JP6077956B2 - Poly (meth) acrylate viscosity index improver, and lubricating oil additive and lubricating oil composition containing the viscosity index improver - Google Patents
Poly (meth) acrylate viscosity index improver, and lubricating oil additive and lubricating oil composition containing the viscosity index improver Download PDFInfo
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- JP6077956B2 JP6077956B2 JP2013142040A JP2013142040A JP6077956B2 JP 6077956 B2 JP6077956 B2 JP 6077956B2 JP 2013142040 A JP2013142040 A JP 2013142040A JP 2013142040 A JP2013142040 A JP 2013142040A JP 6077956 B2 JP6077956 B2 JP 6077956B2
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- viscosity index
- meth
- lubricating oil
- index improver
- acrylate
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- 239000010687 lubricating oil Substances 0.000 title claims description 54
- 229920000193 polymethacrylate Polymers 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title claims description 33
- 239000000654 additive Substances 0.000 title claims description 26
- 230000000996 additive effect Effects 0.000 title claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000002199 base oil Substances 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 230000001050 lubricating effect Effects 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 22
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- GSOYMOAPJZYXTB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GSOYMOAPJZYXTB-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、ポリ（メタ）アクリレート系粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物に関する。 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.
従来、潤滑油の分野では、省エネルギー性の観点から潤滑油の改良が検討されている。特に近年は、地球環境保護の気運が高まり、潤滑油に対する省エネルギー性改善効果の要求は一層強まっている。 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.
例えば、自動車エンジン等の内燃機関に用いられる潤滑油（「内燃機関用潤滑油」又は「エンジン油」とも呼ばれる。）の場合、省燃費性を改善する手段の一つとして、潤滑油基油に粘度指数向上剤を添加することによって、潤滑油の粘度指数を高くする方法が知られている。粘度指数向上剤については、これまで各種の粘度指数向上剤の使用が提案されているが、特にポリ（メタ）クリレート系の粘度指数向上剤の使用が多く提案されている（例えば特許文献１〜７参照）。 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).
しかし、上記従来のポリ（メタ）アクリレート系粘度指数向上剤を使用する場合、実用上十分な省燃費性を達成するためには、高せん断粘度の点で改善の余地がある。特に省燃費性の要求が高い０Ｗ−２０では、１５０℃での高せん断粘度をある程度高いレベルに維持し、その一方で１００℃での高せん断粘度を低下させることが必要である。これに対して、従来のポリ（メタ）アクリレート系粘度指数向上剤では、１５０℃での高せん断粘度を維持しつつ、１００℃での高せん断粘度を低くすることが困難である。 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.
さらに、最近では、省燃費性に加えて低温（特に極低温）での流動性の確保が求められている。しかし、従来のポリ（メタ）アクリレート系粘度指数向上剤は、省燃費性と低温流動性との両立の点で、必ずしも十分とはいえない。 Furthermore, recently, in addition to fuel saving, securing fluidity at low temperatures (particularly extremely low temperatures) has been demanded. However, conventional poly (meth) acrylate viscosity index improvers are not necessarily sufficient in terms of achieving both fuel saving and low temperature fluidity.
そこで、本発明は、１５０℃での高せん断粘度を維持しつつ、１００℃での高せん断粘度を十分に低下させることができ、かつ低温流動性を十分に確保できる粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物を提供することを目的とする。 Therefore, the present invention is a viscosity index improver capable of sufficiently reducing the high shear viscosity at 100 ° C. while maintaining a high shear viscosity at 150 ° C., and sufficiently ensuring low temperature fluidity, and the It is an object to provide a lubricating oil additive and a lubricating oil composition containing a viscosity index improver.
本発明者らは、鋭意検討した結果、特定の構造単位を有し、重量平均分子量Ｍｗ、及び重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが特定条件を満たすポリ（メタ）アクリレート系粘度指数向上剤によって、１５０℃での高せん断粘度を維持しつつ、１００℃での高せん断粘度を十分に低下させることができ、かつ低温流動性を確保できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the inventors of the present invention have a specific structural unit, and the poly (meth) acrylate has a weight average molecular weight Mw and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn satisfies the specific condition The system viscosity index improver finds that the high shear viscosity at 100 ° C. can be sufficiently lowered while maintaining the high shear viscosity at 150 ° C., and the low temperature fluidity can be secured, thereby completing the present invention. It came to.
すなわち、本発明は、下記一般式（１）で表される構造単位及び下記一般式（２）で表される構造単位を含む重合鎖を有し、重量平均分子量Ｍｗが１００，０００以上であり、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが１．６以下である、ポリ（メタ）アクリレート系粘度指数向上剤を提供する。
［式（１）及び（２）中、Ｒ１は水素又はメチル基を示し、Ｒ２は下記一般式（３）で表される基を示し、Ｒ３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 has 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 the weight average molecular weight Mw is 100,000 or more. A poly (meth) acrylate viscosity index improver having a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 1.6 or less is provided.
[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. ]
また、本発明は、上記ポリ（メタ）アクリレート系粘度指数向上剤を含有する潤滑油添加剤を提供する。 Moreover, this invention provides the lubricating oil additive containing the said poly (meth) acrylate type viscosity index improver.
また、本発明は、潤滑油基油と、上記ポリ（メタ）アクリレート系粘度指数向上剤を含有する潤滑油組成物を提供する。 The present invention also provides a lubricating oil composition comprising a lubricating base oil and the poly (meth) acrylate viscosity index improver.
本発明によれば、１５０℃での高せん断粘度を維持しつつ、１００℃での高せん断粘度を十分に低下させることができ、かつ低温流動性を十分に確保できる粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物を提供することができる。 According to the present invention, while maintaining a high shear viscosity at 150 ° C., the viscosity index improver that can sufficiently reduce the high shear viscosity at 100 ° C. and sufficiently ensure low temperature fluidity, and the Lubricating oil additives and lubricating oil compositions containing viscosity index improvers can be provided.
