EP0789069B1 - Additive containing multigrade lubricating oil and engine oil composition - Google Patents

Abstract

Multifunctional engine oil composition consists of a base oil and an additive package (1.5-55 weight %) comprises: (A) 10-100 wt.% polyfunctional, ash-free detergent-dispersant additive or its oily solution comprising polymer components which are produced by reacting a polyolefin derivative, preferably a PIB derivative, injected with dicarboxylic acid (anhydride) and non-acidic comonomers with ethylenic double bond, and having an average molecular weight of 800, with compound containing amino, imino or hydroxyl groups, the polyolefin chain in the polymer component carrying 1.6-20 acid derivatives, the amount of the molecules with more than one acid derivative being at least 25 wt.%, and the derivative being an imide, amide or ester amide derivative, and 0-90 wt.% usual alkenyl succinic acid derivative; (B) usual dispersant-detergent with different base number and metal content, antioxidant, friction reducer, wear inhibitor, corrosion inhibitor, defoamer and flow point reducer; and (C) usual viscosity (index) improving polymer. Weight ratio of A:B:C is 15-85: 15-85: 0-70.

Description

The invention relates to a halogen-free, additive-containing multi-grade engine oil and lubricating oil composition with high stability and optionally low phosphorus content, which consists of base oil and an additive package. The invention further relates to the additive package used.

• viskositäts- und viskositätsindexerhöhende, und fließpunktvermindernde Polymere,
• aschefreie Dispergenzien,
• metallhaltige Detergenzien,
• Inhibitoren (Oxydationsinhibitoren, Korrosionsinhibitoren, Verrostungsinhibitoren und ähnliche Stoffe),
• Abriebinhibitoren.

To meet the requirements of rupture spark ignition or diesel engines, the following groups of additives are used in motor oils:

• viscosity and viscosity index increasing and flow point reducing polymers,
• ashless dispersants,
• metal-containing detergents,
• Inhibitors (oxidation inhibitors, corrosion inhibitors, rust inhibitors and similar substances),
• Wear inhibitors.

The additives of the conventional engine oils can be classified into five groups because of their function and structure. The first group includes the large molecular weight (M _n = 5,000-2,000,000), mostly homo- or co-polymeric additives, which usually have a viscosity and viscosity index increasing and pour point depressant effect.

By incorporation of polar, basic groups in the copolymer structure additives with a detergent-dispersing (in the further DD) side effect can be obtained, the use of which allows a certain reduction of the concentration of small molecular weight DD additives (M _n <2,000) in the motor oil compositions. The most well-known representatives of such additives are the polyalkyl methacrylates (PMA) and their derivatives, ethylene-propylene copolymers (OCP), styrene-butadiene copolymers (SBCP) and polyisoprene (PIP).

Another group of additives that spread very rapidly in use is represented by the so-called ashless DD additives. Their increasing use in terms of their quantitative content is due to the fact that the greater performance requirements imposed by the new engine designs - such as the reduction of black sludge formation, environmentally damaging metal emissions and the effects of damaging sealing materials - can only be achieved by the further development of the ashless DD additives and can be satisfied by their use with increased concentration. As a small molecular weight (M _n <2,000) ashless DD additives mostly imide, amide or ester derivatives of polyalkenylsuccinic, Mannich bases with polyisobutene basic structure, polyolefin amines and similar substances are used.

The third, fourth and fifth groups of additives are formed by additives with additional functions. These additives include a number of compounds which have very important effects in terms of use.

These groups include, for example, the metal-containing detergents, oxidation inhibitors, corrosion inhibitors, friction modifiers and abrasion inhibitors, and foam control agents. A number of metal-containing and ashless variants of these substances are known, and these are generally selected and used on the basis of laboratory and brake test bench tests, taking into account their interactions, which may be synergistic or antagonistic.

During the last fifteen years, the composition of engine oils has been improved, on the one hand, by the use of new enhanced additives, which satisfy the new requirements at a higher level, and on the other hand by a new modification of the structure of the previously successfully used additives, ie changes the production of adjunct additives in addition to the main effect, the use of which makes it possible to further increase the level of performance or to reduce the concentration required for a given level of performance. For example, by chemically modifying the structure of the additives used in the compositions, such unwanted side effects have been successfully reduced, such as damage to the sealing material or corrosion of the bearing metals. The DD effect was achieved, for example, by modifying the ashless succinimide additives with organic acids ( EP 0 537 386 ) or by optimizing the structure of the polyethylene-polyamines used for the synthesis ( EP 0 451 380 ) elevated.

Vaccination of conventional viscosity and viscosity index increasing ethylene-propylene copolymers with polar groups has successfully formed a DD side effect ( EP 0 400 866 ). The mixed polymers of ethylene-propylene copolymers seeded with polymethacrylates are useful for stabilizing the blends of various viscosity and viscosity index increasing polymers.

The effect of the conventional small molecule alkenyl succinimide additives damaging the fluoroelastomer sealing materials could be successfully reduced with strong inorganic acids ( US 5,114,402 ).

By using new polyisobutenylsuccinic acid zinc salt derivatives could after the EP 0 265 658 the resistance of the oil compositions against oxidation at high temperatures and against deposit formation can be successfully increased. In addition to a high DD effect and increased storage stability could after the EP 0 051 998 By using ester derivatives of polyalkenylsuccinic acid, ethylene glycol and fatty acids, a preferred friction-reducing effect can be achieved.

Additives having an increased viscosity and viscosity index-increasing side effect in addition to an increased DD effect and improved compatibility with the sealing materials can be prepared by extending the polymer side chain of polyisobutenyl succinimides to a molecular weight of 5,000 and synthesizing so-called polysuccinimide additives (US Pat. US 4,234,435 . WO 91/04959 . WO 90/03359 and EP 0 271 937 ).

EP 0 677 572 describes such polyisobutylene (PIB), maleic anhydride and other comonomer-synthesized and detergent-dispersing additives and their use in motor oils, in which the ratio of the molecular structure present in polar BA and the oil-solubility required PIB groups 1,6-6, 0 is preferably 1.8-4.0.

