JP2014025040A5 - - Google Patents

Description

（２−９）添加剤Ｃ２：粘度指数向上剤−２
オレフィンコーポリマー系粘度指数向上剤。非分散タイプ。

（２−１０）添加剤Ｄ：消泡剤溶液
軽油にジメチルポリシロキサンタイプのシリコーンオイルを３質量％溶解した消泡剤溶液。
２．潤滑油組成物の調製
上記した組成材料を用いて、表２及び３に示す組成により実施例１〜８、比較例１〜１３の潤滑油組成物を調製した。
３．試験
実施例１〜８及び比較例１〜１３の潤滑油組成物について、その性能を見るために以下に示す各種試験を行った。
（１）１００℃動粘度
１００℃動粘度は、ＪＩＳ Ｋ ２２８３「原油及び石油製品−動粘度試験方法及び粘度指数算出方法」に準拠して測定した。
（２）低温粘度
−３０℃及び−３５℃における低温粘度はＡＳＴＭ Ｄ５２９３に準拠して測定した。
（３）シェル式４球摩耗試験
シェル式４球試験は、ＡＳＴＭ Ｄ４１７２に準拠して、回転数１８００ｒｐｍ、油温５０℃、荷重４０ｋｇｆ、及び時間は３０分の条件で実施した。試験後、試験片を取り出して、摩耗痕幅を測定し、結果を示した。
（４）摩擦係数測定試験
摩擦特性を見るために、ＡＳＴＭ−Ｇ−１３３（Ａｍｅｒｉｃａｎ Ｓｏｃｉｅｔｙ ｆｏｒ Ｔｅｓｔｉｎｇ ａｎｄ Ｍａｔｅｒｉａｌｓ）で使用されるＣＡＭＥＲＯＮ−ＰＬＩＮＴ・ＴＥ７７試験機を用いて摩擦係数を測定、評価した。上部試験片はＳＫ−３製で直径６ｍｍ、長さ１６ｍｍの円筒形とし、下部試験片はＳＫ−３製の板を用い、試験温度８０℃、荷重３００Ｎ、振幅１５ｍｍ、往復振動数１０Ｈｚで１０分間試験を実施し、安定した最後の１分間に測定した摩擦係数の平均値を記した。摩擦係数が小さいほど摩擦低減性が優れていることを示す。
（５）乳化性試験
潤滑油のエマルジョン安定性（水を抱き込む性能）を評価するために、ＡＳＴＭ Ｄ７５６３に準拠した以下の乳油化性試験を実施した。
市販の高速で撹拌が可能なブレンダー、例えば今回の評価では株式会社エム・エフ・アイ社製のステンレス製容器を用いたＷＡＲＩＮＧ ＢＬＥＮＤＥＲ ７０１１Ｈ (現在は７０１１Ｓ)を使用して、試作のＥ８５燃料、蒸留水を使って評価試験を実施した。試験手順は以下の通り。
室温（２０℃±５℃）下で、２００ｍｌメスシリンダーで評価する試験油を１８５ｍｌ計測し、ブレンダー７０１１Ｈへ投入、次に１００ｍｌメスシリンダーで試作Ｅ８５燃料を１５ｍｌ計測、ブレンダー７０１１Ｈへ投入し、最後に１００ｍｌメスシリンダーで蒸留水を１５ｍｌ計測、７０１１Ｈへ投入する。その後直ちに容器のふたをして、回転数１５０００ｒｐｍで、６０秒間撹拌する。撹拌が終了したら、直ちに蓋ができる摺りガラス栓付の１００ｍｌメスシリンダーへ混合溶液を１００ｍｌ入れて、既定の温度（−５〜０℃もしくは２０〜２５℃）の恒温槽へ２４時間静置する。撹拌してから恒温槽に２４時間静置後、油-エマルジョン−水の量をメスシリンダーの目盛で計測し、水の分離が見られたものは水分離、水の分離が見られなかったものは水分離無しで、表２及び表３に示した。
試作Ｅ８５燃料については、市販のＪＩＳ１号自動車ガソリン１５０ｍｌと和光純薬工業の特級エタノール８５０ｍｌをメスシリンダーで測り、常温で混合したものを使用した。
試験に必要な混合は、規定された時間内に短期間で終了し、使用にあたっては軽質分が揮発しないようにしっかりと密閉できる容器に入れて、室内の冷暗所に保管した。
比較例５及び実施例４については、米国の独立研究開発機関であるSouth West Research Institute にてＡＳＴＭ Ｄ７５６３を実施し、同じ結果を得た。
４．考察
比較例１は、グリセリンモノオレエートを含まないエンジン油で、乳化性試験では水の分離は見られなかった。しかし、グリセリンモノオレエートを含まないため、摩擦係数測定試験の結果は摩擦係数が０．１１２と高く、エンジン摩擦低減による省燃費性の効果が得られない。
比較例２及び３は異なる粘度指数向上剤を使用した０Ｗ−２０グレードのエンジン油で、それぞれにグリセリンモノオレエートを添加し、摩擦係数は０．１以下の結果が得られ、摩擦係数低減による省燃費性の効果が得られた。しかし一方では、グリセリンモノオレエートを使用したこれらの油種では、その界面化学作用が強いため、水と油類とが比較的早く分離してしまうことがわかった。
比較例２、３及び４の結果を比較することにより、使用する非分散タイプの粘度指数向上剤のタイプ（ポリ(メタ)アクリレート、オレフィンコーポリマー）、濃度による違いによる乳化性の違いは見られないことが明らかとなった。
比較例９、１０及び１１では、アミンのエチレンオキサイド付加物以外の界面活性剤を添加した。強い塩基性を示すオレイルアミン以外の界面活性剤ではグリセリンモノオレエートによる強い水分離性を解除することができなかった。オレイルアミンは、グリセリンモノオレエートの強い水分離性を改善し、Emulsion-Retention（エマルション安定性）を向上させる効果は非常に高いが、一方ではエンジン油の耐摩耗性を著しく低下させることがシェル式４球摩耗試験の結果からわかった。