以下、本発明の好適な実施形態について詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.
［第１実施形態：ポリ（メタ）アクリレート系粘度指数向上剤］
第１実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤は、下記一般式（１）で表される構造単位及び下記一般式（２）で表される構造単位を含む重合鎖を有する。該ポリ（メタ）アクリレート系粘度指数向上剤の重量平均分子量Ｍｗ（以下、場合により単に「Ｍｗ」という。）は１００，０００以上であり、重量平均分子量Ｍｗと数平均分子量Ｍｎ（以下、場合により単に「Ｍｗ」という。）との比Ｍｗ／Ｍｎ（以下、場合により単に「Ｍｗ／Ｍｎ」という。）は１．６以下である。
［式（１）及び（２）中、Ｒ１は水素又はメチル基を示し、Ｒ２は下記一般式（３）で表される基を示し、Ｒ３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 has a polymer chain including a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). 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. ]
Ｒ１は水素又はメチル基のいずれであってもよいが、好ましくはメチル基である。 R 1 may be either hydrogen or a methyl group, but is preferably a methyl group.
Ｒ２としては、低粘度化の観点から、ｍが５〜１６、ｎが４〜１５であるものが好ましく、ｍが６〜１５、ｎが６〜１０であるものがより好ましく、ｍが７〜１０、ｎが６〜９であるものが更に好ましい。重合鎖に含まれる上記一般式（１）で表される構造単位が２以上の場合、Ｒ１及びＲ２は構造単位同士で同一でも異なっていてもよい。 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.
重合鎖は、上記のとおり、上記一般式（１）で表される構造単位及び上記一般式（２）で表される構造単位を含むが、低粘度化の観点から、上記一般式（１）で表される構造単位を、重合鎖に含まれる構造単位の全量を基準として、２０〜８０質量％含むことが好ましく、２０〜７０質量％含むことがより好ましく、２０〜５０質量％含むことが更に好ましい。また、重合鎖は、省燃費性の観点から、上記一般式（２）で表される構造単位を、重合鎖に含まれる構造単位の全量を基準として、２０〜８０質量％含むことが好ましく、３０〜８０質量％含むことがより好ましく、５０〜８０質量％含むことが更に好ましい。また、重合鎖は、上記一般式（１）で表される構造単位と上記一般式（２）で表される構造単位とを合わせて、重合鎖に含まれる構造単位の全量を基準として、７０質量％以上含むことが好ましく、８０質量％以上含むことがより好ましく、９０質量％以上含むことが更に好ましく、１００質量％含むことが最も好ましい。 As described above, the polymer chain includes the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). From the viewpoint of reducing the viscosity, the general formula (1) Is preferably 20 to 80% by mass, more preferably 20 to 70% by mass, and more preferably 20 to 50% by mass, based on the total amount of structural units contained in the polymer chain. Further preferred. 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, most preferably at least 100% by mass.
重合鎖に含まれる上記一般式（２）で表される構造単位が２以上の場合、Ｒ１及びＲ３は構造単位同士で同一でも異なっていてもよい。Ｒ３の異なる２種以上の構造単位が含まれる場合、ポリ（メタ）アクリレートの溶解性の観点から、Ｒ３がメチル基である構造単位が、重合鎖に含まれる構造単位の全量を基準として、５〜５０質量％含まれることが好ましく、１０〜４５質量％含まれることがより好ましく、２０〜４５質量％含まれることが更に好ましい。また、低温流動性の観点から、Ｒ３が炭素数１８のアルキル基である構造単位が、重合鎖に含まれる構造単位の全量を基準として、５〜５０質量％含まれることが好ましく、１０〜４５質量％含まれることがより好ましく、２０〜４０質量％含まれることが更に好ましい。 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.
重合鎖は、上記一般式（１）で表される構造単位及び上記一般式（２）で表される構造単位のみを含んでいてもよく、あるいは、これら以外の構造単位を更に含んでいてもよい。また、重合鎖の末端は、特に制限されない。このような重合鎖の中でも、上記一般式（１）で表される構造単位及び上記一般式（２）で表される構造単位のみを含んでおり、末端が水素原子である重合鎖、すなわち下記一般式（４）で表される重合鎖であることが好ましい。 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. The terminal of the polymer chain is not particularly limited. Among such polymer chains, the polymer chain contains only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), and the terminal is a hydrogen atom, that is, A polymer chain represented by the general formula (4) is preferable.
式（４）中、Ｒ１は水素又はメチル基を示し、Ｒ４は、上記一般式（３）で表される基、又は直鎖若しくは炭素数５以下の分岐を有する炭素数１〜１８のアルキル基を示し、ｎはＭｗ及びＭｗ／Ｍｎが上記の条件を満たすように選ばれる整数である。ｎは、例えば４００〜２０００の整数である。 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.
重量平均分子量Ｍｗは、１００，０００以上であり、省燃費性能の観点から、１２５，０００以上であることが好ましく、１５０，０００以上であることがより好ましく、１７５，０００以上であることが更に好ましい。Ｍｗの上限は特に制限されないが、Ｍｗは例えば５００，０００以下である。 The weight average molecular weight Mw is 100,000 or more, preferably 125,000 or more, more preferably 150,000 or more, and more preferably 175,000 or more from the viewpoint of fuel saving performance. preferable. The upper limit of Mw is not particularly limited, but Mw is, for example, 500,000 or less.