EP 0 658 572 describes intermediates with a BA / PIB coupling number of from 1.3 to 6, prepared from PIB and maleic anhydride. These serve as acylating agents in the acylation of organic bases and / or alcohols to produce detergent-dispersing and ashless additives.

The preparation of such additives, with an average molecular weight of sometimes several tens of thousands, has been made possible by the synthesis of those acylating agents which have more than one succinic anhydride (BA) attached to one polyolefin chain in their molecules.

By the implementation of such intermediates and polyalkylene polyamines and / or polyalcohols and / or alkanolamines can - even with polyolefins having a higher average molecular weight than the commonly used molecules (M _n = 1,500-5,000) - additives with large polar groups (imide , Amide or ester) and synthesize with high DD activity. The structure of the known additives and the known production processes are different, However, in all cases, in the compositions containing such additives, it is possible to detect the increase in the DD effect and such a viscosity and viscosity index-increasing side effect which reduces the amount of conventional polymers required for a particular viscosity step by 10-30% and thereby the reduction the cost of the addition allows.

Despite the progress described above and achievements in the development of großmolekularischen succinimides (M _n> 2000), the use of conventional viscosity and viscosity index increasing polymers in the production of multi-stage engine oils has remained a fundamental condition. However, to further reduce their use, one can also observe other aspirations.

The amount of viscosity and viscosity index increasing polymers to be used may be e.g. by using hydrocracked base oils or synthetic base oils (polyalphaolefins, diesters and the like) having an ever-increasing viscosity index. The conventional viscosity and viscosity index-increasing polymers exert beneficial effects in the lubricating oils, but the unstable decomposition products resulting from the use of the composition and the action of the formed chemical impurities under the severe circumstances (such as high temperature and mechanical stress) promote the formation of insoluble resin-like ones Deposits, and thus the pollution of the engine. Because of the lowering of the molecular weight associated with the decomposition, these polymers can only ensure the desired viscosity and the desired viscosity index of the lubricating oil to a reduced degree. The quality of engine oils can therefore be further improved by the use of polymers with increased stability.

During our research, we have come to the unexpected realization that by using certain amounts of appropriately selected base oils, various common additives and a new polyfunctional ashless DD additive composition, engine oil and lubricating oil compositions of high shear stability can be prepared which have the usual viscosity characteristics. and viscosity index-increasing polymers are contained or free from a substantially reduced amount.

The invention therefore relates to a lubricating oil composition, preferably motor oil composition, which consists of base oils and additives suitable for lubricating oils, preferably motor oils, and in an amount of 1.5-55 wt.% Contains an additive package, each consisting of one or more additives Components "A", "B" and optionally "C", wherein the individual components have the following composition:

Component "A"

• 10-100% by weight of polyfunctional, ashless, detergent-dispersing additive composition or its oily solution, the polyfunctional, ashless, detergent-dispersing additive composition comprising such polymer components having the same or different average molecular weights by reaction of a polyolefin derivative, preferably PIB derivative which is seeded with one or more dicarboxylic acids and / or dicarboxylic anhydride and with one or more comonomers without free acid group having ethylenic double bond and has a numerical average molecular weight of at least 800, with an amino and / or imino and / or or hydroxy group-containing compound, and in the polymer components the polyolefin chain carries on average more than 6 to 20 acid derivatives, and the amount of the molecules with more than one acid derivative is at least 25% by weight, the derivative being an imide and a non-acid d / or amide and / or ester amide derivative can be, and
• 0-90% by weight of conventional alkenylsuccinic acid derivative, such as imide and / or ester and / or ester amide derivative;

Component "B"

• one or more common additives, such as detergency-dispersing additives having a different base number and different metal content, antioxidants, friction-reducing substances, abrasion inhibitors, corrosion inhibitors, foam control agents and pour point depressants;

Component "C"

• one or more conventional viscosity and viscosity index increasing polymers; wherein the weight ratio of components "A""B" and "C" is 15-85: 15-85: 0-70.

The invention further provides the additive package used in the above compositions, each containing one or more additives components "A", "B" and optionally "C", which have the above composition contains.

As mentioned, the additive package according to the invention consists of three main components (A, B, C), each containing one or more additives. Thus, the component "A" contains as the main component of a new ashless polyfunctional additive composition with DD and viscosity and viscosity index increasing effect of inoculated polyolefin derivatives, preferably from polyisobutylenebemsteinsäureanhydrid derivatives (hereinafter polyfunctional ashless DD additive composition); Component "B" is an additive mixture of common ash-containing and / or ashless additives with various effects; the component "C" is an additional and customary additive or additive mixture with viscosity and viscosity index increasing effect. The component "C" may optionally be omitted.

Component "A" contains in 10-100 wt.% Of a polyfunctional, ashless DD additive composition or its oily solution, wherein the polyfunctional, ashless DD additive composition contains polymer components which by reaction of a polyolefin derivative, preferably a Polyisobutylen- Derivatives (PIB derivative) having a numerical average molecular weight of more than 800, preferably 1,300-30,000, with one or more unsaturated dicarboxylic acids and / or carboxylic acid anhydride, preferably with maleic anhydride and with one or more non-acidic comonomers having ethylenic double bond or with copolymers of such Comonomers (and / or with maleic anhydride homopolymers) is inoculated with a compound containing an amino and / or imino and / or hydroxy group were prepared, wherein the polymer components have the same or different numerical average molecular weights and in which the polyolefin e, whose average molecular weight is preferably equal to that of the starting material, carries on average more than 6 to 20 acid derivatives, the amount of molecules with more than one acid derivative is greater than 25 wt.% And the derivative may be a mid and / or amide and / or ester amide derivative.

The above polyfunctional ashless DD additive composition preferably contains at least two polymer components having different - a lower (M _n1 ) and a higher (M _n11 ) - average _{molecular weight} , wherein the numerical average _{molecular weight of the} lower average _{molecular weight polymer component is} less than six times that Is average molecular weight of the starting polyolefin, and its weight ratio to the higher average molecular weight polymer component is 0.01-5: 1.

