KR100416067B1 - A engine treatment for gasoline engine oil - Google Patents

Abstract

The present invention relates to an engine protective agent for adding a gasoline engine lubricating oil, and more particularly, to a protective coating on an intermetallic friction or abrasion generated from a driving surface during power transmission or direction change by a mechanical driving mechanism of an internal combustion engine. It is added to the existing lubricating oil to form a smooth operation to maintain the present invention relates to an engine protective agent for lubricating oil including synthetic oil, molybdenum compound, amine antioxidant, alkali metal detergent and imide-based dispersant.

Description

A engine treatment for gasoline engine oil

The present invention relates to an engine protective agent for adding a gasoline engine lubricating oil, and more particularly, to a protective coating on an intermetallic friction or abrasion generated from a driving surface during power transmission or direction change by a mechanical driving mechanism of an internal combustion engine. It is added to the existing lubricating oil in order to maintain a smooth operation to form a molybdenum compound, a phosphorus-free molybdenum compound, an amine antioxidant, relates to an engine protective agent for lubricating oil including an alkali metal-based detergent and imide-based dispersant.

As the internal combustion engine runs for a long time, friction and abrasion occur in each driving part, that is, inside the engine such as the inner wall of the cylinder, the cylinder ring, the bearing, and the belt, and in some cases, the internal combustion engine may be damaged. Such wear or damage not only degrades the engine, but also causes environmental pollution such as shortening the life of the engine, deteriorating fuel efficiency, and increasing smoke. In particular, when the engine is started after stopping for a long time, in the place where the protective film is not formed because the lubricating oil returned to the crankcase is coated on the frictional part, friction between metals and wear increases, and the engine degradation phenomenon is intensified. In order to prevent the wear phenomenon of the engine, various kinds of lubricants used in the internal combustion engine are used, and their functions can be largely classified into abrasion resistance, clean dispersion, sealing, cooling and rust prevention. Abrasion resistance refers to the action of lubricating oil circulating inside the engine to form an oil film on the metal surface to reduce direct friction between the metals, smoothing the engine's operation, reducing power loss and reducing wear. The clean dispersion action is because oxidation products generated by byproducts or moisture caused by incomplete combustion of fuel generated inside the cylinder during engine operation form sludge, which prevents the circulation of lubricating oil and increases the viscosity of the oil, thus inhibiting smooth lubrication. It is the action of neutralizing acid oxide and dispersing it in lubricating oil. The sealing action forms an oil film between the cylinder and the piston to facilitate the reciprocating movement of the piston, while preventing the mixing of the blow-by gas generated in the combustion process of the fuel into the cylinder. It is an action that prevents degradation and prevents oxidation of the lubricant. Cooling action occurs when friction heat is generated in the driving part of the engine and the piston receives very high combustion heat, and the metal receives high heat and weakens, causing mechanical failure.Lubricant scatters or circulates inside the engine and absorbs or transfers heat to the engine. Cooling action. Finally, the rust preventive action refers to the role of forming an antirust coating on the metal surface and neutralizing the acid to prevent rust or corrosion caused by corrosive acids, moisture, and oxides generated during operation of the engine.

Since the lubricating oil for internal combustion engines added for the above purpose cannot completely prevent intermetallic frictional wear under severe driving conditions, various engine protection agents have been developed for addition to existing lubricating oils.

The engine protection agent for lubricating oil addition currently being developed and used is a coating agent containing a lubricating film-forming material such as polytetrafluoroethylene resin (hereinafter referred to as 'PTFE'). The coating agent is added to the lubricant in a certain amount so that the PTFE contained in the coating agent is coated on the inner wall of the cylinder or various friction surfaces. Due to the characteristics of PTFE, the metal and the surface of the metal are prevented from rubbing, thereby improving engine performance. The wear of the engine is prevented and the wear of the cylinder inner wall, the crankshaft, etc. is eliminated, so that the life of the parts is extended and the performance is improved. As a patent for such a coating agent, US Patent No. 5,641,731 is to be effective when used in combination with about 20 to 25% by volume of the existing lubricating oil. U.S. Patent No. 4,333,840 adds hybrid PTFE and molybdenum, and is applicable only to limited places such as skis and inorganics, and cannot be used in addition to lubricants for internal combustion engines. Korean Patent No. 282299 discloses a lubricating oil composition comprising PTFE and an oil-soluble molybdenum compound in a synthetic base oil. Korean Patent Laid-Open Publication No. 97-15686 discloses an automotive engine internal coating including PTFE. However, since the PTFE coatings are not compatible with the existing lubricants, the uneven parts such as the inner wall of the cylinder may be coated and the remaining PTFE may be deposited to block the path of the lubricant. Therefore, it is difficult to expect a desired effect and the coating may not be smooth. If the engine oil is replaced without a price, there is an economic disadvantage that expensive PTFE is wasted.