数平均分子量Ｍｎは、Ｍｗ／Ｍｎが上記の条件を満たすように適宜選択される。Ｍｎは、省燃費性能の観点から、７５，０００以上であることが好ましく、９４，０００以上であることがより好ましく、１１０，０００以上であることが更に好ましい。Ｍｎの上限は特に制限されないが、Ｍｎは例えば３００，０００以下である。 The number average molecular weight Mn 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は、１．６以下であるが、省燃費性能の観点から、１．５以下であることが好ましく、１．４以下であることがより好ましく、１．２以下であることが更に好ましい。また、Ｍｗ／Ｍｎは、合成をする上では、１．０以上であることが好ましく、１．０１以上であることがより好ましく、１．０２以上であることが更に好ましい。 Mw / Mn is 1.6 or less, but from the viewpoint of fuel saving performance, it is preferably 1.5 or less, more preferably 1.4 or less, and further preferably 1.2 or less. preferable. In addition, Mw / Mn is preferably 1.0 or more, more preferably 1.01 or more, and further preferably 1.02 or more in the synthesis.
なお、本発明でいう「重量平均分子量Ｍｗ」、「数平均分子量Ｍｎ」及び「重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎ」とは、ＧＰＣ分析により得られるＭｗ、Ｍｎ及びＭｗ／Ｍｎ（ポリスチレン（標準試料）換算値）を意味する。具体的には、例えば以下のように測定される。 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). Specifically, for example, it is measured as follows.
溶剤としてテトラヒドロフランを使用し、希釈して試料濃度を２質量％とした溶液を調製する。その試料溶液をＧＰＣ装置（Ｗａｔｅｒｓ Ａｌｌｉａｎｃｅ２６９５）を用いて分析を行う。溶剤の流速は１ｍｌ／ｍｉｎ、分析可能分子量１０，０００から２５６，０００のカラムを使用し、屈折率を検出器として分析を実施する。なお、分子量が明確なポリスチレン標準を用いてカラム保持時間と分子量との関係を求め、検量線を別途作成した上で、得られた保持時間から分子量を決定する。 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.
本実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤の製造方法としては、特に制限されないが、例えば、アルキル（メタ）アクリレート、重合試薬及び溶媒を含む混合溶液に開始剤を加え、所定の温度でアルキル（メタ）アクリレートを重合する方法が挙げられる。 The production method of the poly (meth) acrylate viscosity index improver according to the present embodiment is not particularly limited. For example, an initiator is added to a mixed solution containing an alkyl (meth) acrylate, a polymerization reagent, and a solvent, A method of polymerizing alkyl (meth) acrylate at a temperature is mentioned.
アルキル（メタ）アクリレートとしては、下記一般式（５）で表されるアルキル（メタ）アクリレート及び下記一般式（６）で表されるアルキル（メタ）アクリレートを用いることができる。 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.
式（５）及び（６）中、Ｒ１は水素又はメチル基を示し、Ｒ２は上記一般式（３）で表される基を示し、Ｒ３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。 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.
Ｒ１はメチル基であることが好ましい。Ｒ２としては、ｍが５〜１６、ｎが４〜１５であるものが好ましく、ｍが６〜１５、ｎが６〜１０であるものがより好ましく、ｍが７〜１０、ｎが６〜９であるものが更に好ましい。 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.
アルキル（メタ）アクリレートとしては、上記のとおり、上記一般式（５）で表されるアルキル（メタ）アクリレート及び上記一般式（６）で表されるアルキル（メタ）アクリレートを用いることができるが、上記一般式（５）で表されるアルキル（メタ）アクリレートの含有量が、アルキル（メタ）アクリレート全量基準で、２０〜８０質量％であることが好ましく、２０〜７０質量％であることがより好ましく、２０〜５０質量％であることが更に好ましい。また、上記一般式（５）で表されるアルキル（メタ）アクリレートの含有量が、アルキル（メタ）アクリレート全量基準で、２０〜８０質量％であることが好ましく、３０〜８０質量％であることがより好ましく、５０〜８０質量％であることが更に好ましい。 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%.
上記一般式（６）で表されるアルキル（メタ）アクリレートとしては、上記一般式（６）で表されるアルキル（メタ）アクリレートの１種を単独で、又は２種以上を混合して用いることができるが、２種以上を混合して用いることが好ましい。２種以上を混合して用いる場合、Ｒ２がメチル基であるメチル（メタ）アクリレートの含有量が、アルキル（メタ）アクリレート全量基準で、５〜５０質量％であることが好ましく、１０〜４５質量％であることがより好ましく、２０〜４５質量％であることが更に好ましい。また、Ｒ２が炭素数１８のアルキル基であるアルキル（メタ）アクリレートの含有量が、アルキル（メタ）アクリレート全量基準で、５〜５０質量％であることが好ましく、１０〜４５質量％であることがより好ましく、２０〜４０質量％であることが更に好ましい。 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%.
重合試薬としては、例えば、クミルジチオ安息香酸、チオカルボニル基を有する化合物を用いることができる。好ましい重合試薬としては、クミルジチオ安息香酸を例示することができる。 As the polymerization reagent, for example, cumyldithiobenzoic acid or a compound having a thiocarbonyl group can be used. As a preferable polymerization reagent, cumyldithiobenzoic acid can be exemplified.
溶媒としては、例えば、高度精製鉱油、アニソール、トルエンを用いることができる。好ましい溶媒としては、高度精製鉱油を例示することができる。 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.
開始剤としては、例えば、アゾビスイソブチロニトリル（ＡＩＢＮ）、アゾビスジメチルバレロニトリル（ＡＭＢＮ）、アゾビスメチルブチルニトリル（ＡＤＶＮ）を用いることができる。好ましい開始剤としては、アゾビスイソブチロニトリルを例示することができる。 As the initiator, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile (AMBN), azobismethylbutylnitrile (ADVN) can be used. As a preferred initiator, azobisisobutyronitrile can be exemplified.
