JP2016210941A - Lubricant oil additive and lubricant oil composition - Google Patents

Lubricant oil additive and lubricant oil composition Download PDF

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JP2016210941A
JP2016210941A JP2015097708A JP2015097708A JP2016210941A JP 2016210941 A JP2016210941 A JP 2016210941A JP 2015097708 A JP2015097708 A JP 2015097708A JP 2015097708 A JP2015097708 A JP 2015097708A JP 2016210941 A JP2016210941 A JP 2016210941A
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lubricating oil
lubricating
oil additive
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JP5866700B1 (en
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和枝 栗原
Kazue Kurihara
和枝 栗原
真爾 山田
Shinji Yamada
真爾 山田
真一 遊佐
Shinichi Yusa
真一 遊佐
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Tohoku University NUC
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Abstract

PROBLEM TO BE SOLVED: To provide an environmentally gentle lubrication oil additive and a lubrication oil composition excellent in friction reduction effect, even in the sliding conditions of a high load and a low shear speed, capable of suppressing the reduction of the film thickness of lubrication oil at the boundary face of material, having the reduced number of blending components, easily treatable and capable of reducing phosphorous and sulfur.SOLUTION: In such a manner that a lubrication part 12 made of a linear polymer is held, a pair of adsorption parts 11 are respectively coupled to both the edges of the polymer of the lubrication part 12. The lubrication part 12 can be dissolved into base oil, and, e.g., includes a polymethacrylate chain, an olefin copolymer chain and a polyisobutylene chain. Each absorption part 11 is made of a functional group adsorbable in a material of metal or the like. Each adsorption part 11, e.g., includes a carboxyl group, a phosphoric acid group, an amino group, a thiol group or the like.SELECTED DRAWING: Figure 1

Description

本発明は、潤滑油添加剤および潤滑油組成物に関する。   The present invention relates to lubricating oil additives and lubricating oil compositions.

近年、エンジンや一般的な機械などの材料間の摩擦を低減するための潤滑油において、摩擦低減および燃費向上のために、潤滑油の基油の粘度をより低くする傾向がある。この傾向は、特にエンジンの潤滑油などにおいて顕著である。そこで、摩擦や摩耗を低減するために、高級脂肪酸や高級アルコールなどの油性向上剤や、リン酸エステルやジチオリン酸亜鉛などの反応性の耐摩耗剤、有機硫黄化合物などが、潤滑油の基油に配合されている。また、温度による粘度変化を抑え、粘度特性を最適化するために、粘度指数向上剤として、ポリメタクリレートやオレフィンコポリマー、ポリイソブチレンなどのポリマーが、別途、基油に配合されている(例えば、特許文献1乃至3参照)。   In recent years, lubricating oils for reducing friction between materials such as engines and general machines tend to lower the viscosity of the base oil of the lubricating oil in order to reduce friction and improve fuel efficiency. This tendency is particularly remarkable in engine lubricating oil and the like. Therefore, in order to reduce friction and wear, oiliness improvers such as higher fatty acids and higher alcohols, reactive antiwear agents such as phosphate esters and zinc dithiophosphate, organic sulfur compounds, etc. It is blended. In addition, polymers such as polymethacrylates, olefin copolymers, and polyisobutylene are separately blended in base oils as viscosity index improvers in order to suppress viscosity changes due to temperature and optimize viscosity characteristics (for example, patents) References 1 to 3).

特開2010−95664号公報JP 2010-95664 A 特開2011−57758号公報JP 2011-57758 A 特開2001−19990号公報Japanese Patent Laid-Open No. 2001-19990

しかしながら、特許文献1乃至3に記載のような低粘度の潤滑油は、高荷重、低せん断速度での滑り条件では、材料の境界面から容易に排出されてしまうため、材料の表面同士が接触して摩擦が増大してしまうという課題があった。材料の表面同士の接触を防ぐためには、材料の境界面での潤滑油の膜厚を大きくする必要があるが、潤滑油の膜厚を大きくするためには潤滑油の粘度を大きくしなければならず、やはり摩擦が増大してしまうという課題があった。   However, the low-viscosity lubricating oils described in Patent Documents 1 to 3 are easily discharged from the interface between the materials under sliding conditions at a high load and a low shear rate. As a result, there is a problem that friction increases. In order to prevent contact between the surfaces of the material, it is necessary to increase the thickness of the lubricating oil at the interface between the materials, but in order to increase the thickness of the lubricating oil, the viscosity of the lubricating oil must be increased. However, there was still a problem that the friction increased.

また、特許文献1乃至3に記載のような潤滑油は、配合成分数が多いため、処方が複雑であるという課題もあった。また、低温条件では、リン酸エステルやジチオリン酸亜鉛などの反応性の添加剤が反応しにくいため、摩擦低減効果が不十分になるという課題もあった。また、添加剤に含まれるリンや硫黄が環境破壊の原因になるため、これらを低減する必要があるという課題もあった。   In addition, the lubricating oils described in Patent Documents 1 to 3 have a problem that the formulation is complicated due to the large number of blending components. Moreover, since reactive additives, such as phosphate ester and zinc dithiophosphate, are difficult to react under low temperature conditions, there is also a problem that the friction reducing effect becomes insufficient. Moreover, since phosphorus and sulfur contained in the additive cause environmental destruction, there is a problem that it is necessary to reduce them.

本発明は、このような課題に着目してなされたもので、摩擦低減効果に優れ、高荷重、低せん断速度での滑り条件であっても、材料の境界面での潤滑油の膜厚の低下を抑制することができ、配合成分数が少なく容易に処方可能であり、リンや硫黄を低減可能で環境にやさしい潤滑油添加剤および潤滑油組成物を提供することを目的とする。   The present invention has been made paying attention to such problems, and is excellent in the friction reduction effect. Even under slip conditions at a high load and a low shear rate, the film thickness of the lubricating oil at the interface of the material is improved. An object of the present invention is to provide a lubricating oil additive and a lubricating oil composition that can suppress the decrease, can be easily formulated with a small number of components, can reduce phosphorus and sulfur, and are environmentally friendly.