An engine oil coating agent containing paraffin chloride as an anti-wear agent has been developed and used. Patents related to these are Korean Patent Publication No. 2000-0049969, Korean Patent Application No. 94-40243, 96-62793, and 96-20415. No. 96-20416. However, paraffin chloride has excellent boundary lubrication and extreme pressure lubrication activity and is used as an extreme pressure wear agent. However, paraffin chloride may be decomposed at high temperatures inside the engine, so it is not easy to expect desired physical properties and causes air pollution.

In addition, oil-soluble engine protectors have been developed. Korean Patent Publication No. 2000-0063052 discloses a lubricating oil composition containing a molybdenum compound, a diarylamine-based antioxidant, and an alkaline earth metal phenate, which is oil-soluble and does not contain active sulfur. There is a disadvantage that the characteristics are not excellent. U.S. Patent No. 3,285,942, U.S. Patent No. 4,394,279, U.S. Patent 4,832,857, and U.S. Patent 4,846,983 relate to the use of molybdenum complexes in lubricating oils. Patents for lubricating compositions containing molybdenum as antiwear agents include US Pat. Nos. 4,889,647, 4,812,246, 5,137,647, 5,143,633, 5,650,381, 5,840,672 and WO 95/07963. Poor property of clean and clean. WO 95/07962 and WO 95/07966 relate to lubricating compositions for use in motor vehicle or truck engines containing molybdenum and amine antioxidants. The amines use primary amines and do not have good antioxidant performance. U.S. Pat.Nos. 5,650,880 and WO 95/27022 disclose base oils, alkyldiphenylamines and / or phenyl-alpha-naphthylamines and oxymolybdenum sulfide dithiocarbamates and / or oxymolybdenum sulfide organophosphorodithioates Since the lubricating oil composition does not suggest the use of a molybdenum compound in which active sulfur is not present, there is a problem in that the wear resistance is not excellent.

In order to solve the above problems, the present inventors have developed a synthetic oil of polyalphaolefin (hereinafter referred to as "PAO") and diester oil, a molybdenum compound containing no phosphorus, an oil-soluble secondary amine antioxidant, and an alkaline earth metal sulfonate. And an ashless imide-based dispersant were added in an appropriate amount to prepare an engine protector to complete the present invention.

Therefore, the present invention has an excellent compatibility with the existing lubricating oil, while maintaining the function of the lubricating oil, while easily forming a protective film on the internal combustion engine to prevent damage to the engine inner surface, improve fuel efficiency and reduce soot engines for environmentally friendly lubricating oil The purpose is to provide a protective agent.

The present invention provides a lubricating component composition containing a mixed synthetic oil of polyalphaolefin and diester oil, a molybdenum compound, a secondary amine antioxidant, an alkali earth metal sulfonate, and an ashless imide-based dispersant. Mixed synthetic oil of a polyalphaolefin having a viscosity of 3 to 8 cSt at 40 ° C. and 100 ° C., and a diester oil composed of a condensate of an alcohol and an acid having a viscosity of 40 ° C. to 20 to 40 cSt and a viscosity of 3 to 8 cSt at 100 ° C. 90 wt%, 2-15 wt% molybdenum compound containing no phosphorus, 2-10 wt% oil-soluble secondary amine antioxidant, 2-10 wt% alkaline earth metal sulfonate, and ashless imide-based dispersant It is characterized by an engine protectant for adding lubricating oil containing 10% by weight.

The present invention will be described in more detail as follows.

The present invention uses a mixed synthetic oil of PAO and diester oil as lubricating base oil.

The PAO has a low volatility and excellent effect even at low temperatures while improving flowability in an internal combustion engine at a high temperature, and is a material that increases oxidation stability, hydrolysis stability and oil film stability, and is preferably obtained by polymerizing an olefin. It is preferable that 40 degreeC viscosity is 15-40 cSt, and 100 degreeC viscosity is 3-8 cSt with synthetic oil.

It is preferable that the diester oil is a condensate of an alcohol and an acid having a 40 ° C viscosity of 20 to 40 cSt and a 100 ° C viscosity of 3 to 8 cSt.

The PAO and the diester oil are preferably mixed in a weight ratio of 9: 1 to 1: 1, and if out of the above range, there is a problem in that lubrication characteristics are lowered.