アルキル（メタ）アクリレートを重合する際の反応温度としては、７０〜１２０℃であることが好ましく、８０〜１１０℃であることがより好ましく、９０〜１１０℃であることが更に好ましい。反応温度を上記範囲内にすることで、得られるポリ（メタ）アクリレート系粘度指数向上剤のＭｗ／Ｍｎが１．６以下となりやすくなる。例えば、反応温度が９０〜１１０℃であるとＭｗ／Ｍｎが１．０〜１．２となる傾向にあり、反応温度が８０〜１１０℃であるとＭｗ／Ｍｎが１．２〜１．４となる傾向にあり、反応温度が７０〜１２０℃であるとＭｗ／Ｍｎが１．４〜１．６となる傾向にある。 The reaction temperature for polymerizing the alkyl (meth) acrylate is preferably 70 to 120 ° C, more preferably 80 to 110 ° C, and still more preferably 90 to 110 ° C. 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 90 to 110 ° C., Mw / Mn tends to be 1.0 to 1.2, and when the reaction temperature is 80 to 110 ° C., Mw / Mn is 1.2 to 1.4. When the reaction temperature is 70 to 120 ° C., Mw / Mn tends to be 1.4 to 1.6.
反応時間は、原料であるアルキル（メタ）アクリレート、重合試薬、溶媒及び開始剤の種類及び使用量、反応温度等の反応条件、目的とするポリ（メタ）アクリレートのＭｗ及びＭｗ／Ｍｎに応じて適宜選定することができる。好ましい反応時間としては、例えば１０〜１４時間を例示することができる。 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. As preferable reaction time, 10 to 14 hours can be illustrated, for example.
アルキル（メタ）アクリレートの重合は、窒素雰囲気下で行うことが好ましい。 The polymerization of the alkyl (meth) acrylate is preferably performed in a nitrogen atmosphere.
［第２実施形態：潤滑油添加剤］
本発明の第２実施形態に係る潤滑油添加剤は、上記一般式（１）で表される構造単位及び上記一般式（２）で表される構造単位を含む重合鎖を有し、重量平均分子量Ｍｗが１００，０００以上であり、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが１．６以下であるポリ（メタ）アクリレート系粘度指数向上剤を含有する。なお、本実施形態におけるポリ（メタ）アクリレート系粘度指数向上剤は、上記第１実施形態における粘度指数向上剤と同様であり、ここでは重複する説明を省略する。
[Second Embodiment: Lubricating Oil Additive]
The lubricating oil additive according to the second embodiment of the present invention has a polymer unit containing a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and has a weight average. A poly (meth) acrylate viscosity index improver having a 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 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.
潤滑油添加剤は、上記のポリ（メタ）アクリレート系粘度指数向上剤のみからなるものであってもよく、あるいは、当該粘度指数向上剤と他の添加剤との混合物（すなわち添加剤組成物）であってもよい。潤滑油添加剤が当該粘度指数向上剤と他の添加剤との混合物である場合、これらの混合割合は特に制限されず、用途に応じて適宜選定することができる。 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.
他の添加剤としては、上記のポリ（メタ）アクリレート系粘度指数向上剤以外の粘度指数向上剤、酸化防止剤、摩耗防止剤（又は極圧剤）、腐食防止剤、防錆剤、粘度指数向上剤、流動点降下剤、抗乳化剤、金属不活性化剤、消泡剤、無灰摩擦調整剤等の添加剤等が挙げられる。これらの添加剤は、１種を単独で、又は２種以上を組み合わせて用いることができる。 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.
上記のポリ（メタ）アクリレート系粘度指数向上剤以外の粘度指数向上剤としては、上記のポリ（メタ）アクリレート系粘度指数向上剤以外のポリ（メタ）アクリレート系粘度指数向上剤、ポリイソブテン系粘度指数向上剤、エチレン−プロピレン共重合体系粘度指数向上剤、スチレン−ブタジエン水添共重合体系粘度指数向上剤などが挙げられる。 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.
酸化防止剤としては、フェノール系、アミン系等の無灰酸化防止剤、亜鉛系、銅系、モリブデン系等の金属系酸化防止剤が挙げられる。 Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as zinc, copper, and molybdenum.
フェノール系酸化防止剤としては、例えば、４，４'−メチレンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４’−ビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４'−ビス（２−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２'−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、２，２'−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４'−ブチリデンビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−イソプロピリデンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−ノニルフェノール）、２，２'−イソブチリデンビス（４，６−ジメチルフェノール）、２，２’−メチレンビス（４−メチル−６−シクロヘキシルフェノール）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェノール、２，４−ジメチル−６−ｔｅｒｔ−ブチルフェノール、２，６−ジ−ｔｅｒｔ−α−ジメチルアミノ−ｐ−クレゾール、２，６−ジ−ｔｅｒｔ−ブチル−４−（Ｎ，Ｎ−ジメチルアミノメチルフェノール）、４,４'−チオビス（２−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４'−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２'−チオビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、ビス（３−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルベンジル）スルフィド、ビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）スルフィド、２，２'−チオ−ジエチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、トリデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、ペンタエリスリチル−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクチル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、ステアリル３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、オクチル−３−（３−メチル−５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等が挙げられる。これらは二種以上を混合して使用してもよい。 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.
アミン系酸化防止剤としては、例えば、芳香族アミン化合物、アルキルジフェニルアミン、アルキルナフチルアミン、フェニル−α−ナフチルアミン、アルキルフェニル−α−ナフチルアミン等の潤滑油用として一般に使用されている公知のアミン系酸化防止剤が挙げられる。 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.
腐食防止剤としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、又はイミダゾール系化合物等が挙げられる。 Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.
防錆剤としては、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、又は多価アルコールエステル等が挙げられる。 Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、アルキルチアジアゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール又はその誘導体、１，３，４−チアジアゾールポリスルフィド、１，３，４−チアジアゾリル−２，５−ビスジアルキルジチオカーバメート、２−（アルキルジチオ）ベンゾイミダゾール、又はβ−（ｏ−カルボキシベンジルチオ）プロピオンニトリル等が挙げられる。 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.
消泡剤としては、例えば、２５℃における動粘度が１，０００〜１００，０００ｍｍ２／ｓのシリコーンオイル、アルケニルコハク酸誘導体、ポリヒドロキシ脂肪族アルコールと長鎖脂肪酸のエステル、メチルサリチレートとｏ−ヒドロキシベンジルアルコール等が挙げられる。 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.