The ratio of the numerical average molecular weights of the higher and lower average molecular weight polymer components is $${\mathrm{M}}_{\mathrm{nll}}/{\mathrm{M}}_{\mathrm{nl}}-3-50.\mathrm{prefers}10-\mathrm{20th}$$

In preparing the polyfunctional ashless DD additive composition, an acylating agent is preferably first prepared by employing a polyolefin, preferably PIB, having a number average molecular weight of at least 800, preferably at least 1300, a polar copolymeric side chain of maleic anhydride and a polar or apolar, non-acidic comonomer with ethylenic double bond or a mixture of such comonomers. The comonomer may be a separately added compound or an initiator (used in the process), or an incorporation-controlling compound or unsaturated decomposition product of the polyolefin precursor, or an unsaturated component from the degradation of the polyolefin (US Pat. EP 0 658 572 ) be. The vaccination may be carried out by a stepwise coupling of maleic anhydride and comonomers to the polyolefin molecule and / or by addition of a copolymer chain previously prepared from maleic anhydride and one or more comonomer or portions thereof to the polyolefin. The preparation of the acylating agent is carried out in addition to a maleic anhydride / comonomer / polyolefin molar ratio of 1.2-5.5: 0.01--3.5: 1 in the presence or absence of solvent and in the presence of 5--25 wt % (relative to the maleic anhydride) of a free-radical initiator and from 0.1-5% by weight of a compound which controls the incorporation ratio of the monomers, at a pressure of between 100 and 1500 kPa, in an inert and / or hydrocarbon atmosphere, at a temperature between 80-180 ° C. If necessary, the intermediate is diluted with base oil and, after clarification, purified by filtration. The recovered acylating agent is reacted with one or more at least bifunctional compounds having amino and / or imino and / or hydroxy groups at an acylating agent / amine and / or alcohol molar ratio of 0.7-5.5: 1 at a temperature between 120- 235 ° C in the presence or absence of a catalyst reacted for 2-15 hours, optionally diluted with base oil, purified and modified in a known manner.

The recovered intermediate, which consists of a long apolar polyolefin chain and a tethered, highly polar copolymer chain having a random or alternating structure, is high in the production of imide and / or ester and / or amide and / or ester amide derivatives dispersing action, wherein the groups attached to the same polyolefin chain may be the same or different. In these precursors, the polyfunctional, mostly terminal, groups, usually consisting of a large number of carboxyl groups, allow the acylation, using appropriate at least bifunctional basic reagents, to form polymer structures which advantageously modify the flow properties of lubricating oils. It has been recognized that when using polyisobutylenes having a numerical average molecular weight of greater than 800, preferably higher than 2,000 additives are obtained which have in addition to the favorable DD effect such a viscosity and viscosity index-increasing effect, which is higher than in the polyisobutylene raw materials. High alpha-olefin content polyisobutylenes (greater than 70 weight percent) are particularly preferred for making such polymer components.

It can be considered to be a particularly advantageous fact that polyisobutylenes can be used by the invention as viscosity modifying additives, both in terms of hot viscosity and cold viscosity.

According to our experimental experience, the polyfunctional ashless DD additive composition has better thermal and oxidation stability than the usual viscosity index increasing additives, and thus the stability of the engine oil compositions is increased to an unexpected extent.

The component "A" contains - in addition to the main component described above - optionally 0-90 wt.% Of conventional and commercially available small molecule alkenylsuccinic acid derivatives, such as esters, ester amides, polyisobutenylsuccinimides, Succinimidamide or mixtures thereof. Particular preference is given to the HU 197 936 and 205 778 manufactured products.

As component "B" in the composition according to the invention, such further additives with known effect are used, which are practically indispensable in the production of modern, high-performance oil compositions. Here one preferably uses one or more such DD additives with different metal content and different base number (TBN), such as basic and hyperbasic calcium and magnesium sulphonates, phenates and salicylates; Antioxidants, such as zinc dialkyldithiophosphates and dithiocarbamates, sterically hindered phenols, cresols, aromatic amines and their derivatives; friction and abrasion reducing additives, such as aliphatic amines, amides, esters, ester amides, phosphates, thiophosphates, sulfides, polysulfides and their derivatives; Corrosion inhibitors, such as alkyltriazoles, Merkaptobenztriazole, monocarboxylic acids, dicarboxylic acids and their derivatives; Foam control agents such as dialkyl silicone polymers; pour point reducing additives, such as polyalkyl methacrylates, polyalkyl acrylates, ethylene-vinyl acetate copolymers, dialkyl fumarate copolymers and similar substances.

Preferred constituents of component "B" are, as metal-containing DD additives, the basic and hyperbasic calcium and magnesium sulfonates, phenates and salicylates, as inhibitors the zinc dialkyldithiophosphates, ashless dithiocarbamates, sterically hindered phenols and aromatic amines, the fatty acid as friction-reducing substances - And phosphoric acid derivatives and polyalkyl siloxanes, as abrasion inhibitors, the dithiocarbamates, sulfurized vegetable oil derivatives and as solidification point-reducing substances, the polyalkyl methacrylates, and mixtures of the above substances.

The commercially available additives which can be used as component "B" can easily be selected by a skilled person on the basis of previous experience and results of technical preliminary investigations.

Component "C" is a known viscosity and viscosity index increasing polymer or a correspondingly selected mixture of such polymers. For multigrade engine oil compositions, polyalkyl methacrylates, Ethylene-propylene copolymers, styrene-diolefin copolymers, and their nitrogen-containing derivatives used.

The ratio of the additives used in the components "A", "B" and "C" within the components as well as the ratios of the individual components with each other are determined by various parameters. As an example of these parameters may be mentioned the viscosity level and performance of the composition to be prepared, the properties of the base oil used, as well as the concentration-dependent effect of the additives.