In addition, the synthetic oil of the PAO and diester oil is preferably contained in the total engine protective agent 50 to 90% by weight, if the content is less than 50% by weight, the flowability is poor and the lubrication properties are reduced, 90% by weight If it exceeds, there is an increase in oil film stability and chemical resistance, but there is a problem in that the cost is increased.

As the molybdenum compound used in the present invention, it is preferable to use an oil-soluble molybdenum compound which does not contain phosphorus as a liquid lubricant having excellent extreme pressure, heat resistance, abrasion resistance, and chemical resistance. As an oil-soluble molybdenum compound which does not contain the said phosphorus, molybdenum carbamate, an organic molybdenum mixture, etc. can be used, for example. In addition, the molybdenum compound is preferably contained in an amount of 2 to 15% by weight in the total engine protective agent, and if the content is less than 2% by weight, it is difficult to achieve the desired performance, and when it exceeds 15% by weight, physical properties such as extreme pressure performance required are improved. Compared with the increase in raw material costs there is an economic disadvantage.

In general, lubricating oils are degraded by temperature, metal catalysts and oxygen to produce organic acids, which cause metal corrosion. Therefore, the antioxidant in the present invention inactivates the free radicals generated in the early stages to no longer participate in the growth reaction, or decomposes the oxidized product generated once so as not to convert into a stable compound or catalyze the oxidation of the metal. It serves to prevent.

In the present invention, an antioxidant capable of performing such a role may be an oil-soluble secondary amine, and preferably, a secondary arylamine represented by the following Chemical Formula 1 may be used.

In Chemical Formula 1; R 'and R "each represent an aryl group having 6 to 30 carbon atoms.

The secondary arylamine is diphenylamine, various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, dibutyl Diphenylamine, dioctyldiphenylamine, dinonyldiphenylamine, etc. can be used.

It is preferable to contain 2-10 weight% of secondary arylamines used as the said antioxidant, More preferably, 4-7 weight% is good. If the content is less than 2% by weight, there is no antioxidant effect or minimal effect. If the content is more than 10% by weight, it is not economical and there is a risk of metal corrosion.

The alkaline earth metal sulfonate used in the present invention serves to disperse and neutralize waxes, sludges and acid oxides produced by the oxidation products of fuel and lubricating oil when operating an internal combustion engine, and a metal alkylbenzene sulfo represented by the following Chemical Formula 2 Preference is given to using nates.

In Formula 2, R represents an alkyl group having 8 to 20 carbon atoms, and M represents a metallic element.

The metal alkylbenzene sulfonate preferably has a total base number (TBN) of 100 to 400, more preferably 200 to 350. If the total number of bases of the metal alkylbenzene sulfonate is less than 100, there is a possibility of causing corrosion by not neutralizing the organic acid generated by oxidation of the lubricating oil, and if it exceeds 400, there is a problem of poor compatibility with other additives. In the metal alkylbenzene sulfonate represented by Formula 2, M is preferably Ca, Ba, Mg or the like.

The alkaline earth metal sulfonate is preferably used in an amount of 2 to 10% by weight, preferably 3 to 7% by weight, in all engine protective agents. If the content is less than 2% by weight, it is difficult to exert the desired effect. If the content is more than 10% by weight, it is not economical and there is a risk of metal corrosion.

The dispersant used in the present invention serves to suspend the lubricating oil decomposition product, and it is preferable to use a ashless imide-based dispersant. As the ashless imide-based dispersant, for example, polybutene-maleic acid ester copolymer, substituted succinimide, polyamide succinimide, polyhydroxy succinic acid ester, substituted Mannich base, and the like can be used. The dispersant is preferably contained in an amount of 2 to 10% by weight, preferably 4 to 6% by weight, in the total engine protective agent. If the content is less than 2% by weight, the desired dispersing effect cannot be obtained and exceeds 10% by weight. This is not economical compared to the increase in dispersion effect.

The engine protecting agent for adding a gasoline engine lubricant of the present invention may be prepared by adding a molybdenum compound, a diamine antioxidant, an alkaline earth metal sulfonate and an ashless imide dispersant to a polyalphaolefin / ester mixed synthetic oil. The same target object can be manufactured even if the order of addition is different.

The engine protection agent according to the present invention improves the physical properties such as friction coefficient, viscosity index, low temperature fluidity, oxidative stability, etc., which has a close influence on engine performance, maximizing engine efficiency, output power 1.4 hp, fuel saving 12.2%, noise reduction It can improve 68.3% and can be used in addition to conventional car and truck crankcase lubricants, transmission lubricants, gear lubricants, working fluids and compressed oils, to create a protective shield in the engine during cold start to prevent fatal engine wear It works.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

Examples 1 to 5.