無灰摩擦調整剤としては、潤滑油用の無灰摩擦調整剤として通常用いられる任意の化合物が使用可能であり、例えば、炭素数６〜３０のアルキル基又はアルケニル基、特に炭素数６〜３０の直鎖アルキル基又は直鎖アルケニル基を分子中に少なくとも１個有する、アミン化合物、脂肪酸エステル、脂肪酸アミド、脂肪酸、脂肪族アルコール、脂肪族エーテル等の無灰摩擦調整剤等が挙げられる。また特開２００９−２８６８３１号公報に記載の窒素含有化合物及びその酸変性誘導体等、国際公開第２００５／０３７９６７号パンフレットに例示されている各種無灰摩擦調整剤を用いることもできる。 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.
また、本実施形態に係る潤滑油添加剤は、溶剤を更に含有していてもよい。溶剤としては、高度精製鉱油、溶剤精製鉱油、合成油を用いることができる。これらの中でも、高度精製鉱油、溶剤精製鉱油を用いることが好ましい。潤滑油添加剤が溶剤を含有する場合、溶剤の含有量は、潤滑油添加剤の全量を基準として、好ましくは５〜７５質量％、より好ましくは３０〜６０質量％である。 Moreover, the lubricating oil additive according to this embodiment may further contain a solvent. As the solvent, highly refined mineral oil, solvent refined mineral oil, and synthetic oil can be used. Among these, highly refined mineral oil and solvent refined mineral oil are preferably used. 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.
［第３実施形態：潤滑油組成物］
第３実施形態に係る潤滑油組成物は、潤滑油基油と、上記一般式（１）で表される構造単位及び上記一般式（２）で表される構造単位を含む重合鎖を有し、重量平均分子量Ｍｗが１００，０００以上であり、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが１．６以下であるポリ（メタ）アクリレート系粘度指数向上剤と、を含有する。ここで、本実施形態に係る潤滑油組成物には、潤滑油基油と上記第２の実施形態に係る潤滑油添加剤とを含有する態様が包含される。本実施形態におけるポリ（メタ）アクリレート系粘度指数向上剤は上記第１実施形態及び第２実施形態におけるポリ（メタ）アクリレート系粘度指数向上剤と同様であり、また、潤滑油組成物に含まれ得るその他の添加剤及び溶剤は第２実施形態におけるその他の添加剤及び溶剤と同様であり、ここでは重複する説明を省略する。
[Third Embodiment: Lubricating Oil Composition]
The lubricating oil composition according to the third embodiment includes a lubricating base oil, a structural unit represented by the general formula (1), and a polymer chain including the structural unit represented by the general formula (2). 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. . 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.
潤滑油基油としては、特に制限されず、通常の潤滑油に使用される潤滑油基油を使用できる。具体的には、鉱油系潤滑油基油、合成油系潤滑油基油又はこれらの中から選ばれる２種以上の潤滑油基油を任意の割合で混合した混合物等を使用できる。 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.
鉱油系潤滑油基油としては、例えば、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、水素化精製等の処理を１つ以上行って精製したもの、あるいはワックス異性化鉱油、ＧＴＬワックス（ガストゥリキッドワックス）を異性化する手法で製造される基油等が挙げられる。 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).
合成油系潤滑油としては、例えば、ポリブテン又はその水素化物；１−オクテンオリゴマー、１−デセンオリゴマー等のポリ−α−オレフィン又はその水素化物；ジトリデシルグルタレート、ジ−２−エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ−２−エチルヘキシルセバケート等のジエステル；トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール−２−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等のポリオールエステル；アルキルナフタレン、アルキルベンゼン等の芳香族系合成油又はこれらの混合物等が例示できる。 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.
潤滑油基油の１００℃における動粘度は、好ましくは２．５〜１０．０ｍｍ２／ｓ、より好ましくは３．０〜８．０ｍｍ２／ｓ、更に好ましくは３．５〜６．０ｍｍ２／ｓである。また、潤滑油基油の粘度指数は、好ましくは９０〜１６５、より好ましくは１００〜１５５、更に好ましくは１２０〜１５０である。 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.
潤滑油基油のクロマト分析による飽和分は、第１実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤等の添加剤の効果を発揮しやすくするため、好ましくは８０％以上、より好ましくは８５％以上、更に好ましくは９０％以上、最も好ましくは９５％以上である。 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.
第１実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤の含有量は、潤滑油組成物全量を基準として、好ましくは０．１〜２０．０質量％、より好ましくは０．５〜１５．０質量％、更に好ましくは１．０〜１０．０質量％である。当該含有量が上記下限値以上であると、十分な添加効果を得られやすくなり、一方、当該含有量が上記上限値以下であると、せん断安定性が高くなり、燃費持続性が向上する。 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.
潤滑油組成物の１００℃における動粘度は、好ましくは３．０〜１６．３ｍｍ２／ｓ、より好ましくは３．５〜１２．５ｍｍ２／ｓ、更に好ましくは４．０〜９．３ｍｍ２／ｓである。１００℃における動粘度が上記下限値以上であると、潤滑性を確保しやすくなり、一方、１００℃における動粘度が上記上限値以下であると、より省燃費性が向上する。なお、本発明での１００℃における動粘度は、ＪＩＳ Ｋ−２２８３−１９９３に規定される１００℃における動粘度を意味する。 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.
潤滑油組成物の粘度指数は、好ましくは１５０〜２５０、より好ましくは１６０〜２４０、更に好ましくは１７０〜２３０である。粘度指数が上記下限値以上であると、ＨＴＨＳ粘度を維持しながら、より省燃費性を向上させることができ、また低温粘度を低下させやすくなる。一方、粘度指数が上記上限値以下であると、低温流動性、添加剤の溶解性、及びシール材料との適合性を確保することができる。なお、本発明での粘度指数は、ＪＩＳ Ｋ ２２８３−１９９３に規定される粘度指数を意味する。 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.