For the preparation of lubricating oil compositions and motor oil compositions with highly effective and favorable properties, the concentration of the additives used in the individual components (A, B, C) are preferably selected within the ranges given in Table 1. <b> Table 1: </ b> Concentration ranges of the additives component additive Concentration range (% by weight) * A Polyfunctional ashless DD 0.6 to 20 Alkenylsuccinic derivative 0-6 Metal-containing DD 0.1-10 Copper corrosion inhibitor 0.0-0.5 B antioxidant 0.1-2 Rostungsverhinderungsstoff 0.001-1 Friction and abrasion inhibitor 0.1-3 Schaumbekämpungsmittel 0, 0001-0,1 Pour point reduction material 0-2 C Viscosity and viscosity index increasing polymer 0-25 * Based on the total preparation, including the diluent oil present in the additives.

In cases of multi-grade engine oil compositions, the amount of the individual components is preferably set in the ranges shown in Table 2. <b> Table 2: </ b> Preferred concentration ranges of the components based on the additive package component Quantity (% by weight) A 15-85 B 15-85 C 0-70

It is noteworthy that it is also possible to use such additives which can simultaneously provide a plurality of functions, which effects can increase or decrease each other. Their concentration is therefore determined under consideration of their interaction effects.

The additive package according to the invention can also be used as a concentrate. In such cases, the additive package is preferably incorporated in 0-85% by weight of diluent to facilitate handling. As diluents, for example, the base oils used in the composition, such as the usual in motor oil compositions base oils with low viscosity, VK100 <15 mm ² / s can be used.

In the composition according to the invention, the base oil used may be those customary base oils based on mineral oils which can be prepared by solvent refining and / or hydrogenation refining and / or solvent and / or catalytic dewaxing and / or bleacher derivatization and / or hydrogenation final refining and / or hydrocracking processes, and optionally by subsequent solvent and / or catalytic dewaxing, the composition of these base oils being preferably adjusted by mixing commercial base oils of various viscosities with respect to the desired level of viscosity and performance. Also preferred are the synthetic oils, such as polyalphaolefins, dicarboxylic acid esters or polyol esters, as well as vegetable oils and / or derivatives thereof, the proportion of which should be adjusted according to the requirements of use. When using the additive package according to the invention are various mixtures of base oils, which consists of paraffinic crude oils by a combination of solvent and / or hydrogenation refining were evaluated with Polyalphaolefinen and dicarboxylic acid esters as particularly advantageous, the proportions are adjusted with respect to the desired viscosity.

By using the additive package according to the invention corresponding engine oil compositions can be made to the known power levels. Thus, for example, according to the API classification (ASTM D4485), the level SG and SH, or according to the CCMC classification (Lecture of GF Cahill: Evolution of the CCMC Engine Lubricant Sequences, at CEC's Illrd International Symposium of Performance Evolution to Automotive Fuels and Lubricants, April 13, 1989 ) reach level PD-2 and GL-5.

The additive package according to the invention can, in addition to the engine oil compositions in other lubricating oil compositions, such as gear oils, hydraulic fluids, automatic transmission oils (ATF), cooling oils and machine oils; as well as in other compositions, such as brake fluids, heat supply oils, and hard oils, as well as in motor fuels to improve the properties of these are used. However, the preferred field of use is the production of additive-containing multigrade engine oil compositions.

The preparation of the compositions is carried out by the usual mixture. Here you can proceed by adding the additives used in the components individually to the base oil, and the entire composition thoroughly mixed. The other possibility is the prior production of the additive package, wherein the additives are mixed together in the desired amounts, then the viscosity, in order to facilitate further processing, is adjusted to the desired level with any base oil preferably used for the composition. The concentrate thus obtained is mixed with the desired base oil for composition.

In the preparation of the compositions, the order of addition of the additives should be determined taking into account the possible chemical reactions. The various additive components are preferably blended into the base oil in such an order as to minimize the likelihood of reaction between the compounds having different chemical structures and reaction capabilities. In order to avoid thermal decomposition, work is carried out at a temperature between 40-80 ° C.

A significant advantage of the invention is that the large molecular weight PIB base material used for the halogen-free and ashless additive allows for the production of a higher performance DD additive which will only slightly damage the elastomeric sealing materials used with appropriate amounts of other conventional additives just protected. Furthermore, it has an increased shear, heat and oxidation stability, viscosity and viscosity index-increasing effect, and an additional abrasion-inhibiting side effect, thereby enabling the reduction or omission of the usual polymers or phosphorus-containing abrasion inhibitors, and thus the production of highly stable and environmentally friendly compositions.

The invention will be explained in more detail with reference to the following examples, without restricting the protection sought to the examples. In the examples engine oil compositions are presented, which according to the most widely used API classification have the level SG.

example 1

The production parameters and characteristics of intermediates for new structure polyisobutylene-polysuccinimide derivatives used in component "A" as a polyfunctional ashless DD additive composition are shown in Table 3 and the characteristics of the final product synthesized therefrom are shown in Table 4 summarized. <b> Table 3: </ b> The main synthesis parameters and features of the intermediary of the polyfunctional ashless DD additive composition parameter intermediary PIBPOBAO-KA PIBPOBAO-KB synthesis parameters PIB average molecular weight, M _n 2250 8000 solvent base oil xylene its quantity, weight% 27 27 MSA: PIB molar ratio 2 4 Initiator,% by weight (relative to MSA) 30 35 Reaction rate impairing compound, wt% (butyl alcohol 0.05 0.05 Comonomer (CM) iC ₄ ^- styrene CM: MSA molar ratio 1: 3 Temperature, ° C 130-150 130-160 (180-200) (180-200) Pressure, kPa 101.3 (~ 10) 101.3 (~ 10) (to drive out the unreacted MSA) Reaction time, hour 9 10 Diluent oil,% by weight (relative to the intermediary) 50 70 Clarification, filtration Yes Yes Quality characteristics of the intermediate VK _{100 ° C} , mm ² / s 256.2 330.5 Acid number, mg KOH / g 44.6 10.5 MSA content, mg / g 3.1 1.2 Average BA / PIB link number Amount of connections with more than three 2.4 3.3 BA groups per molecule, wt.%. Increase in the average molecular weight 0.4 of intermediates based on PIB,% amount of compounds with more than one 13 20 BA group per molecule, wt.% 42 PIBPOBAO-KA, PIBPOBAO-KB: Oily solution of PIB succinic anhydride intermediate. The most important synthesis parameters and quality features of the polyfunctional ashless DD additive composition parameter intermediary PIBPSI-1 ** PIBPSI-2 ** synthesis parameters PIBPOBAO * sign KA KB Amount, mol 20 10 Polyamine, mol TEPA *** mol 5 4 DETA *** mol 2 - Catalyst, wt.% triethanolamine malic acid 0.1 0.2 Heating at 175-180 ° C, hour 101.3 kPa 5 - 50 kPa 1 5 30 kPa 1 - 10 kPa 1 3 Quality characteristics of the finished product VK _{100 ° C} , mm ² / s 456 689 Nitrogen content, wt.% 0.8 0.17 TBN, mg KOH / g 6.4 3.1 Diluent oil,% by weight 50 25 Ratio of polymers with higher and lower molecular weight 0.33 - * Polyisobutylenepolysuccinic anhydride, oily solution
** polyisobutylene polysuccinimide
*** TEPA tetraethylenepentamine
DETA diethylenetriamine