シェル式４球摩耗試験結果で０．５０ｍｍ以上のものは、耐摩耗性が好ましくない。比較例-1は摩耗痕径０．３９ｍｍであり、この結果と比べて摩耗痕径が大きくなるものは、耐摩耗剤の働きを阻害するため、摩耗痕径が増加し、悪化する。ゆえに好ましくない。０．４５ｍｍ以下が好ましく、比較例−１本来の耐摩耗性を保持するためには０．３９ｍｍの＋１０％以内の摩耗痕径（＝０．４３ｍｍ）がより好ましい。
比較例５、及び６、７では、モノラウリルアミンのエチレンオキサイド付加物を、濃度０．３〜０．９質量％の範囲で変化させた時の乳化性、耐摩耗性、摩擦係数を測定した。
その結果、アルキル基の炭素数がＣ１２では、耐摩耗性、摩擦係数に対しては大きな影響を与えない一方、乳化性に対しても全く改善効果が見られず、アミンのエチレンオキサイド付加物でも炭素数が短くては乳化性を改善することが非常に困難であることがわかった。
比較例８及び比較例１２では、オレイルアミンのエチレンオキサイド付加物の濃度が０．４質量％未満では、グリセリンモノオレエートの水分離性を解除することが困難であった。
実施例１〜６では、基油の硫黄含有量及び不飽和度が少ないグループ２、３、及び４の場合では、オレイルアミンのエチレンオキサイド付加物が０．４質量％以上添加されていれば、グリセリンモノオレエートの強い界面活性効果による水分離性を解除し、Emulsion-Retentionを改善することができた。また、耐摩耗性及び、摩擦係数低減効果も維持できることも明らかとなった。実施例７では、既定の性状を示すＡＰＩのグループ３基油の中でも、フィッシャートロプシュ法によって合成されたＧＴＬ（ガストゥリキッド）基油を使用した。
アミンのエチレンオキサイド付加物による特定の濃度範囲であればフィッシャートロプシュ法によって合成された基油に対しても、良好な耐摩耗性及び摩擦低減効果を維持しながら、水分離性を解除し、Emulsion-Retentionを維持することができることが明らかとなった。

Below, it has the excellent wear resistance and fuel saving performance of the present invention, and also has the ability to prevent the corrosion and rust of the internal combustion engine by dispersing condensed water due to water vapor generated by fuel combustion etc. in the oil. The lubricating oil composition for an internal combustion engine will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.
1. Composition material In preparation of an Example and a comparative example, the following composition material was prepared.
(1) Base oil Base oils 1 to 4 used in Examples and Comparative Examples have the properties shown in Table 1. Here, the kinematic viscosity at 40 ° C. and the kinematic viscosity at 100 ° C. are values obtained by JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”. The viscosity index is a value obtained according to JIS-K-2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”. JIS K 2269 was used for the pour point (PP), JIS K 2265-4 (COC: Cleveland open method) was used for the flash point, and JIS K 2541 (radiation-excited method) was used for the sulfur content. _{Additionally,%} C A, for% _{C N} and% _{C P} using ASTM D3238.