潤滑油組成物の１５０℃におけるＨＴＨＳ粘度は、好ましくは１．７ｍＰａ・ｓ以上、より好ましくは２．０ｍＰａ・ｓ以上、更に好ましくは２．３ｍＰａ・ｓ以上、最も好ましくは２．６ｍＰａ・ｓ以上である。１５０℃におけるＨＴＨＳ粘度が上記下限値以上であると、潤滑油組成物の蒸発を抑制でき、潤滑性を確保することができる。また、潤滑油組成物の１００℃におけるＨＴＨＳ粘度は、好ましくは５．２ｍＰａ・ｓ以下、より好ましくは５．１ｍＰａ・ｓ以下、更に好ましくは５．０ｍＰａ・ｓ以下である。１００℃におけるＨＴＨＳ粘度が上記上限値以下であると、より高い省燃費性を得られる。なお、本発明での１５０℃又は１００℃におけるＨＴＨＳ粘度は、ＡＳＴＭ Ｄ−４６８３に規定される１５０℃又は１００℃における高温高せん断粘度を意味する。 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.
潤滑油組成物の−４０℃におけるＭＲＶ粘度は、好ましくは６０，０００ｍＰａ・ｓ以下、より好ましくは４０，０００ｍＰａ・ｓ以下、更に好ましくは３０，０００ｍＰａ・ｓ以下である。−４０℃におけるＭＲＶ粘度が上記上限値以下であると、低温時のポンピング特性に優れる。なお、本発明での−４０℃におけるＭＲＶ粘度は、ＡＳＴＭ Ｄ−４６８４に規定される−４０℃におけるＭＲＶ粘度を意味する。 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.
以上説明した第１実施形態に係る粘度指数向上剤、第２実施形態に係る潤滑油添加剤、及び第３実施形態に係る潤滑油組成物は、内燃機関用潤滑油、駆動系潤滑油等の幅広い分野で使用することができるが、特に、内燃機関用潤滑油の分野において有用である。この場合の内燃機関の燃料は、ガソリン又はディーゼル燃料のいずれであってもよい。 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.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 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.
［実施例１］
下記の条件（「合成条件１」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Example 1]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 1”).
錨型金属製攪拌翼（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入口を装着した３００ｍｌの５口セパラブルフラスコに、メチルメタクリレート（式（６）中のＲ１及びＲ３が共にメチル基である化合物。以下「Ｃ１−ＭＡ」と表記する。）１２ｇ、２−オクチルドデシルメタクリレート（式（５）中のＲ１がメチル基、Ｒ２が式（３）でｍ＝９、ｎ＝６である化合物。以下「Ａ２」と表記する。）９ｇ、ステアリルメタクリレート（式（６）中のＲ１がメチル基、Ｒ３がステアリル基（炭素数１８の直鎖アルキル基）である化合物。以下「Ｃ１８−ＭＡ」と表記する。）９ｇ、クミルジチオ安息香酸（ＣＤＴＢＡ）０．０３１ｇ、及び溶媒として高度精製鉱油３０ｇを投入し、攪拌下で均一溶液とした。本溶液を氷浴にて０℃まで冷却し、ダイヤフラムポンプを用いて反応系の真空脱気／窒素パージを５回実施した。さらに、窒素フロー下でサンプル導入口よりラジカル開始剤としてアゾビスイソブチロニトリル（ＡＩＢＮ）０．００５ｇを投入した後、窒素雰囲気下にて溶液温度１１０℃で１２時間重合を実施し、ポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。 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 A compound in which R 3 is a methyl group, hereinafter referred to as “C1-MA”) 12 g, 2-octyldodecyl methacrylate (R 1 in formula (5) is a methyl group, R 2 is m in formula (3)) = 9, n = 6 (hereinafter referred to as “A2”) 9 g, stearyl methacrylate (R 1 in formula (6) is a methyl group, R 3 is a stearyl group (linear alkyl group having 18 carbon atoms) ) 9 g, cumyldithiobenzoic acid (CDTBA) 0.031 g, and 30 g of highly purified mineral oil as a solvent were added to obtain 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. Furthermore, after introducing 0.005 g of azobisisobutyronitrile (AIBN) as a radical initiator from the sample inlet under a nitrogen flow, polymerization was carried out at a solution temperature of 110 ° C. for 12 hours in a nitrogen atmosphere, and poly ( A solution containing a (meth) acrylate viscosity index improver was obtained.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、ＧＰＣ分析により、重量平均分子量Ｍｗ及び数平均分子量Ｍｎを測定した。その結果、重量平均分子量Ｍｗは２３３，０００、数平均分子量Ｍｎは１５０，０００、Ｍｗ／Ｍｎは１．５５であった。ＧＰＣ分析の手順は以下のとおりである。 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 233,000, the number average molecular weight Mn was 150,000, and Mw / Mn was 1.55. The procedure of GPC analysis is as follows.
溶剤としてテトラヒドロフランを使用し、希釈して試料濃度を２質量％とした溶液を調製した。その試料溶液をＧＰＣ装置（Ｗａｔｅｒｓ Ａｌｌｉａｎｃｅ２６９５）を用いて分析を行った。溶剤の流速は１ｍｌ／ｍｉｎ、分析可能分子量１０，０００から２５６，０００のカラムを使用し、屈折率を検出器として分析を実施した。なお、分子量が明確なポリスチレン標準を用いてカラム保持時間と分子量との関係を求め、検量線を別途作成した上で、得られた保持時間から分子量を決定した。 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.
［実施例２］
下記の条件（「合成条件２」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Example 2]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 2”).