Example 2

The following engine oil compositions are prepared using the polyfunctional ashless DD additive compositions according to Example 1 (PIBPSI-1, PIBPSI-2). The test motor oil compositions K-1-K-14 are prepared as follows:

In a device, which is equipped with a jacket heating to a temperature of 120 ° C, or equivalent jacket cooling and an internal mechanical stirrer, first sets the present in the composition oil component with the lowest viscosity (including the synthetic components) at ambient temperature. Thereafter, with heating and constant stirring, add the further oil components in an order corresponding to the increase in viscosity at ambient temperature. The oil mixture is heated to a temperature of 70 ° C, and in an appropriate amount for ease of handling optionally up to 60 ° C heated pour point depressants (PPD), various viscosity index-increasing additives (VII-1, 2, 3 and 4), and together with these are mixed with the ashless dispersants used.

The mixture of the above materials is then stirred for one hour, then to a temperature of cca. 60 ° C cooled mixture added the desired amount of zinc dithiophosphate, detergent mixture and antioxidant. After stirring for 1 hour, the mixture is cooled to ambient temperature. The composition of the thus obtained 14 Testkomposi tions with a performance level of SG / CD according to API is summarized in Table 5.

The most important quality features of the fabrics used to make the test compositions are as follows:

Mineral oil raffinates SN-80, SN-150 and SN-350 are dewaxed fractions of N-methyl-pyrrolidone solvent-refined and hydrogenated fractions of distillates made from Hungarian mineral oil. Its kinematic viscosity at 100 ° C is 3.42 mm ² / s, 5.40 mm ² / s and 8.62 mm ² s, its viscosity index is 102, 106 and 95, its aromatic content after firing is 4.9%, 4.6% and 7.7%, their pour point is -18 ° C, -18 ° C and -15 ° C. The base oil SAE 10 / 95H is a refined, dewaxed oil obtained by a light hydrocracking process and subsequent Redistillation was prepared. The oil SAE 10 / 95H shows a kinematic viscosity at 100 ° C and 40 ° C of 5.29 and 31.7 mm ² / s, a viscosity index of 100, a aromatics content after fire of 7.7%, a sulfur content of 0 , 04%, a pour point of -18 ° C. The components PAO-4 and PAO-6 are commercially available polyalphaolefins.

The pour point depressant PPD is a polymethacrylate additive.

Of the four viscosity index modifiers, VII-1 is a polymethacrylate commonly used in engine oils, VII-2 is a solution of styrene-isoprene copolymer in base oil SN-150, VII-3 is a viscosity-modifying polyisoprene, VII-4 is a solution of olefin copolymer in base oil SN 150. The base oil SN-150 used in V.I.I.-2, 3 and 4 has the quality characteristics presented in the base oils.

The ZDDP component is a zinc dialkyldithiophosphate which is widely used as an additive of engine oil compositions for diesel and gasoline engines, and has been made with mixed primary and secondary alcohols. It has a zinc content of 9.2% by weight and a phosphorus content of 8.4% by weight, and contains diphenylamine derivatives as antioxidant (AO).

The component DET is a detergent of a mixture of basic calcium and magnesium salicylates, it has a CA content of 4.9% by weight, a Mg content of 2.6% by weight and a basic number of 2.53 mg KOH / g according to ASTM D 2896. <b> Table 5: </ b> Composition of motor oil compositions according to the invention and of reference oil compositions composition K-1 K-2 K-3 K-4 K-5 K-6 K-7 K-8 K-9 K-10 K-11 K-12 K-13 K-14 SAE level 15W-- -40 15W-- -40 15W-- -40 15W-- -40 10W-- -40 10W-- -40 10W-- -40 10W-- -40 10W-- -30 10W-- -30 10W-- -30 5W-50 5W-50 5W-50 Composition,% by weight Base oil SN-80 5.2 8.6 6.7 Base oil SN-150 44.1 53.8 44.6 34.8 47.0 45.8 59.1 63.6 65.2 77.5 Base oil SAE10 / 95 H 57.2 Base oil SN-350 35.0 27.9 24.4 40.0 29.4 19.3 22.2 5.4 PAO-4 15.0 15.0 15.0 6.4 2.9 6.6 PAO-6 15.0 70.6 75.6 73.0 PPD (PMA) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 VII-1 1.0 1.0 11.0 9.5 3.6 (PMA) VII-2 19.0 14.0 (SIC) VII-3 8.6 6.5 6.0 (PIB) VII-4 (OCP) 8.7 6.0 5.2 ZDDP 1.3 1.4 1.3 1.3 1.3 1.3 1.3 1.4 1.3 1.3 1.3 1.3 1.3 1.3 AO 0.2 DET 3.5 3.5 3.5 3.5 3.5 3.5 3.5 4.5 3.5 3.5 3.5 3.5 3.5 3.5 Komad-301 * 7.2 7.2 7.2 7.2 PIBPSI-1 7.2 7.2 2.4 7.2 7.6 7.2 1.8 7.2 PIBPSI-2 8.0 12.0 9.0 12.0 * Komad-301 commercial bissuccinimide ( M _{n PIB} = 1000, polyamine = tetraethylenepentamine)

Example 3

The beneficial effects of the invention are demonstrated by the properties of compositions K-1-K-14.