上記目的を達成するために、本発明に係る潤滑油添加剤は、材料間の摩擦を低減するための潤滑油に添加して使用される潤滑油添加剤であって、前記潤滑油の基油に溶解可能な高分子量の潤滑部と、前記材料に吸着可能な官能基を有し、前記潤滑部を挟むよう前記潤滑部に結合された1対の吸着部とを、有することを特徴とする。   In order to achieve the above object, the lubricating oil additive according to the present invention is a lubricating oil additive used by being added to a lubricating oil for reducing friction between materials, wherein the base oil of the lubricating oil is used. A high-molecular-weight lubricating portion that can be dissolved in the material, and a pair of adsorbing portions that have a functional group that can be adsorbed to the material and are coupled to the lubricating portion so as to sandwich the lubricating portion. .

本発明に係る潤滑油添加剤は、高分子量の潤滑油添加剤(ポリマー)であり、潤滑油の基油に添加して使用される。その潤滑油を材料間に使用したとき、1対の吸着部が材料に吸着し、各吸着部に挟まれた、基油に溶解可能な高分子量の潤滑部も材料間に残る。この材料間の潤滑部や各吸着部が油性向上剤としての役割を果たすことにより、摩擦や摩耗を低減する効果を発揮することができる。また、それと同時に、未吸着の潤滑部が基油中に溶解しているため、温度による粘度変化を抑え、粘度特性を最適化する粘度指数向上効果を十分に発揮することができる。このように、本発明に係る潤滑油添加剤によれば、優れた摩擦低減効果が得られる。   The lubricating oil additive according to the present invention is a high molecular weight lubricating oil additive (polymer), which is used by being added to the base oil of the lubricating oil. When the lubricating oil is used between the materials, a pair of adsorbing portions are adsorbed on the material, and a high molecular weight lubricating portion which is sandwiched between the adsorbing portions and is soluble in the base oil remains between the materials. Since the lubrication part and each adsorption part between these materials play a role as an oiliness improver, the effect of reducing friction and wear can be exhibited. At the same time, since the non-adsorbed lubricating part is dissolved in the base oil, the viscosity index improvement effect of suppressing the viscosity change due to temperature and optimizing the viscosity characteristics can be sufficiently exhibited. Thus, according to the lubricating oil additive of the present invention, an excellent friction reducing effect can be obtained.

また、潤滑部が各吸着部に挟まれて結合しているため、高荷重、低せん断速度での滑り条件であっても、材料の境界面から排出されにくく、材料の境界面での潤滑油の膜厚の低下を抑制することができる。このため、高荷重、低せん断速度での滑り条件であっても、摩擦の増大を防ぐことができ、摩擦低減効果を維持することができる。   In addition, since the lubrication part is sandwiched between the adsorbing parts and joined, even when the sliding condition is high load and low shear rate, it is difficult to drain from the material interface, and the lubricating oil at the material interface Can be suppressed. For this reason, even if it is a sliding condition with a high load and a low shear rate, an increase in friction can be prevented and a friction reduction effect can be maintained.

本発明に係る潤滑油添加剤は、材料に吸着して効果を発揮する吸着系の添加剤であるため、反応系の添加剤が効きにくい低温条件(常温付近)でも十分に摩擦低減効果を発揮することができる。また、従来の油性向上剤や反応系の添加剤、粘度指数向上剤などを基油に別々に配合する場合と比べて配合成分数が少なく、容易に処方可能である。また、リンや硫黄を極力使用せずに摩擦低減効果を得ることができ、リンや硫黄を低減可能で環境にやさしい。   Since the lubricating oil additive according to the present invention is an adsorbent additive that is adsorbed to the material and exhibits its effect, it exhibits a sufficient friction reducing effect even at low temperature conditions (near room temperature) where the reaction additive is not effective. can do. In addition, the number of blending components is small compared to the case where conventional oiliness improvers, reaction system additives, viscosity index improvers and the like are separately blended into the base oil, and can be easily formulated. Moreover, the friction reduction effect can be obtained without using phosphorus and sulfur as much as possible, and phosphorus and sulfur can be reduced, which is environmentally friendly.

本発明に係る潤滑油添加剤で、前記潤滑部は、ポリメタクリレート鎖、オレフィンコポリマー鎖、およびポリイソブチレン鎖のうちの1種以上を含んでいることが好ましい。この場合、優れた粘度指数向上効果を得ることができる。また、各吸着部は、カルボキシル基、リン酸基、アミノ基およびチオール基のうちの1種以上を含んでいることが好ましい。この場合、各吸着部が油性向上剤としての役割を果たし、優れた摩擦低減効果を得ることができる。   In the lubricating oil additive according to the present invention, the lubricating part preferably contains one or more of a polymethacrylate chain, an olefin copolymer chain, and a polyisobutylene chain. In this case, an excellent viscosity index improvement effect can be obtained. Moreover, it is preferable that each adsorption part contains 1 or more types among a carboxyl group, a phosphate group, an amino group, and a thiol group. In this case, each adsorption part plays a role as an oiliness improver, and an excellent friction reducing effect can be obtained.

本発明に係る潤滑油添加剤で、前記潤滑部は鎖状のポリマーから成り、各吸着部は前記ポリマーの両端にそれぞれ結合されていることが好ましい。この場合、高荷重、低せん断速度での滑り条件であっても、鎖状のポリマーから成る潤滑部を材料間に留めることができ、優れた摩擦低減効果を得ることができる。   In the lubricating oil additive according to the present invention, it is preferable that the lubricating part is made of a chain polymer, and each adsorbing part is bonded to both ends of the polymer. In this case, even under sliding conditions with a high load and a low shear rate, the lubrication part made of a chain polymer can be retained between the materials, and an excellent friction reducing effect can be obtained.

本発明に係る潤滑油添加剤は、前記潤滑部がメタクリル酸エステルユニットを含み、各吸着部がカルボキシル基を含む一般式(1)で表される化合物を有していてもよい。この場合、特に優れた摩擦低減効果が得られる。
(式中、m,n,pおよびqは、1以上の整数である。)
The lubricating oil additive according to the present invention may have a compound represented by the general formula (1) in which the lubricating portion includes a methacrylic acid ester unit and each adsorption portion includes a carboxyl group. In this case, a particularly excellent friction reducing effect can be obtained.
(In the formula, m, n, p and q are integers of 1 or more.)

