2-ethyl A solution in which 0.17 g of tin (II) hexanoate was dissolved in 3 g of highly refined mineral oil was added, followed by polymerization by stirring at a solution temperature of 70 ° C. for 12 hours under a nitrogen atmosphere. A solution containing a poly (meth) acrylate viscosity index improver was obtained.

  The obtained poly (meth) acrylate viscosity index improver was subjected to GPC analysis in the same manner as in Example 1. As a result, the weight average molecular weight Mw was 252,000, the number average molecular weight Mn was 227,000, and Mw / Mn was 1.11.

[Reference Example 3]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 3”).

A 300 ml 5-neck separable flask equipped with a vertical metal stirring blade (with vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen, and a sample inlet, 24 g of methyl methacrylate (C1-MA), 2-octyl 18 g of dodecyl methacrylate (A2), 18 g of stearyl methacrylate (C18-MA), 0.021 g of cumyldithiobenzoic acid (CDTBA), and 60 g of highly purified mineral oil (kinematic viscosity at 100 ° C .: 4.2 mm ² / s) as a solvent are charged. A uniform solution was obtained under stirring. This solution was cooled to 0 ° C. in an ice bath, and vacuum degassing / nitrogen purging of the reaction system was performed 5 times using a diaphragm pump. Furthermore, after introducing 0.003 g of azobisisobutyronitrile (AIBN) as an initiator from a sample inlet under a nitrogen flow, polymerization was carried out at a solution temperature of 90 ° C. for 12 hours in a nitrogen atmosphere, and poly (meta ) A solution containing an acrylate viscosity index improver was obtained.

  The obtained poly (meth) acrylate viscosity index improver was subjected to GPC analysis in the same manner as in Example 1. As a result, the weight average molecular weight Mw was 285,000, the number average molecular weight Mn was 172,000, and Mw / Mn was 1.65.

[Comparative Example 1]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 4”).

A 300 ml four-necked reaction flask equipped with a stirring blade (with a vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen, and a dropping funnel for introducing sample is charged with 60 g of highly purified mineral oil as a solvent, The mixture was stirred for 1 hour while purging with nitrogen in the bath. In a dropping funnel for sample introduction, 24 g of methyl methacrylate (C1-MA) as a raw material monomer, 18 g of stearyl methacrylate (C18-MA), and dodecyl methacrylate (R ¹ in formula (6) is a methyl group, R ² is a dodecyl group ( A straight-chain alkyl group having 12 carbon atoms, hereinafter referred to as “C12-MA”), and a raw material mixed with 0.035 g of azobisisobutyronitrile (AIBN) as an initiator was added. Was dropped into the reaction flask over 120 minutes. Thereafter, polymerization was carried out for 8 hours while maintaining stirring at 85 ° C. under a nitrogen flow to obtain a solution containing a poly (meth) acrylate viscosity index improver. Thereafter, vacuum distillation was performed at 130 ° C. and 1 mmHg for 3 hours to remove unreacted monomers from the solution.

  The obtained poly (meth) acrylate viscosity index improver was subjected to GPC analysis in the same manner as in Example 1. As a result, the weight average molecular weight Mw was 108,000, the number average molecular weight Mn was 44,000, and Mw / Mn was It was 2.44.

[Examples 2-6, 8-24, Comparative Examples 2-5, Reference Examples 1-2]
The blending amount of the raw materials is changed as shown in Tables 1, 3, 5, 7, 9, and 11, and the other conditions are the same as those in any one of the above synthesis conditions 1 to 4, and the poly (meth) acrylate viscosity index is improved. The agent was synthesized. In the table, Y represents pentaerythritol tetrakis (2-bromoisobutyrate) which is a tetrafunctional initiator, and Z represents dipentaerythritol hexakis (2-bromoisobutyrate) which is a hexafunctional initiator. A1: m = 7, n = 6, and the like represent compounds in which R ¹ in formula (5) is a methyl group, R ² is formula (3), and m = 7 and n = 6. Tables 2, 4, 6, 8, 10, and 12 show Mw, Mn, and Mw / Mn of the obtained poly (meth) acrylate viscosity index improvers.

<Preparation of lubricating oil composition>
Poly (meth) acrylate viscosity index improvers obtained in Examples 1 to 24, Comparative Examples 1 to 5 and Reference Examples 1 to 3, metal (calcium sulfonate) detergents, ashless dispersants (succinic acid) Imide), a friction additive (glycerin monooleate) and an anti-wear agent (zinc dithiophosphate) and a highly refined mineral oil (Group III base oil, kinematic viscosity at 100 ° C .: 4.2 mm ² / s, VI : 125) was blended at the ratios shown in Tables 2, 4, 6, 8, 10, and 12 to prepare lubricating oil compositions.

<Evaluation of lubricating oil composition>
About each lubricating oil composition of Examples 1-24, Comparative Examples 1-5, and Reference Examples 1-3, kinematic viscosity at 100 ° C., viscosity index, HTHS viscosity at 100 ° C. and 150 ° C., and MRV viscosity at −40 ° C. Were measured by methods based on the following. The results are shown in Tables 2, 4, 6, 8, 10, and 12. In the table, “YS” in the item of MRV viscosity represents the yield stress and means out of specification.
Kinematic viscosity: JIS K-2283-1993
Viscosity index: JIS K 2283-1993
HTHS viscosity: ASTM D-4683
MRV viscosity: ASTM D-4684

  Moreover, the viscosity decreasing rate was measured as follows about each lubricating oil composition of Examples 1-24, Comparative Examples 1-5, and Reference Examples 1-3. That is, in accordance with JASO M347-95 (Automatic Transmission Oil Shear Stability Test Method), the rate of decrease in thickening by the viscosity index improver when evaluated under the condition where only the sample volume was increased was measured. More specifically, after adjusting the output with the standard oil A defined in the ASTM test method, a shear test was performed under the conditions of an amplitude of 28 μm, a vibration frequency of 10 KHz, an irradiation time of 10 minutes, and a sample volume of 50 mL. The permanent shear stability index PSSI of the polymer calculated based on the measured kinematic viscosity was calculated.

Claims (3)

A polymer chain comprising a core part, a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), based on the total amount of structural units contained in the polymer chain, The structural unit represented by the general formula (1) is 20% by mass or more, the structural unit represented by the general formula (2), wherein R ³ is a methyl group, 20 to 50% by mass, and the general formula (2) Three or more arm portions each consisting of a polymer chain containing 20 to 50% by mass of a structural unit in which R ³ is an alkyl group having 18 carbon atoms and one end of the polymer chain is bonded to the core portion; A poly (meth) acrylate viscosity index improver having a weight average molecular weight Mw of 100,000 or more and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 1.6 or less.

Wherein (1) and (2), _{R 1} represents hydrogen or a methyl group, _{R 2} represents a group represented by the following general formula (3), _{R 3} is C1-18 linear An alkyl group is shown.

In formula (3), m and n are integers that satisfy m ≧ 5, n ≧ 4, and m + n ≦ 31. ]   A lubricating oil additive comprising the poly (meth) acrylate viscosity index improver according to claim 1. A lubricating oil composition comprising a lubricating base oil and the poly (meth) acrylate viscosity index improver according to claim 1.