Compatibility with the sealing material

The known disadvantage of the usual succinimide detergents, especially in concentrations above 3-4% by weight, is the undesirable damage to the sealing materials used in the engines. The good compatibility of the invention with the sealing materials is proved by investigations of motor oil compositions K-6, K-7, K-8 and K-3. As a reference oil composition, the information of the composition K-5, the usual succinimide (Komad-301) contains indicated. The compositions were tested in addition to the four elastomers CEC test also with the fluoroelastomer, but under more severe circumstances performed VW 3344 test. The results are shown in Table 6.

The partially synthetic compositions K-5, K-6, K-7 and K-8 corresponding to SAE viscosity grade 10W-40 show the same composition except for succinimides (Composition K-8 contains PAO-6 containing the other three compositions PAO-4). Composition K-3 is based on mineral oil, contains mineral oil raffinate produced by a light hydrocracking process, and has an SAE viscosity level of 15W-40.

The good and very good evaluations of the compositions K-3, K-6, K-7 and K-8 given in Table 6 show the advantage of the invention in comparison with the poor results of the composition K-5. <b> Table 6: </ b> Compatibility of engine oil compositions with sealing materials preparation K-5 K-6 K-7 K-8 K-3 limits SAE level 10W-40 10W-40 10W-40 10W-40 15W-40 Dispersant, wt.% Komad-301 7.2 - - - - PIBPSI-1 - 7.2 - 7.6 7.2 PIBPSI-2 - - 12.0 - - CEC test RE1, Change in breaking strength,% -68 +2.0 -1.0 +1.9 -9.8 -50-0 Change of elongation at break,% -75 -35 -16 -29 -20 -60-0 Change of DIDC hardness +6 +1 +1 -2 0 0- + 5 Change in volume,% +10 +1.0 +1.2 +0.5 +0.2 0- + 5 RE2, Change in breaking strength,% +11 +8 +1.1 +13 +3.8 -15- + 10 Change of elongation at break,% +2 -18 -10 -22 -23 -35 + 10 Change of DIDC hardness +6 +5 +2 +3 +4 -5 + 5 Change in volume,% +2.0 0 +0.7 +1.4 +1.5 -5 + 5 RE3, Change in breaking strength,% -36 -25 -12 -19 -26 -30- + 10 Change of the Bruck strain,% -11 +4 -6.0 +0.7 -13 -20- + 10 Change of DIDC hardness -7 -22 -15 -16 -19 -25-0 Change in volume,% +17.0 +12.1 +8.0 +14.4 +17.0 0- + 30 RE + Change in breaking strength,% -33.0 -6.1 -3.8 -8.8 -4.2 -20-0 Change of elongation at break,% -51.0 -31 -26 -47 -39 -50-0 Change of DIDC hardness +3 0 0 +1 0 -5 + 5 Change in volume,% +8.0 +1.5 +0.5 +0.3 +1.0 -5 + 5 VW 3344 test Breaking strength, MPa 5.0 9.1 10.4 9.9 8.3 > 8.0 Strain,% 119 209 235 228 183 > 160 fracture 52 - - - - not possible rating bad Good Good Good Good

Abrasion-inhibiting effect

According to the data in Table 7, the new preparations show an abrasion-inhibiting effect in certain circumstances.

Composition K-9 made with standard dispersant and composition K-10 made with the additive package of the present invention show in a Timken apparatus an OK load (ASTM D 2782) equal to 45 lb (22 kg). , After a 3-hour abrasion test at a load of 40 lb (19.5 kg), however, the inventive composition K-11 shows a 60% smaller abrasion. <b> Table 7: </ b> Abrasion-inhibiting effect of engine oil compositions composition K-9 K-11 SAE level 10W-30 10W-30 Dispersant, wt.% Komad-301 7.2 PIBPSI-1 1.8 PIBPSI-2 3.0 Timken-OK load, lb 45 45 Timken abrasion of ring and block, 3 h, 40 Ib, mg 4.7 1.9

Viscosity-modifying effect, replacement of viscosity-modifying polymers

One of the greatest advantages of the new compositions of the invention arises from the increased viscosity and viscosity index increasing effect of the new additives.

This effect is shown by the data given in Table 8 of three compositions in which the conventional additive Komad-301 and the inventive polyfunctional ashless DD additive composition in compositions based on mineral oil and SAE stage 15W-40, in partially synthetic compositions of SAE stage 10W -40, as well as in synthetic compositions of SAE grade 5W-50 were tested, the compositions show the same composition with respect to the other ingredients. The most important rheological information are given in Tables 8 and 9. The compositions were adjusted to nearly the same levels within each viscosity step by changing the viscosity of the base oil and the amount of the viscosity modifying polymer.

Of the two polyfunctional ashless DD additive compositions of the present invention, PIBPSI-1 exhibits the smaller viscosity-increasing effect, but this also allows a one-third reduction in the amount of viscosity-modifying polymers in the SAE 15W-50 compared to the amount used in the DD Reference additive Komad-301 was used. For SAE grade 10W-40, the reduction in polymer content, i. the savings about 25%, and at the level 5W-50 about 15%.