前記一般式(1)中のmは100〜1000の整数であることが好ましい。また、nは11〜21の整数であることが好ましい。また、pは2〜10の整数であることが好ましい。また、qは5〜18の整数であることが好ましい。これらの場合、さらに優れた摩擦低減効果が得られる。   M in the general formula (1) is preferably an integer of 100 to 1,000. Moreover, it is preferable that n is an integer of 11-21. Moreover, it is preferable that p is an integer of 2-10. Moreover, it is preferable that q is an integer of 5-18. In these cases, a further excellent friction reducing effect can be obtained.

本発明に係る潤滑油組成物は、前記潤滑油の基油に、本発明に係る潤滑油添加剤が添加されていることを特徴とする。   The lubricating oil composition according to the present invention is characterized in that the lubricating oil additive according to the present invention is added to the base oil of the lubricating oil.

本発明に係る潤滑油組成物は、本発明に係る潤滑油添加剤が添加されているため、摩擦低減効果に優れ、高荷重、低せん断速度での滑り条件であっても、材料の境界面での潤滑油の膜厚の低下を抑制することができる。また、容易に処方可能であり、リンや硫黄が少なく環境にやさしい。   Since the lubricating oil composition according to the present invention is added to the lubricating oil composition according to the present invention, it has an excellent friction reducing effect, and even under sliding conditions at high load and low shear rate, the boundary surface of the material It is possible to suppress a decrease in the film thickness of the lubricating oil. In addition, it can be formulated easily and is low in phosphorus and sulfur and is environmentally friendly.

本発明に係る潤滑油組成物は、前記潤滑油の基油100質量部に対して、前記潤滑油添加剤が0.1〜10質量部含有されていることが好ましい。この場合、特に優れた摩擦低減効果が得られる。   The lubricating oil composition according to the present invention preferably contains 0.1 to 10 parts by mass of the lubricating oil additive with respect to 100 parts by mass of the base oil of the lubricating oil. In this case, a particularly excellent friction reducing effect can be obtained.

本発明によれば、摩擦低減効果に優れ、高荷重、低せん断速度での滑り条件であっても、材料の境界面での潤滑油の膜厚の低下を抑制することができ、配合成分数が少なく容易に処方可能であり、リンや硫黄を低減可能で環境にやさしい潤滑油添加剤および潤滑油組成物を提供することができる。   According to the present invention, the friction reduction effect is excellent, and even under sliding conditions at a high load and a low shear rate, it is possible to suppress a decrease in the film thickness of the lubricating oil at the material interface, Therefore, it is possible to provide a lubricating oil additive and a lubricating oil composition that can be easily formulated with a small amount, can reduce phosphorus and sulfur, and are environmentally friendly.

本発明の実施の形態の潤滑油添加剤を示す化学式である。It is a chemical formula which shows the lubricating oil additive of embodiment of this invention. 本発明の実施の形態の潤滑油添加剤の、平滑表面間のナノ摩擦特性を評価するための試験方法を示す側面図である。It is a side view which shows the test method for evaluating the nano friction characteristic between smooth surfaces of the lubricating oil additive of embodiment of this invention. 図2に示す平滑表面間のナノ摩擦特性を評価するための試験の(a)せん断速度V=0.011μm/sのとき、(b)せん断速度V=1.1μm/sのときの試験結果を示すグラフである。FIG. 2 shows the test results for evaluating the nanofriction characteristics between the smooth surfaces shown in FIG. 2 when (a) the shear rate V = 0.011 μm / s and (b) the shear rate V = 1.1 μm / s. It is a graph. 本発明の実施の形態の潤滑油添加剤の、凹凸表面間のマクロ摩擦特性を評価するためのボールオンディスク試験の試験方法を示す斜視図である。It is a perspective view which shows the test method of the ball-on-disk test for evaluating the macro friction characteristic between the uneven | corrugated surfaces of the lubricating oil additive of embodiment of this invention. 図4に示すボールオンディスク試験の試験結果を示すグラフである。It is a graph which shows the test result of the ball on disk test shown in FIG.

図1乃至図5は、本発明の実施の形態の潤滑油添加剤を示している。
以下、摩擦特性を評価するための試験の結果に基づいて、本発明の実施の形態の潤滑油添加剤について説明する。
1 to 5 show a lubricating oil additive according to an embodiment of the present invention.
Hereinafter, the lubricating oil additive according to the embodiment of the present invention will be described based on the result of the test for evaluating the friction characteristics.

[試験に使用する潤滑油添加剤]
摩擦特性評価試験に使用する本発明の実施の形態の潤滑油添加剤として、図1の(2)式に示すABA型のブロックコポリマーを製造した。図1に示すように、本発明の実施の形態の潤滑油添加剤は、「A」に該当する1対の吸着部11と、「B」に該当する潤滑部12とを有している。各吸着部11は、金属などの材料の表面に吸着可能なカルボキシル基を含む分子から成っている。潤滑部12は、基油に溶解可能であるメタクリル酸エステルユニットを含む鎖状のポリマーから成っている。本発明の実施の形態の潤滑油添加剤は、1対の吸着部11が、潤滑部12を挟むようそれぞれ潤滑部12の両端に結合されている。
[Lubricating oil additive used for testing]
An ABA type block copolymer represented by the formula (2) in FIG. 1 was produced as the lubricating oil additive of the embodiment of the present invention used for the friction characteristic evaluation test. As shown in FIG. 1, the lubricant additive according to the embodiment of the present invention has a pair of adsorbing portions 11 corresponding to “A” and a lubricating portion 12 corresponding to “B”. Each adsorption part 11 consists of the molecule | numerator containing the carboxyl group which can adsorb | suck to the surface of materials, such as a metal. The lubrication part 12 consists of the chain | strand-shaped polymer containing the methacrylic acid ester unit which can be melt | dissolved in base oil. In the lubricating oil additive according to the embodiment of the present invention, a pair of adsorbing portions 11 are coupled to both ends of the lubricating portion 12 so as to sandwich the lubricating portion 12.