(2) Additive (2-1) Additive A1: Glycerol monooleate (product name: Excel O-95R, manufactured by Kao Corporation)
・ Molecular distillation monoglyceride
Melting point: 41 ° C
・ Hydroxyl value 222mgKOH / g
(2-2) Additive A2: Lauryl diethanolamine (manufactured by ADEKA, product name: Adeki Kluve FM812)
Density: 0.91 g / cm ³ molecular weight
Flash point: 182 ° C
・ Hydroxyl value: 393 mgKOH / g
・ Base number: 192 mgKOH / g
(2-3) Additive A3: Oleyldiethanolamine (manufactured by ADEKA, product name: Adeki Kluve FM832)
Melting point: 31 ° C
Density: 0.92 g / cm ³ (25 ° C.)
Kinematic viscosity: 69.3 mm ² / s @ 40 ° C
Flash point: 230 ° C (JIS K2265-4, COC)
・ Hydroxyl value: 322 mgKOH / g
・ Base number: 160 mgKOH / g
(2-4) Additive A4: Polyester-polyethylene oxide-polyester-block copolymer (manufactured by Croda, product name: HYPERMER B246)
・ EINECS No. 215-535-7
Density: 0.94 g / cm ³
Surfactant, polyester-polyethylene oxide-polyester-block copolymer (2-5) additive A5: oleylamine produced by reaction of condensed 12-hydroxystearic acid with polyethylene oxide having a molar mass> 1000 g / mol (Lion Akzo, product name: Armin OD)
・ Oleylamine 99% or more
-Iodine value, 70 or more (2-6) Additive A6: Polyethylene-polyoxypropylene condensate (manufactured by ADEKA, surfactant for detergent, product name: Adeka Pluronic L101)
Melting point: 15 ° C
Specific gravity: 1.02
-Weight average molecular weight: 3800
Viscosity: 756 mPa · s @ 25 ° C
(2-7) Additive B: GF-5 Package In the additive package for internal combustion engine oil, when 8.9-10.55% by mass of this additive is blended in the lubricating oil, API-SN, ILSAC GF-5 It is described in the product catalog of Oronite that performance suitable for the standard can be obtained. In Examples, the additive amount of the additive B is 9.05% by mass, and the additive amount suitable for the ILSAC GF-5 standard is used. However, the additive amount of the additive B is not particularly limited. .
(2-8) Additive C1: Viscosity index improver-1
Polymethacrylate viscosity index improver. Non-distributed type.

(2-9) Additive C2: Viscosity index improver-2
Olefin copolymer viscosity index improver. Non-distributed type.

(2-10) Additive D: Antifoaming agent solution An antifoaming agent solution in which 3% by mass of a dimethylpolysiloxane type silicone oil is dissolved in light oil.
2. Preparation of Lubricating Oil Composition Lubricating oil compositions of Examples 1 to 8 and Comparative Examples 1 to 13 were prepared with the compositions shown in Tables 2 and 3 using the composition materials described above.
3. Tests Various tests shown below were performed on the lubricating oil compositions of Examples 1 to 8 and Comparative Examples 1 to 13 in order to see the performance.
(1) 100 ° C. Kinematic viscosity The 100 ° C. kinematic viscosity was measured in accordance with JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
(2) Low temperature viscosity The low temperature viscosity at -30 ° C and -35 ° C was measured according to ASTM D5293.
(3) Shell-type four-ball wear test The shell-type four-ball test was performed under the conditions of a rotation speed of 1800 rpm, an oil temperature of 50 ° C., a load of 40 kgf, and a time of 30 minutes in accordance with ASTM D4172. After the test, the test piece was taken out, the wear scar width was measured, and the result was shown.
(4) Friction coefficient measurement test In order to see the friction characteristics, the friction coefficient was measured and evaluated using a CAMERON-PLINT / TE77 tester used in ASTM-G-133 (American Society for Testing and Materials). The upper test piece is made of SK-3 and has a cylindrical shape with a diameter of 6 mm and a length of 16 mm. The lower test piece is a plate made of SK-3, and the test temperature is 80 ° C., the load is 300 N, the amplitude is 15 mm, and the reciprocating frequency is 10 Hz. A minute test was performed and the average value of the coefficient of friction measured during the last stable minute was noted. A smaller friction coefficient indicates better friction reduction.
(5) Emulsification test In order to evaluate the emulsion stability (the ability to embed water) of the lubricating oil, the following milk oil test was performed in accordance with ASTM D7563.
Using a commercially available blender capable of stirring at high speed, for example, WARING BLENDER 7011H (currently 7011S) using a stainless steel container manufactured by MIF Co., Ltd. An evaluation test was conducted using water. The test procedure is as follows.