Additive composition PIBPSI-2, exhibiting a higher viscosity modifying effect, allows replacement of the entire amount of viscosity modifying polymers for SAE stages 15W-40 and 15 in compositions K-4 and K-6 at a DD concentration required for API grade SG 10W-40, in the composition of grade 5W-50, only one-third of viscosity-modifying polymers were required by their application compared to the DD reference composition. As is apparent from the cold and hot viscosities, which are nearly equal in viscosity, and from the similar viscosities of the base oils, the DD additives used in the additive package according to the invention do not increase the cold viscosity of the oils as viscosity-modifying polymers any more than the conventional polymers. <b> Table 8: </ b> Replacement of Viscosity Modifying Polymers (VII) with PIBPSI-1 and PIBPSI-2 composition K-1 K-2 K-4 K-5 K-6 K-7 K-12 K-13 K-14 SAE Level: 15W-40 15W-40 15W-40 10W-40 10W-40 10W-40 5W-50 5W-50 5W-50 VII used, wt.% VII-1 - - - - - - 11.0 9.5 3.6 VII-3 - - - 8.6 6.5 - - - - VII-4 8.7 6.0 - - - - - - - Dispersant used,% by weight Komad-301 7.2 - - 7.2 - - 7.2 - - PIBPSI-1 - 7.2 2.4 - 7.2 - - 7.2 - PIBPSI-2 - - 8.0 - - 12.0 - - 12.0 Kinematic viscosity of the base oil at 100 ° C, mm ² / s 6.6 6.3 6.7 5.9 5.6 5.7 6.1 6.0 6.1 end product kinematic visc. at 100 ° C, mm ² / s 14.61 14.62 14.33 13.93 14.64 14.25 18.53 18.69 18.2 viscosity Index 134 138 137 148 152 158 217 217 194 dynamic Visk. at -15 ° C, mPas 3320 3110 3390 - - - - - - at -20 ° C, mPas - - - 3370 3480 3370 - - - at -25 ° C, mPas - - - - - - 3410 3310 3480 Pour point, ° C -30 -30 -30 -36 -36 -36 below -40 below -40 below -40

shear stability

According to the shear stability data shown in Table 9, the Bosch injector shear stability (ASTM D3934) of the engine oil compositions K-7, K-13 and K-14 containing partially or entirely succinimides as the viscosity modifying additive, the shear stability of the engine oil composition K 12 containing reference succinimide (Komad-301) and VII-1 polymethacrylate-based is similar. <b> Table 9: </ b> Shear stability of the oil compositions according to the invention composition K-7 K-12 K-13 K-14 SAE level 10W-40 5W-50 5W-50 5W-50 Used VII% by weight PPD 0.2 - - - VII-1 - 11.0 9.5 3.6 Dispersant used,% by weight Komad-301 - 7.2 - - PIBPSI-1 - - 7.2 - PIBPSI-2 12.0 - - 12.0 characteristics Kinem.Visk 100 ° C, mm ² / s 14.95 18.53 18.69 17.94 40 ° C, mm ² / s 97.2 94.7 95.7 102.4 viscosity Index 161 217 217 194 CCS-15 ° C, mPas 3100 CCS-25 ° C, mPas 3410 3310 3260 Bosch shear KV / 100 ° C, 30 cycles, mm ² / s 12.09 13.99 14.77 14.43 SSI,% 31 37 31 30 VI 30 cycles 150 KV / 100 ° C 250 cycles, mm ² / s 11,70 13.38 14,21 14.01 SSI,% 36 41 35 31 VI 250 cycles 148 Viscosity of the base oil at 100 ° C, mm ² / s 5.8 6.1 6.0 6.1

Detergent-dispersing effect, performance on brake tester

The tests on the brake tester, as a decisive feature for the qualification of engine oil compositions, have been summarized in Table 10. The oil compositions K-2 and K-3 were tested on brake testers Petter W-1, M 102 E, Sequence IIIE and PV 1431. The engine mud scores of the M 102 E and Sequence IIIE brake testers show excellent dispersing properties, and the piston cleanliness values at the Sequence IIIE and PV 1431 brake testers have a corresponding detergency effect on the additives used in the oil compositions. The advantageous composition of the compositions according to the invention was further demonstrated by the good abrasion properties measured on the brake tester Petter M 102 E and in particular on the Sequeence IIIE brake tester and by the very small bearing wear measured on the brake tester Petter W-1. <b> Table 10: </ b> Brake tester testing of PIBPSI-1 polyfunctional, ashless DD additive composition containing composition CCMC G4 / PD-2 limits composition K-2 K-3 SAE level 15W-40 15W-40 Additive content, wt.% PPD 0.2 - VII -1 - 1.0 VII -2 6.0 5.2 ZDDP 1.3 1.3 AO - 0.2 PIBPSI-1 7.2 7.2 characteristics 1st Petter W-1 Bearing wear, mg 4.7 Max. 25 2. M 102 E Average engine sludge 9.4 minute 8.5 Ringfest run ASF = 16 ASF = max. 30 piston siege Groove 1 30.0 Max. 30 Groove 2 19.1 Max. 25.9 cam wear 3.0 Max. 5.7 Average, μm Stoßfußabnutzung, 1.9 Max. 3.1 Average, μm 3. Sequence III 40 ° C increase in viscosity,% 38 Max. 300 piston varnish 9.38 minute 8.9 Ringzonenverlackung 7.40 minute 3.5 Mud value number 9.57 minute 9.2 Ring and valve lever test run no no Cam and butt foot wear, average, μm 3.7 Max. 30 max., μm 11.0 Max. 60 4. W 1.6; TC brake tester (PV 1431) Ringfest run no no (ASF = 0) (ASF = 0) piston cleanliness 70 minute 69.4

Example 4

The composition of the additive package concentrate of this invention and the engine oil composition diluted therefrom are shown in Table 11. <b> Table 11: </ b> Additive package concentrate and the diluted motor oil composition (% by weight) composition P-1 P-2 P-3 P-4 M-1 M-2 Component "A" 10.4 7.2 Komad-301 - 11.4 6.1 - PIBPSI-1 15.6 - 33.0 7.8 PIBPSI-2 52 57.0 - 26.0 Component "B" 5.0 5.0 PPD (PMD) 1.3 1.3 1.0 0.7 ZDDP 8.4 8.2 6.6 4.2 DET 22.7 22.1 17.8 11.3 Component "C" 6.5 VII-3 (PIP) 35.5 Base oil SN-150 50.0 Base oil mixture 84.6 81.3 15W-40