試験には、表1に示す4種類の潤滑油添加剤を使用した。表1には、各潤滑油添加剤の図1の(2)式中のm(潤滑部12の鎖長)およびn(潤滑部12の側鎖アルキル基の鎖長)、ならびに、数平均分子量(Mn)および、重量平均分子量(Mw)と数平均分子量(Mn)との比である多分散度(Mw/Mn)を示す。   In the test, four types of lubricating oil additives shown in Table 1 were used. Table 1 shows m (the chain length of the lubrication part 12) and n (the chain length of the side chain alkyl group of the lubrication part 12) and the number average molecular weight in the formula (2) of FIG. (Mn) and the polydispersity (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) are shown.

これらの潤滑油添加剤は、二官能性マクロ連鎖移動剤(PAaU10)とアルキルメタクリレートとの重合により製造された。具体的には、(3)式に示すBMATを連鎖移動剤として使用し、ラジカル重合開始剤を用いて、11-アクリルアミドウンデカン酸を、メタノール中、アルゴン雰囲気下、70℃で重合を行って、吸着部位となるPAaU10を合成した。続いて、このPAaU10を連鎖移動剤として用いて、メタクリル酸エステルのラジカル重合を行うことにより、目的の潤滑油添加剤を合成した。   These lubricating oil additives were made by polymerization of a bifunctional macro chain transfer agent (PAaU10) and an alkyl methacrylate. Specifically, using BMAT represented by the formula (3) as a chain transfer agent, using a radical polymerization initiator, 11-acrylamide undecanoic acid is polymerized in methanol at 70 ° C. in an argon atmosphere, PAaU10 was synthesized as an adsorption site. Subsequently, by using this PAaU10 as a chain transfer agent, radical polymerization of a methacrylic acid ester was performed to synthesize the target lubricating oil additive.

なお、比較のため、(4)式に示すホモポリマー(以下、「PSMA174」と示す)、および、(5)式に示すランダムポリマー(以下、「p(S/A4)184」と示す)についても試験を行った。なお、PSMA174は、吸着部11がないポリマーであり、Mn=59,200、Mw/Mn=1.86である。また、p(S/A4)184は、吸着部11と潤滑部12とがランダムに結合されたポリマーであり、Mn=61,900、Mw/Mn=1.79である。 For comparison, a homopolymer represented by the formula (4) (hereinafter referred to as “PSMA 174 ”) and a random polymer represented by the formula (5) (hereinafter referred to as “p (S / A 4 ) 184 ”). ) Was also tested. Note that PSMA 174 is a polymer without the adsorbing portion 11, and Mn = 59,200 and Mw / Mn = 1.86. Further, p (S / A 4 ) 184 is a polymer in which the adsorbing part 11 and the lubricating part 12 are randomly bonded, and Mn = 61,900 and Mw / Mn = 1.79.

[平滑表面間のナノ摩擦特性評価]
本発明の実施の形態の潤滑油添加剤による摩擦低減効果の極限を把握するために、表面力測定装置(SFA)を用いて摩擦力を測定する試験を行った。試験では、図2に示すように、平滑な表面を有する1対の雲母21a,21bの間に試験試料の潤滑油(潤滑油組成物)を挟み、各雲母21a,21bの間隔を狭める方向に荷重Lをかけた状態で、一方の雲母21aをせん断速度Vで滑らせたときの、他方の雲母21bにかかる摩擦力Fを測定した。荷重Lは、5〜40mNの範囲とし、せん断速度Vは、0.011μm/s、1.1μm/sの2種類とした。面積Aは、1200〜4000μm2程度である。
[Nano-friction characteristics evaluation between smooth surfaces]
In order to grasp the limit of the friction reduction effect by the lubricating oil additive according to the embodiment of the present invention, a test for measuring the friction force using a surface force measuring device (SFA) was performed. In the test, as shown in FIG. 2, the lubricating oil (lubricating oil composition) of the test sample is sandwiched between a pair of mica 21a and 21b having a smooth surface, and the interval between the mica 21a and 21b is narrowed. The frictional force F applied to the other mica 21b when one mica 21a was slid at the shear rate V with the load L applied was measured. The load L was in the range of 5 to 40 mN, and the shear rate V was two types of 0.011 μm / s and 1.1 μm / s. The area A is about 1200 to 4000 μm 2 .

試験試料の潤滑油としては、ポリアルファオレフィン(PAO)から成る基油に、表1のA5S992A5を添加した潤滑油(「PAO+ A5S992A5」)、(4)式のホモポリマーPSMA174を添加した潤滑油(「PAO+ PSMA174」)、および、汎用の潤滑油添加剤であるパルミチン酸(PA)を添加した潤滑油(「PAO+PA」)を用いた。これらの濃度は、0.5wt%である。また、基油のみの場合についても試験を行った(「PAO」)。 As a lubricant for the test sample, a lubricant obtained by adding A 5 S 992 A 5 in Table 1 to a base oil composed of polyalphaolefin (PAO) (“PAO + A 5 S 992 A 5 ”), formula (4) The lubricating oil to which the homopolymer PSMA 174 was added ("PAO + PSMA 174 ") and the lubricating oil to which palmitic acid (PA), a general-purpose lubricating oil additive, was added ("PAO + PA") were used. These concentrations are 0.5 wt%. A test was also conducted with only the base oil ("PAO").