At room temperature (20 ° C ± 5 ° C), measure 185 ml of test oil to be evaluated with a 200 ml graduated cylinder and put it into blender 7011H, then measure 15 ml of prototype E85 fuel with 100 ml graduated cylinder and throw it into blender 7011H. Measure 15 ml of distilled water with a 100 ml graduated cylinder and put into 7011H. Immediately after that, the container is covered and stirred for 60 seconds at a rotational speed of 15000 rpm. When the stirring is completed, 100 ml of the mixed solution is immediately put into a 100 ml graduated cylinder with a sliding glass stopper that can be covered, and left in a constant temperature bath at a predetermined temperature (−5 to 0 ° C. or 20 to 25 ° C.) for 24 hours. After stirring, let stand in a thermostatic chamber for 24 hours, measure the amount of oil-emulsion-water with a graduated cylinder scale, water separation was seen, water separation was not seen, water separation was not seen Are shown in Tables 2 and 3 without water separation.
As the prototype E85 fuel, a commercial JIS No. 1 automobile gasoline 150 ml and Wako Pure Chemical Industries' special grade ethanol 850 ml were measured with a graduated cylinder and mixed at room temperature.
The mixing required for the test was completed in a short period of time within a specified time, and was kept in a cool and dark place indoors in a container that could be tightly sealed so that light components would not evaporate.
For Comparative Example 5 and Example 4, ASTM D7563 was conducted at South West Research Institute, an independent research and development organization in the United States, and the same results were obtained.
4). Discussion Comparative Example 1 was an engine oil containing no glycerin monooleate, and no water separation was observed in the emulsification test. However, since it does not contain glycerin monooleate, the result of the friction coefficient measurement test has a high coefficient of friction of 0.112, and the fuel saving effect by reducing engine friction cannot be obtained.
Comparative Examples 2 and 3 are 0W-20 grade engine oils using different viscosity index improvers, and glycerin monooleate was added to each, resulting in a coefficient of friction of 0.1 or less. A fuel-saving effect was obtained. However, on the other hand, it was found that these oil types using glycerin monooleate have a strong interfacial chemical action, so that water and oils are separated relatively quickly.
By comparing the results of Comparative Examples 2, 3 and 4, the type of non-dispersion type viscosity index improver used (poly (meth) acrylate, olefin copolymer), and the difference in emulsification depending on the concentration can be seen. It became clear that there was no.
In Comparative Examples 9, 10 and 11, surfactants other than amine ethylene oxide adducts were added. Surfactants other than oleylamine showing strong basicity could not release strong water separability by glycerin monooleate. Although oleylamine improves the strong water separability of glycerin monooleate and improves the Emulsion-Retention (emulsion stability), it is highly effective in reducing the wear resistance of engine oil. It was found from the results of the 4-ball wear test.
A shell type 4-ball wear test result of 0.50 mm or more is not preferable in wear resistance. Comparative Example-1 has a wear scar diameter of 0.39 mm. When the wear scar diameter is larger than this result, the wear scar diameter increases and deteriorates because the action of the antiwear agent is inhibited. Therefore, it is not preferable. 0.45 mm or less is preferable, and in order to maintain the original wear resistance of Comparative Example-1, a wear scar diameter (= 0.43 mm) within + 10% of 0.39 mm is more preferable.
In Comparative Examples 5, 6, and 7, the emulsifiability, wear resistance, and coefficient of friction were measured when the ethylene oxide adduct of monolaurylamine was changed in a concentration range of 0.3 to 0.9% by mass. .
As a result, when the carbon number of the alkyl group is C12, there is no significant effect on the wear resistance and friction coefficient, but no improvement effect is seen on the emulsification property. It was found that it is very difficult to improve the emulsifiability when the carbon number is short.
In Comparative Examples 8 and 12, when the concentration of the oleylamine ethylene oxide adduct was less than 0.4% by mass, it was difficult to release the water separability of glycerin monooleate.
In Examples 1 to 6, in the case of groups 2, 3, and 4 where the sulfur content of the base oil and the degree of unsaturation are low, glycerin is added if 0.4 wt% or more of the oleylamine ethylene oxide adduct is added. Emulsion-Retention could be improved by removing the water separability due to the strong surfactant effect of monooleate. It was also revealed that the wear resistance and the friction coefficient reducing effect can be maintained. In Example 7, a GTL (gas-to-liquid) base oil synthesized by the Fischer-Tropsch method was used among API group 3 base oils exhibiting predetermined properties.
Emulsion is released from the base oil synthesized by the Fischer-Tropsch method within the specific concentration range of amine oxide oxide adduct while maintaining good wear resistance and friction reduction effect. It became clear that -Retention can be maintained.