A stirring tank having a capacity of 1 kL was prepared, and the temperature was maintained at 45 to 55 ° C and polyalphaolefin (PAO, Mobil SHF-63, manufactured by EXXONMOBIL) was injected. While maintaining the temperature, diester oil (Mobil Ester DB-51, manufactured by EXXONMOBIL) was added at a rate of 30% by weight based on PAO. After the addition, the mixture was stirred for about 30 minutes, followed by amine antioxidant (Irganox L57, CIBA-GEIGY), overbased calcium sulfonate (HiTec 611, TBN 300 mgKOH / g, product of ETHYL), polybutenyl succinimide dispersant ( An engine protector was prepared by injecting HiTec 638, N 2.0%, TBN 43 mgKOH / g, manufactured by ETHYL, and molybdenum compounds (Sakura Lube 165, Mo-DTC, manufactured by ASAHIDENKA), followed by stirring. Table 1 shows the composition and content of the engine protective agent.

Comparative Examples 1 and 2.

Next, the engine protective agent was prepared according to the method of Example 1 with the components and contents shown in Table 1.

Comparative Examples 3 to 7.

In order to compare with the engine protection agent (Examples 1-5) which concerns on this invention, the engine protection agent marketed and basic physical property were compared. The engine protectors to be compared are Molidrive (Comparative Example 3, manufactured by KU Kodo Industries Co., Ltd.) as an antiwear agent with an oil-soluble molybdenum compound, Motor-Up (Comparative Example 4, manufactured by MotorUp America Inc., USA) as an antiwear agent with chlorinated paraffin, Miralube (Comparative Example 5, Shalom International Co., Ltd.), Prolong (Comparative Example 6, Prolong Super Lubricants Inc., USA, Ltd.), T-Plus (Comparative Example 7, T-Plus Product) , USA), respectively.

Each engine protection agent was measured by the following method, the results are shown in Table 1 below.

<Test method>

1.Kinematic viscosity (cSt): measured by ASTM D445.

2. Total salt value (mgKOH / g): measured by ASTM D2896.

3. Acid value (mgKOH / g): Measured by ASTM D664.

4. 4-Ball WSD (mm): Measured by ASTM D2266.

5. Carbide generation degree: In order to check the formation of carbide in the high temperature cylinder head when added to the engine, a certain amount of the engine protective agent was put in a fructose and heated at 250 ℃ for 3 hours and observed for the formation of carbide.

As shown in Table 1, the viscosity index (VI) of Examples 1 to 5 according to the present invention was 117 to 152, which was higher than that of Comparative Examples 1 to 7. That is, when the engine protection agent of the present invention is added to the lubricating oil, it was confirmed that the change in kinematic viscosity with the change of temperature is small. The infectious group showing acid neutralizing ability was 20-25 mgKOH / g in Examples 1 to 5 of the present invention, and the infectious group of Comparative Example 4 except for 22.0 mgKOH / g of Comparative Example 4 was higher than (3.65 to 17.6 mgKOH / g). In particular, Comparative Example 3 using an anti-wear agent as in the present invention had a very low infectivity of 3.65 mgKOH / g. Comparing the diameter of the 4-Ball wear scar showing the wear resistance performance, Examples 1 to 5 of the present invention had a wear scar diameter of 0.3646 to 0.4057 mm and a wear scar diameter of the comparative example was 0.6310 to 1.0463 mm. That is, the abrasion resistance performance of the engine protective agent in this invention was excellent compared with the comparative examples 1-7. In particular, the chlorinated paraffins used in Comparative Examples 2, 4, 5, and 6 are extreme pressure additives widely used for metal processing, such as cutting oil, because the chlorine component in the molecule gives extreme pressure. There is a tendency to ban the use worldwide. In addition, since the Mo-DTP anti-wear agent used in Comparative Example 1 contains phosphorus in the compound, the phosphorus compound in the combustion product may be discharged. Such phosphorus compounds are known to be highly poisonous to exhaust gas catalysts and are subject to regulation. The engine protective agent (T-Plus) of Comparative Example 7, which uses Teflon powder as an anti-wear agent, disperses very fine Teflon powder in oil and expects to reduce friction as Teflon powder fills the voids on the metal surface. There is a disadvantage of being deposited which obstructs the oil path. Accordingly, it can be seen that Examples 1 to 5, which are the engine protecting agent of the present invention, add an oil-soluble molybdenum compound that does not contain phosphorus in place of chlorinated paraffin and teflon, so that it is not harmful to the environment or human body.

Test Example

5 wt% of the engine protective agents of Examples 1 to 5 and Comparative Examples 1 to 7 were added to 10W-40 gasoline lubricating oil of domestic company H, and the effect of the engine protective agent on the physical properties of the lubricating oil was measured by the following method. Table 2 shows.