試験結果を図3に示す。図3には、試験結果から得られた各潤滑油の摩擦係数μも示している。図3(b)に示すように、V=1.1μm/sのとき、本発明の実施の形態の潤滑油添加剤A5S992A5を添加した潤滑油PAO+ A5S992A5、および、ホモポリマーPSMA174を添加した潤滑油PAO+ PSMA174で、摩擦係数μが0.01よりも小さくなっており、優れた摩擦低減効果を有することが確認された。これに対し、図3(a)に示すように、V=0.011μm/sの低せん断速度のときには、PAO+ PSMA174では摩擦係数μが大きくなっているが、PAO+ A5S992A5では摩擦係数μがほとんど増大せず、依然として0.01よりも小さく、優れた摩擦低減効果を維持できることが確認された。 The test results are shown in FIG. FIG. 3 also shows the friction coefficient μ of each lubricating oil obtained from the test results. As shown in FIG. 3B, when V = 1.1 μm / s, the lubricating oil PAO + A 5 S 992 A 5 to which the lubricating oil additive A 5 S 992 A 5 of the embodiment of the present invention is added, and The lubricating oil PAO + PSMA 174 added with the homopolymer PSMA 174 has a friction coefficient μ smaller than 0.01, and it was confirmed that it has an excellent friction reducing effect. On the other hand, as shown in FIG. 3A, at a low shear rate of V = 0.011 μm / s, the friction coefficient μ is large in PAO + PSMA 174 , but in PAO + A 5 S 992 A 5 , It was confirmed that the coefficient μ hardly increased and was still smaller than 0.01, and an excellent friction reducing effect could be maintained.

なお、せん断速度Vで滑らせる前の静的な膜厚Dを、荷重L=5mNにおいて測定したところ、PAO+ A5S992A5で20nm以下、PAO+ PSMA174で5nm以下、PAOのみで1.4nm以下であった。このように、本発明の実施の形態の潤滑油添加剤PAO+ A5S992A5は、材料の境界面から排出されにくく、材料の境界面での潤滑油の膜厚の低下を抑制することができるといえる。これにより、PAO+ A5S992A5は、高荷重、低せん断速度での滑り条件であっても、優れた摩擦低減効果を示すものと考えられる。 When the static film thickness D before sliding at the shear rate V was measured at a load L = 5 mN, it was 20 nm or less with PAO + A 5 S 992 A 5 , 5 nm or less with PAO + PSMA 174 , and 1.4 nm with PAO alone. It was the following. As described above, the lubricant additive PAO + A 5 S 992 A 5 according to the embodiment of the present invention is less likely to be discharged from the interface of the material, and suppresses a decrease in the film thickness of the lubricant at the interface of the material. Can be said. Thus, PAO + A 5 S 992 A 5 is considered to exhibit an excellent friction reducing effect even under sliding conditions at high load and low shear rate.

[凹凸を有する実用表面間のマクロ摩擦特性評価]
実用に近い材料および条件での、本発明の実施の形態の潤滑油添加剤の摩擦特性を評価するために、トライボメータを使用してボールオンディスク試験を行った。試験では、図4に示すように、スチール(SUJ2)製のディスク22の上に試験試料の潤滑油(潤滑油組成物)を載せ、その上からスチール(SUJ2)製のボール23を荷重Lで押し付けた状態で、せん断速度Vで往復運動させて測定を行った。荷重Lは5mNとした。この荷重は、圧力がエンジンのピストンリングにかかる圧力と同程度の119MPaになる荷重である。また、せん断速度Vは、3×10−3、10−2、3×10−2、10−1、3×10−1、1、3mm/sの7種類とした。
[Evaluation of macro friction characteristics between practical surfaces with irregularities]
In order to evaluate the friction characteristics of the lubricant additive according to the embodiment of the present invention with materials and conditions close to practical use, a ball-on-disk test was performed using a tribometer. In the test, as shown in FIG. 4, a lubricating oil (lubricating oil composition) as a test sample is placed on a steel (SUJ2) disk 22, and a steel (SUJ2) ball 23 is loaded thereon with a load L. In the pressed state, the measurement was performed by reciprocating at a shear rate V. The load L was 5 mN. This load is a load at which the pressure becomes 119 MPa, which is similar to the pressure applied to the piston ring of the engine. Further, the shear velocity V, 3 × 10 -3, 10 -2 , 3 × 10 -2, 10 -1, 3 × 10 -1, and the seven 1,3mm / s.

試験試料の潤滑油としては、ポリアルファオレフィン(PAO)から成る基油に、表1の4種類の潤滑油添加剤を添加した潤滑油(「PAO+ A5L216A5」、「PAO+ A5L946A5」、「PAO+ A5S170A5」、「PAO+ A5S992A5」)、(4)式のホモポリマーPSMA174を添加した潤滑油(「PAO+ PSMA174」)、および、(5)式のランダムポリマーp(S/A4)184を添加した潤滑油(「PAO+p(S/A4)184」)を用いた。これらの濃度は、0.5wt%(0.5質量部)である。また、基油のみの場合(「PAO」)についても試験を行った。 The lubricating oil of the test sample was a lubricating oil ("PAO + A 5 L 216 A 5 ", "PAO + A 5 ", which is a base oil composed of polyalphaolefin (PAO) with the four lubricating oil additives listed in Table 1. L 946 A 5 ”,“ PAO + A 5 S 170 A 5 ”,“ PAO + A 5 S 992 A 5 ”), lubricating oil added with homopolymer PSMA 174 of formula (4) (“ PAO + PSMA 174 ”), and The lubricating oil ("PAO + p (S / A 4 ) 184 ") added with the random polymer p (S / A 4 ) 184 of the formula (5) was used. These concentrations are 0.5 wt% (0.5 parts by mass). A test was also conducted for the case of base oil only ("PAO").

試験結果として摩擦係数の速度依存性を、図5に示す。図5に示すように、本発明の実施の形態の潤滑油添加剤を添加した4種類の潤滑油PAO+ A5L216A5、PAO+ A5L946A5、PAO+ A5S170A5、およびPAO+ A5S992A5は、せん断速度Vが3×10−3〜3mm/sの範囲で、ホモポリマーやランダムポリマーを添加した潤滑油PAO+ PSMA174およびPAO+p(S/A4)184よりも摩擦係数が小さくなっていることが確認された。また、基油のみの場合PAOと比べて、25〜70%程度まで摩擦係数が小さくなっており、優れた摩擦低減効果を有していることが確認された。この結果から、潤滑部12の両端に吸着部11が結合していることにより、摩擦低減効果が顕著に向上するものと考えられる。 FIG. 5 shows the speed dependence of the friction coefficient as a test result. As shown in FIG. 5, four types of lubricating oils PAO + A 5 L 216 A 5 , PAO + A 5 L 946 A 5 , PAO + A 5 S 170 A 5 , to which the lubricating oil additive of the embodiment of the present invention is added, And PAO + A 5 S 992 A 5 are lubricating oils PAO + PSMA 174 and PAO + p (S / A 4 ) having a shear rate V in the range of 3 × 10 −3 to 3 mm / s and containing a homopolymer or a random polymer. It was confirmed that the friction coefficient was smaller than 184 . Further, in the case of only the base oil, the friction coefficient is reduced to about 25 to 70% as compared with PAO, and it was confirmed that the base oil has an excellent friction reducing effect. From this result, it is considered that the friction reducing effect is remarkably improved by the fact that the adsorbing portion 11 is coupled to both ends of the lubricating portion 12.