錨型金属製攪拌翼（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入口を装着した３００ｍｌの５口セパラブルフラスコにメチルメタクリレート（Ｃ１−ＭＡ）１２ｇ、２−オクチルドデシルメタクリレート（Ａ２）９ｇ、ステアリルメタクリレート（Ｃ１８−ＭＡ）９ｇ、クミルジチオ安息香酸（ＣＤＴＢＡ）０．０３０ｇ、及び溶媒として高度精製鉱油３０ｇを投入し、攪拌下で均一溶液とした。本溶液を氷浴にて０℃まで冷却し、ダイヤフラムポンプを用いて反応系の真空脱気／窒素パージを５回実施した。さらに、窒素フロー下でサンプル導入口よりラジカル開始剤としてアゾビスイソブチロニトリル（ＡＩＢＮ）０．００５ｇを投入した後、窒素雰囲気下にて溶液温度１００℃で１２時間重合を実施し、ポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。 A 300 ml five-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, 12 g of methyl methacrylate (C1-MA), 2-octyldodecyl 9 g of methacrylate (A2), 9 g of stearyl methacrylate (C18-MA), 0.030 g of cumyldithiobenzoic acid (CDTBA), and 30 g of highly purified mineral oil as a solvent were added to obtain 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. Furthermore, after introducing 0.005 g of azobisisobutyronitrile (AIBN) as a radical initiator from the sample inlet under a nitrogen flow, polymerization was carried out at a solution temperature of 100 ° C. for 12 hours in a nitrogen atmosphere, and poly ( A solution containing a (meth) acrylate viscosity index improver was obtained.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、実施例１と同様にＧＰＣ分析を行った結果、重量平均分子量Ｍｗは２２８，０００、数平均分子量Ｍｎは１７１，０００、Ｍｗ／Ｍｎは１．３３であった。 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 228,000, the number average molecular weight Mn was 171,000, and Mw / Mn was It was 1.33.
［実施例３］
下記の条件（「合成条件３」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Example 3]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 3”).
錨型金属製攪拌翼（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入口を装着した３００ｍｌの５口セパラブルフラスコに、メチルメタクリレート（Ｃ１−ＭＡ）１２ｇ、２−オクチルドデシルメタクリレート（Ａ２）９ｇ、ステアリルメタクリレート（Ｃ１８−ＭＡ）９ｇ、クミルジチオ安息香酸（ＣＤＴＢＡ）０．０３２ｇ、及び溶媒として高度精製鉱油３０ｇを投入し、攪拌下で均一溶液とした。本溶液を氷浴にて０℃まで冷却し、ダイヤフラムポンプを用いて反応系の真空脱気／窒素パージを５回実施した。さらに、窒素フロー下でサンプル導入口よりラジカル開始剤としてアゾビスイソブチロニトリル（ＡＩＢＮ）０．００５ｇを投入した後、窒素雰囲気下にて溶液温度９０℃で１２時間重合を実施し、ポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。 A 300 ml 5-neck separable flask equipped with a vertical metal stirring blade (with vacuum seal), a Dimroth cooler, a 3-way cock for introducing nitrogen, and a sample inlet, 12 g of methyl methacrylate (C1-MA), 2-octyl 9 g of dodecyl methacrylate (A2), 9 g of stearyl methacrylate (C18-MA), 0.032 g of cumyldithiobenzoic acid (CDTBA), and 30 g of highly purified mineral oil as a solvent were added to obtain 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. Furthermore, after introducing 0.005 g of azobisisobutyronitrile (AIBN) as a radical initiator from the 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 ( A solution containing a (meth) acrylate viscosity index improver was obtained.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、実施例１と同様にＧＰＣ分析を行った結果、重量平均分子量Ｍｗは２１０，０００、数平均分子量Ｍｎは１９４，０００、Ｍｗ／Ｍｎは１．０８であった。 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 210,000, the number average molecular weight Mn was 194,000, and Mw / Mn was 1.08.
［比較例３］
下記の条件（「合成条件４」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Comparative Example 3]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 4”).
撹拌羽（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入用滴下ロートを装着した３００ｍｌの４口の反応フラスコに、溶媒として高度精製鉱油３０ｇを投入し、８５℃の油浴内で窒素パージを実施しながら１時間撹拌した。サンプル導入用滴下ロートに、原料モノマーとしてメチルメタクリレート（Ｃ１−ＭＡ）１２ｇ、２−オクチルドデシルメタクリレート（Ａ２）９ｇ及びステアリルメタクリレート（Ｃ１８−ＭＡ）９ｇ、ラジカル開始剤としてアゾビスイソブチロニトリル（ＡＩＢＮ）０．０９１ｇを混合した原料を投入し、この原料を７０分かけて反応フラスコ内に滴下した。その後、窒素フロー下にて８５℃で撹拌を保持して８時間重合を実施し、ポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。その後、１３０℃、１ｍｍＨｇで３時間真空蒸留を実施して、上記溶液から未反応モノマーを除去した。 A 300 ml four-necked reaction flask equipped with a stirring blade (with vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen, and a dropping funnel for introducing sample was charged with 30 g of highly purified mineral oil as a solvent, and an oil at 85 ° C. The mixture was stirred for 1 hour while purging with nitrogen in the bath. In a dropping funnel for sample introduction, 12 g of methyl methacrylate (C1-MA), 9 g of 2-octyldodecyl methacrylate (A2) and 9 g of stearyl methacrylate (C18-MA) as raw materials monomers, azobisisobutyronitrile (AIBN) as a radical initiator ) A raw material mixed with 0.091 g was added, and this raw material was dropped into the reaction flask over 70 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.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、実施例１と同様にＧＰＣ分析を行った結果、重量平均分子量Ｍｗは８８，０００、数平均分子量Ｍｎは７２，０００、Ｍｗ／Ｍｎは１．２２であった。 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 88,000, the number average molecular weight Mn was 72,000, and Mw / Mn was 1.22.