<Test method>

1. Low Temperature Viscosity (CCS, cP): Measured by ASTM D5293.

2. Rust protection: measured by ASTM D5844.

3. Oxidation stability (%): measured according to ASTM D4742.

4. Hot-Tube (%): Insert the glass tube (inner diameter ID: 2mm, outer diameter OD: 7.5∼8 mm, length: 37.8 cm) vertically into a perforated aluminum block heater, and then lower one side of the glass tube. Air was flowed at a flow rate of 10 mL / min, the other side was injected with lubricant at a rate of 0.35 cc / hr with a syringe pump, and then passed through a glass tube for 24 hours at 250 ° C. ℃ kinematic viscosity, the acid value was measured and compared with the value of the control company H lubricant.

As shown in Table 2, after adding 5% by weight of the engine protective agent of Examples and Comparative Examples to the H company lubricant, the low temperature viscosity (CCS) was lower than the low temperature viscosity (3540 cP) of the company H lubricant. In addition, it was found that the low temperature viscosity characteristics of the engine protective agent of the example were superior to those of the comparative example. According to the results, it was confirmed that the base group showing acid neutralizing ability was increased from 5.80 mgKOH / g, which is the lubricating oil value of H company before adding the engine protective agent, to 6.31 to 7.86 mgKOH / g for the example and 5.60 to 7.37 mgKOH / g for the comparative example. .

The wear scar diameter (WSD, mm) of the 4-Ball exhibiting wear resistance was 0.3732 to 0.4076 mm for the examples and 0.3949 to 0.5283 mm for the comparative example at 0.4732 mm before addition. The smaller the diameter, the better the effect of the additive, and in particular, the case of adding the engine protective agent of the example was about 30% smaller than the wear scar of the engine protective agent of the comparative example. This shows that the engine protector of the present invention is superior in abrasion resistance than the engine protector of the comparative example.

The oxidative stability and high temperature thermal stability were observed through the change of the acid value after the oxidative stability test and the hot-tube test. As a result of the oxidative stability test, the change in the acid value was increased by 325%, Example 0 to 30%, and Comparative Examples 52 to 355%. In other words, this means that the oxidation stability is remarkably improved when the engine protectant of the embodiment is added to commercial lubricating oil. As a result of the high temperature thermal stability test, the change in the computer value of the engine protector of the Example was almost unchanged, and the increase of the comparative example 6.4 to 431% and the increase of 70.4% before addition showed that the engine protector of the example was superior to the engine protector of the comparative example. Could know.

As described above, the engine protector according to the present invention has excellent compatibility with lubricating oils such as conventional car and truck crankcase lubricants, transmission lubricants, gear lubricants, hydraulic fluids and compressed oils, and maintains the function of the lubricating oils while maintaining friction. By improving physical properties such as coefficient, viscosity index, low temperature fluidity, oxidation stability, etc., the engine efficiency is maximized to prevent engine damage, improve fuel efficiency and reduce soot.

Claims (10)

delete delete delete In a lubricating component composition comprising a mixed synthetic oil of polyalphaolefin and diester oil, a molybdenum compound, a secondary amine antioxidant, an alkali earth metal sulfonate, and an ashless imide dispersant, A diester consisting of a polyalphaolefin having a viscosity of 40 ° C. of 15 to 40 cSt and a viscosity of 3 to 8 cSt of 100 ° C., and an condensate of an alcohol and an acid having a viscosity of 40 ° C. of 20 to 40 cSt and a viscosity of 3 to 8 cSt of 100 ° C. 50 to 90% by weight of mixed synthetic oil of oil, 2 to 15% by weight of molybdenum compound containing no phosphorus, 2 to 10% by weight of oil-soluble secondary amine antioxidant, 2 to 10% by weight of alkaline earth metal sulfonate, and ashless An engine protective agent for lubricating oil, characterized in that 2 to 10% by weight of the type imide-based dispersant is contained. The engine protecting agent for lubricating oil additives according to claim 4, wherein the molybdenum compound not containing phosphorus is selected from molybdenum carbamate and organic molybdenum compounds. delete The method of claim 4, wherein the secondary amine is diphenylamine, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, dibutyldi An engine protective agent for lubricating oil additives, characterized in that selected from phenylamine, dioctyldiphenylamine and dinonyldiphenylamine. delete delete The ashless imide-based dispersant is at least one member selected from polybutene-maleic acid ester copolymer, substituted succinimide, polyimide succinimide, polyhydroxy succinic acid ester and substituted Mannich base. Engine protection agent for lubricant additives.