また、図5に示すように、本発明の実施の形態の潤滑油添加剤を添加した4種類の潤滑油のうち、PAO+ A5L946A5よりもPAO+ A5L216A5の方が、またPAO+ A5S992A5よりもPAO+ A5S170A5の方が、摩擦係数が小さくなっていることが確認された。このことから、潤滑部12の鎖長が短い方が、摩擦低減効果が高いといえる。また、PAO+ A5L946A5よりもPAO+ A5S992A5の方が、またPAO+ A5L216A5よりもPAO+ A5S170A5の方が、摩擦係数が小さくなっていることが確認された。このことから、潤滑部12の側鎖アルキル基の鎖長が長い方が、摩擦低減効果が高いといえる。 Further, as shown in FIG. 5, among the four types of lubricating oils to which the lubricating oil additive according to the embodiment of the present invention is added, PAO + A 5 L 216 A 5 is more preferable than PAO + A 5 L 946 A 5. , also towards the PAO + a 5 S 170 a 5 than PAO + a 5 S 992 a 5, it was confirmed that the friction coefficient is small. From this, it can be said that the shorter the chain length of the lubrication part 12, the higher the friction reduction effect. Further, towards the PAO + A 5 S 992 A 5 than PAO + A 5 L 946 A 5 is also towards the PAO + A 5 S 170 A 5 than PAO + A 5 L 216 A 5 is, the friction coefficient is small It was confirmed. From this, it can be said that the friction reducing effect is higher when the chain length of the side chain alkyl group of the lubricating portion 12 is longer.

また、図5に示すように、本発明の実施の形態の潤滑油添加剤を添加した潤滑油のうち、PAO+ A5L216A5、PAO+ A5S992A5およびPAO+ A5S170A5では、摩擦係数の最小値が0.04程度になっている。従来のMoSなどの無機系の添加剤を使用した潤滑油では、摩擦係数の最小値は、高温・高圧のときに0.05程度であることから、本発明の実施の形態の潤滑油添加剤を使用することにより、無機系添加剤よりも摩擦低減効果を高めることができると考えられる。また、無機系添加剤では、硫黄などを含んでおり、環境破壊の原因となるおそれがあるのに対し、本発明の実施の形態の潤滑油添加剤は、連鎖移動剤として用いたBMAT由来の硫黄原子を3個含むのみで、リンは含んでおらず、環境にやさしいといえる。 Further, as shown in FIG. 5, among the lubricating oils to which the lubricating oil additive according to the embodiment of the present invention is added, PAO + A 5 L 216 A 5 , PAO + A 5 S 992 A 5 and PAO + A 5 S 170 A In 5 , the minimum value of the friction coefficient is about 0.04. In the case of a lubricating oil using an inorganic additive such as conventional MoS 2 , the minimum value of the friction coefficient is about 0.05 at high temperature and high pressure. By using the agent, it is considered that the friction reducing effect can be enhanced as compared with the inorganic additive. In addition, the inorganic additive contains sulfur and may cause environmental destruction, whereas the lubricant additive according to the embodiment of the present invention is derived from the BMAT used as the chain transfer agent. It contains only three sulfur atoms, does not contain phosphorus, and can be said to be environmentally friendly.

以上の試験結果から、本発明の実施の形態の潤滑油添加剤の作用について説明する。すなわち、本発明の実施の形態の潤滑油添加剤は、潤滑油の基油に添加して使用され、その潤滑油を金属等の材料間に使用したとき、1対の吸着部11が材料に吸着し、各吸着部11に挟まれた、潤滑部12も材料間に残る。このため、潤滑部12や各吸着部11が油性向上剤としての役割を果たすことにより、摩擦や摩耗を低減する効果を発揮することができる。また、それと同時に、未吸着の潤滑部12が基油中に溶解しているため、温度による粘度変化を抑え、粘度特性を最適化する粘度指数向上効果を十分に発揮することができる。このように、本発明の実施の形態の潤滑油添加剤によれば、優れた摩擦低減効果が得られる。例えば、基油のみの場合と比べて最大で70%、従来の高級脂肪酸や高級アルコールなどの添加剤と比べても最大で50%程度まで、潤滑油の摩擦係数を低下させることができる。   From the above test results, the operation of the lubricating oil additive according to the embodiment of the present invention will be described. That is, the lubricating oil additive according to the embodiment of the present invention is used by being added to the base oil of the lubricating oil, and when the lubricating oil is used between materials such as metals, the pair of adsorbing portions 11 is used as the material. The lubricating portion 12 that is adsorbed and sandwiched between the adsorbing portions 11 also remains between the materials. For this reason, the lubrication part 12 and each adsorption | suction part 11 can exhibit the effect which reduces friction and abrasion by playing the role as an oil-based improvement agent. At the same time, since the unadsorbed lubricating part 12 is dissolved in the base oil, the viscosity index improvement effect of suppressing the viscosity change due to temperature and optimizing the viscosity characteristic can be sufficiently exhibited. Thus, according to the lubricant additive of the embodiment of the present invention, an excellent friction reducing effect can be obtained. For example, the friction coefficient of the lubricating oil can be reduced to a maximum of 70% compared to the case of the base oil alone and to a maximum of about 50% compared to conventional additives such as higher fatty acids and higher alcohols.