［実施例４〜２３、比較例１〜２、４〜７、参考例１］
原料の配合量を表１、３、５、７、９、１１に示すとおりに変更し、それ以外は上記の合成条件１〜４のいずれかと同様にして、ポリ（メタ）アクリレート系粘度指数向上剤を合成した。なお、表中、Ｃ１２−ＭＡは式（６）中のＲ１がメチル基、Ｒ２がドデシル基（炭素数１２の直鎖アルキル基）である化合物、また、Ａ１：ｍ＝７、ｎ＝６等は式（５）中のＲ１がメチル基、Ｒ２が式（３）でｍ＝７、ｎ＝６である化合物等をそれぞれ表す。得られたポリ（メタ）アクリレート系粘度指数向上剤のＭｗ、Ｍｎ及びＭｗ／Ｍｎを表２、４、６、８、１０、１２に示す。
[Examples 4-23, Comparative Examples 1-2, 4-7, Reference Example 1]
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, C12-MA is a compound in which R 1 in formula (6) is a methyl group and R 2 is a dodecyl group (a linear alkyl group having 12 carbon atoms), and A1: m = 7, n = 6 etc. represents a compound in which R 1 in the formula (5) is a methyl group and R 2 is m = 7 and n = 6 in the formula (3). Tables 2, 4, 6, 8, 10, and 12 show Mw, Mn, and Mw / Mn of the obtained poly (meth) acrylate viscosity index improvers.
＜潤滑油組成物の調製＞
実施例１〜２３、比較例１〜７及び参考例１でそれぞれ得られたポリ（メタ）アクリレート系粘度指数向上剤と、金属系（カルシウムスルホネート系）清浄剤、無灰分散剤（コハク酸イミド）、摩擦調整剤（グリセリンモノオレート）及び摩耗防止剤（亜鉛ジチオフォスフェート）を含む性能添加剤と、高度精製鉱油（ＧｒｏｕｐＩＩＩ基油、１００℃における動粘度：４．２ｍｍ２／ｓ、ＶＩ：１２５）とを、表２、４、６、８、１０、１２に示す割合で配合し、潤滑油組成物を調製した。
<Preparation of lubricating oil composition>
Poly (meth) acrylate viscosity index improvers obtained in Examples 1 to 23, Comparative Examples 1 to 7 and Reference Example 1, metal (calcium sulfonate) detergents, ashless dispersant (succinimide) , A performance additive including a friction modifier (glycerin monooleate) and an antiwear 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) ) In the proportions shown in Tables 2, 4, 6, 8, 10, and 12 to prepare lubricating oil compositions.
＜潤滑油組成物の評価＞
実施例１〜２３、比較例１〜７及び参考例１の各潤滑油組成物について、１００℃における動粘度、粘度指数、１００℃及び１５０℃におけるＨＴＨＳ粘度、並びに−４０℃におけるＭＲＶ粘度を、それぞれ下記に準拠した方法により測定した。結果を表２、４、６、８、１０、１２に示す。なお、表中、ＭＲＶ粘度の項目における「Ｙ．Ｓ．」は降伏応力を表し、規格外れを意味する。
動粘度：ＪＩＳ Ｋ−２２８３−１９９３
粘度指数：ＪＩＳ Ｋ ２２８３−１９９３
ＨＴＨＳ粘度：ＡＳＴＭ Ｄ−４６８３
ＭＲＶ粘度：ＡＳＴＭ Ｄ−４６８４
<Evaluation of lubricating oil composition>
About each lubricating oil composition of Examples 1-23, Comparative Examples 1-7, and Reference Example 1, kinematic viscosity at 100 ° C., viscosity index, HTHS viscosity at 100 ° C. and 150 ° C., and MRV viscosity at −40 ° C. Each was measured by a method 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
Claims (5)
［式（１）及び（２）中、Ｒ１は水素又はメチル基を示し、Ｒ２は下記一般式（３）で表される基を示し、Ｒ３は直鎖の炭素数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。］ A polymer chain comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) , wherein the general formula (1) is based on the total amount of structural units contained in the polymer chain. 20% by mass or more of the structural unit represented by the general formula (2), 20 to 50% by mass of the structural unit in which R 3 is a methyl group, and represented by the general formula (2), R 3 has a polymer chain containing 20 to 50% by mass of a structural unit of an alkyl group having 18 carbon atoms , the weight average molecular weight Mw is 100,000 or more, and the ratio Mw between the weight average molecular weight Mw and the number average molecular weight Mn A poly (meth) acrylate viscosity index improver having a / Mn of 1.5 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. ]
The lubricating oil composition has a kinematic viscosity at 100 ° C. of 3.0 to 12.5 mm 2 / s, an HTHS viscosity at 150 ° C. of 1.7 mPa · s or more, and an HTHS viscosity at 100 ° C. of 5.0 mPa · s. The lubricating oil composition according to claim 3 or 4, which is s or less.
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| CN201380034032.7A CN104395445A (en) | 2012-07-24 | 2013-07-24 | Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver |
| US14/413,792 US20150175926A1 (en) | 2012-07-24 | 2013-07-24 | Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver |
| PCT/JP2013/070088 WO2014017554A1 (en) | 2012-07-24 | 2013-07-24 | Poly(meth)acrylate viscosity index improver, and lubricating oil composition and lubricating oil additive containing said viscosity index improver |
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| GB1559952A (en) * | 1977-10-26 | 1980-01-30 | Shell Int Research | Lubricating oil compositions |
| JPS54149704A (en) * | 1978-05-16 | 1979-11-24 | Japan Synthetic Rubber Co Ltd | Reduction of flow resistance of non-aqueous liquid |
| HUT69298A (en) * | 1993-07-23 | 1995-09-28 | Rohm & Haas | Method of making a copolymer useful as viscosity index improving additive for hydraulic fluids |
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| US5817606A (en) * | 1996-08-08 | 1998-10-06 | Rohm And Haas Company | Viscosity index improving additives for phosphate ester-containing hydraulic fluids |
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