また、潤滑部12が各吸着部11に挟まれて結合しているため、高荷重、低せん断速度での滑り条件であっても、金属等の材料の境界面から排出されにくく、材料の境界面での潤滑油の膜厚の低下を抑制することができる。このため、高荷重、低せん断速度での滑り条件であっても、摩擦の増大を防ぐことができ、摩擦低減効果を維持することができる。   In addition, since the lubrication part 12 is sandwiched between the adsorbing parts 11 and coupled to each other, it is difficult for the lubrication part 12 to be discharged from the boundary surface of the material such as a metal even under slip conditions at a high load and a low shear rate. A reduction in the film thickness of the lubricating oil on the surface can be suppressed. For this reason, even if it is a sliding condition with a high load and a low shear rate, an increase in friction can be prevented and a friction reduction effect can be maintained.

本発明の実施の形態の潤滑油添加剤は、材料に吸着して効果を発揮する吸着系の添加剤であるため、反応系の添加剤が効きにくい低温条件(常温付近)でも十分に摩擦低減効果を発揮することができる。このため、例えば、ハイブリッドカーなどではエンジンの温度上昇が小さく反応性の添加剤は効きにくいが、本発明の実施の形態の潤滑油添加剤を使用することにより、潤滑油の摩擦低減効果を十分に発揮することができる。   The lubricant additive according to the embodiment of the present invention is an adsorbent additive that adsorbs on the material and exhibits its effect, so that friction is sufficiently reduced even at low temperature conditions (near room temperature) where the reaction additive is not effective. The effect can be demonstrated. For this reason, for example, in a hybrid car or the like, the engine temperature rise is small and the reactive additive is hardly effective. However, by using the lubricating oil additive according to the embodiment of the present invention, the friction reducing effect of the lubricating oil is sufficiently obtained. Can be demonstrated.

本発明の実施の形態の潤滑油添加剤は、2つの吸着部11と1つの潤滑部12とが結合した1つの成分が、油性向上剤および粘度指数向上剤などの複数の機能を有するため、従来の油性向上剤や反応系の添加剤、粘度指数向上剤などを基油に別々に配合する場合と比べて配合成分数が少なくなり、容易に処方可能である。また、リンや硫黄を極力使用せずに摩擦低減効果を得ることができ、リンや硫黄を低減可能で環境にやさしい。   In the lubricating oil additive according to the embodiment of the present invention, one component in which two adsorbing portions 11 and one lubricating portion 12 are combined has a plurality of functions such as an oiliness improver and a viscosity index improver. Compared to the case where conventional oiliness improvers, reaction system additives, viscosity index improvers, and the like are separately blended into the base oil, the number of blending components is reduced and can be easily formulated. Moreover, the friction reduction effect can be obtained without using phosphorus and sulfur as much as possible, and phosphorus and sulfur can be reduced, which is environmentally friendly.

なお、本発明の実施の形態の潤滑油添加剤で、潤滑部12は、ポリメタクリレート鎖に限らず、オレフィンコポリマー鎖やポリイソブチレン鎖を含んでいてもよい。これらの場合にも、優れた粘度指数向上効果を得ることができる。また、各吸着部11は、カルボキシル基に限らず、リン酸基やアミノ基、チオール基を含んでいてもよい。これらの場合にも、各吸着部11が油性向上剤としての役割を果たし、優れた摩擦低減効果を得ることができる。また、一般式(1)中のmは100〜1000の整数であることが好ましい。また、nは11〜21の整数であることが好ましい。また、pは2〜10の整数であることが好ましい。また、qは5〜18の整数であることが好ましい。これらの場合、優れた摩擦低減効果が得られる。   In the lubricating oil additive according to the embodiment of the present invention, the lubricating portion 12 is not limited to a polymethacrylate chain, and may include an olefin copolymer chain or a polyisobutylene chain. Also in these cases, an excellent viscosity index improving effect can be obtained. Moreover, each adsorption part 11 may contain not only a carboxyl group but a phosphoric acid group, an amino group, and a thiol group. Also in these cases, each adsorption | suction part 11 plays the role as an oil improvement agent, and can acquire the outstanding friction reduction effect. Moreover, it is preferable that m in General formula (1) is an integer of 100-1000. Moreover, it is preferable that n is an integer of 11-21. Moreover, it is preferable that p is an integer of 2-10. Moreover, it is preferable that q is an integer of 5-18. In these cases, an excellent friction reducing effect can be obtained.

21a,21b 雲母
22 ディスク
23 ボール
21a, 21b Mica 22 Disc 23 Ball

上記目的を達成するために、本発明に係る潤滑油添加剤は、材料間の摩擦を低減するための潤滑油に添加して使用される潤滑油添加剤であって、前記潤滑油の基油に溶解可能な高分子量の潤滑部と、前記材料に吸着可能な官能基を有し、前記潤滑部を挟むよう前記潤滑部に結合された1対の吸着部とを有し、前記潤滑部がメタクリル酸エステルユニットを含み、各吸着部がカルボキシル基を含む一般式(1)で表される化合物を有することを特徴とする。
(式中、m,n,pおよびqは、1以上の整数である。)
To achieve the above object, the lubricating oil additive of the present invention, the lubricating oil for reducing friction between the materials, a lubricating oil additive used is added, the lubricating oil base A lubricating part having a high molecular weight that can be dissolved in oil; and a pair of adsorbing parts that have a functional group that can adsorb to the material and are coupled to the lubricating part so as to sandwich the lubricating part. Has a compound represented by the general formula (1) containing a methacrylic acid ester unit and each adsorbing part containing a carboxyl group .
(In the formula, m, n, p and q are integers of 1 or more.)

本発明に係る潤滑油添加剤、前記潤滑部がメタクリル酸エステルユニットを含んでいるため、優れた粘度指数向上効果を得ることができる。また、各吸着部、カルボキシル基を含んでいるため、各吸着部が油性向上剤としての役割を果たし、優れた摩擦低減効果を得ることができる。
The lubricating oil additive of the present invention, since the lubricant portion contains a methacrylic acid ester unit, it is possible to obtain an excellent viscosity index improving effect. Further, each suction part, because it contains a carboxyl group, can each suction portion serves as the oiliness improver, to obtain a good friction reducing effect.

本発明に係る潤滑油添加剤、前記潤滑部鎖状のポリマーから成り、各吸着部前記ポリマーの両端にそれぞれ結合されているため、高荷重、低せん断速度での滑り条件であっても、鎖状のポリマーから成る潤滑部を材料間に留めることができ、優れた摩擦低減効果を得ることができる。
The lubricating oil additive of the present invention comprises the lubricating unit is a chain-like polymer, for each suction unit is coupled to both ends of the polymer, high load, a slip condition at low shear rates However, the lubrication part which consists of chain polymers can be stopped between materials, and the outstanding friction reduction effect can be acquired.

[試験に使用する潤滑油添加剤]
摩擦特性評価試験に使用する本発明の実施の形態の潤滑油添加剤として、図1の(2)式に示すABA型のブロックコポリマーを製造した。図1に示すように、本発明の実施の形態の潤滑油添加剤は、「A」に該当する1対の吸着部11と、「B」に該当する潤滑部12とを有している。各吸着部11は、金属などの材料の表面に吸着可能なカルボキシル基を含む分子から成っている。潤滑部12は、基油に溶解可能であるメタクリル酸エステルユニットを含む鎖状のポリマーから成っている。本発明の実施の形態の潤滑油添加剤は、1対の吸着部11が、潤滑部12を挟むようそれぞれ潤滑部12の両端に結合されている。
[Lubricating oil additive used for testing]
An ABA type block copolymer represented by the formula (2) in FIG. 1 was produced as the lubricating oil additive of the embodiment of the present invention used for the friction characteristic evaluation test. As shown in FIG. 1, the lubricant additive according to the embodiment of the present invention has a pair of adsorbing portions 11 corresponding to “A” and a lubricating portion 12 corresponding to “B”. Each adsorption part 11 consists of the molecule | numerator containing a carboxyl group which can adsorb | suck to the surface of materials, such as a metal. The lubrication part 12 consists of the chain | strand-shaped polymer containing the methacrylic acid ester unit which can be melt | dissolved in base oil. In the lubricating oil additive according to the embodiment of the present invention, a pair of adsorbing portions 11 are coupled to both ends of the lubricating portion 12 so as to sandwich the lubricating portion 12.

Claims (11)

材料間の摩擦を低減するための潤滑油に添加して使用される潤滑油添加剤であって、
前記潤滑油の基油に溶解可能な高分子量の潤滑部と、
前記材料に吸着可能な官能基を有し、前記潤滑部を挟むよう前記潤滑部に結合された1対の吸着部とを、
有することを特徴とする潤滑油添加剤。
A lubricating oil additive used in addition to a lubricating oil to reduce friction between materials,
A high molecular weight lubricating part that is soluble in the base oil of the lubricating oil;
A pair of adsorbing portions having functional groups capable of adsorbing to the material and coupled to the lubricating portions so as to sandwich the lubricating portions;
Lubricating oil additive characterized by having.
前記潤滑部は、ポリメタクリレート鎖、オレフィンコポリマー鎖、およびポリイソブチレン鎖のうちの1種以上を含んでいることを特徴とする請求項1記載の潤滑油添加剤。   The lubricating oil additive according to claim 1, wherein the lubricating part contains one or more of a polymethacrylate chain, an olefin copolymer chain, and a polyisobutylene chain. 各吸着部は、カルボキシル基、リン酸基、アミノ基およびチオール基のうちの1種以上を含んでいることを特徴とする請求項1または2記載の潤滑油添加剤。   The lubricating oil additive according to claim 1 or 2, wherein each adsorption part contains one or more of a carboxyl group, a phosphate group, an amino group, and a thiol group. 前記潤滑部は鎖状のポリマーから成り、
各吸着部は前記ポリマーの両端にそれぞれ結合されていることを
特徴とする請求項1乃至3のいずれか1項に記載の潤滑油添加剤。
The lubricating part is made of a chain polymer,
The lubricating oil additive according to any one of claims 1 to 3, wherein each adsorbing portion is bonded to both ends of the polymer.
前記潤滑部がメタクリル酸エステルユニットを含み、各吸着部がカルボキシル基を含む一般式(1)で表される化合物を有することを特徴とする請求項1記載の潤滑油添加剤。
(式中、m,n,pおよびqは、1以上の整数である。)
The lubricating oil additive according to claim 1, wherein the lubricating part includes a methacrylic acid ester unit, and each adsorbing part includes a compound represented by the general formula (1) including a carboxyl group.
(In the formula, m, n, p and q are integers of 1 or more.)
前記一般式(1)中のmは100〜1000の整数であることを特徴とする請求項5記載の潤滑油添加剤。   The lubricating oil additive according to claim 5, wherein m in the general formula (1) is an integer of 100 to 1,000. 前記一般式(1)中のnは11〜21の整数であることを特徴とする請求項5または6記載の潤滑油添加剤。   The lubricating oil additive according to claim 5 or 6, wherein n in the general formula (1) is an integer of 11 to 21. 前記一般式(1)中のpは2〜10の整数であることを特徴とする請求項5乃至7のいずれか1項に記載の潤滑油添加剤。   The lubricating oil additive according to any one of claims 5 to 7, wherein p in the general formula (1) is an integer of 2 to 10. 前記一般式(1)中のqは5〜18の整数であることを特徴とする請求項5乃至8のいずれか1項に記載の潤滑油添加剤。   The lubricating oil additive according to any one of claims 5 to 8, wherein q in the general formula (1) is an integer of 5 to 18. 前記潤滑油の基油に、請求項1乃至9のいずれか1項に記載の潤滑油添加剤が添加されていることを特徴とする潤滑油組成物。   A lubricating oil composition, wherein the lubricating oil additive according to any one of claims 1 to 9 is added to a base oil of the lubricating oil. 前記潤滑油の基油100質量部に対して、前記潤滑油添加剤が0.1〜10質量部含有されていることを特徴とする請求項10記載の潤滑油組成物。   The lubricating oil composition according to claim 10, wherein the lubricating oil additive is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the base oil of the lubricating oil.
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