Claims (18)

1. A multigrade dope motor oil composition comprising a base oil, useable for a motor oil, and additives, characterized in that it contains in an amount of 1.5-55% by weight an additive pack that contains components "A", "B" and, if desired, "C", consisting of one or more additives each, wherein the individual components have the following composition:

   component "A"

   - in an amount of 10-100% by weight a polyfunctional ashless additive mixture acting detergently-dispersingly or an oily solution thereof, where the polyfunctional ashless additive mixture acting detergently-dispersingly consists of polymeric components of identical or different numerical average molecular weight that were prepared by reacting a polyolefine derivative of a numerical average molecular weight of at least 800, preferably a PIB-derivative, that was grafted with one or more dicarboxylic acids and/or dicarboxylic anhydrides and one or more comonomers with olefinic double bond but without any free acid group, and compounds containing an amino and/or imino and/or hydroxyl group, where in the polymeric components the polyolefine chain carries in average more than 6-20 acid derivatives, and the amount of the molecules carrying more than one acid derivative is at least 25% by weight, where the derivative may be an imide and/or amide and/or ester amide derivative, and

   - in an amount of 0-90% by weight a usual alkenyl succinyl acid derivative like an imide and/or ester and/or ester amide derivative;

   component "B"

   - one or more usual additives such as detergently-dispersingly acting additives with different base number and different metal content, antioxidants, materials decreasing friction and abrasion, corrosion-inhibiting agents, anti-foam additives and flow-point decreasing agents;

   component "C"

   - one or more usual polymers increasing viscosity and viscosity index;

   wherein the weight ratio of components "A", "B" and "C" amounts to 15-85:15-85:0-70.
2. A motor oil composition as claimed in claim 1, characterized by a content of polymer components grafted with maleic anhydride in component "A".
3. A motor oil composition as claimed in claim 1 or 2, characterized in component "A" by a content of polymeric polyolefine components that were prepared by reacting polyisobutylene having a numerical average molecular weight of 1300-30,000.
4. A motor oil composition as claimed in any of claims 1 to 3, characterized in component "A" by a content of at least two polymeric components that have different - a lower (M_n1) and a higher (M_n11) - numerical average molecular weight, wherein the numerical average molecular weight of the polymeric component with lower numerical average molecular weight is smaller than the sixfold value of the average molecular weight of the starting polyolefine, the ratio of the average molecular weight of the polymeric component with lower numerical average molecular weight to that of the polymeric component with higher numerical average molecular weight amounts to 3-50:1, preferably 10-20:1, and the weight ratio of the polymeric component with lower numerical average molecular weight to the component with higher numerical average molecular weight amounts to 0.01-5:1.
5. A motor oil composition as claimed in any of claims 1 to 4, characterized by a content in component "B" of organic calcium or magnesium salts like sulfonates, phenates, salicylates or their mixture as detergently-dispersingly acting additive with different base number and different metal content.
6. A motor oil composition as claimed in any of claims 1 to 5, characterized by a content of 0.6-26% by weight of component "A", 03-18.6% by weight of component "B" and 0-25% by weight of compound "C".
7. A lubricating oil composition comprising a base oil, useable for a lubricating oil, and additives, characterized by a content of 1.5-55% by weight of an additive pack that contains components "A", "B" and, if desired, "C", consisting of one or more additives each, wherein the individual components have the following composition:

   component "A"

   - in an amount of 10-100% by weight a polyfunctional ashless additive mixture acting detergently-dispersingly or an oily solution thereof, where the polyfunctional ashless additive mixture acting detergently-dispersingly consists of polymeric components of identical or different numerical average molecular weight that were prepared by reacting a polyolefine derivative of a numerical average molecular weight of at least 800, preferably a PIB-derivative, that was grafted with one or more dicarboxylic acids and/or dicarboxylic anhydrides and one or more comonomers with olefinic double bond but without any free acid group, and compounds containing an amino and/or imino and/or hydroxyl group, where in the polymeric components the polyolefine chain carries in average more than 6-20 acid derivatives, and the amount of the molecules carrying more than one acid derivative is at least 25% by weight, where the derivative may be an imide and/or amide and/or ester amide derivative, and

   - in an amount of 0-90% by weight a usual alkenyl succinyl acid derivative like an imide and/or ester and/or ester amide derivative; component "B"

   - one or more usual additives such as detergently-dispersingly acting additives with different base number and different metal content, antioxidants, materials decreasing friction and abrasion, corrosion-inhibiting agents, anti-foam additives and flow-point decreasing agents;

   component "C"

   - one or more usual polymers increasing viscosity and viscosity index;

   wherein the weight ratio of components "A", "B" and "C" amounts to 15-85:15-85:0-70.
8. A lubricating oil composition as claimed in claim 7, characterized by a content of polymer components grafted with maleic anhydride in component "A".
9. A lubricating oil composition as claimed in claim 7 or 8, characterized in component "A" by a content of polymeric polyolefine components that were prepared by reacting polyisobutylene having a numerical average molecular weight of 1300-30,000.
10. A lubricating oil composition as claimed in any of claims 7 to 9, characterized in component "A" by a content of at least two polymeric components that have different - a lower (M_n1) and a higher (M_n11) - numerical average molecular weight, wherein the numerical average molecular weight of the polymeric component with lower numerical average molecular weight is smaller than the sixfold value of the average molecular weight of the starting polyolefine, the ratio of the average molecular weight of the polymeric component with lower numerical average molecular weight to that of the polymeric component with higher numerical average molecular weight amounts to 3-50:1, preferably 10-20:1, and the weight ratio of the polymeric component with lower numerical average molecular weight to the component with higher numerical average molecular weight amounts to 0.01-5:1.
11. A lubricating oil composition as claimed in any of claims 7 to 10, characterized by a content in component "B" of organic calcium or magnesium salts like sulfonates, phenates, salicylates or their mixture as detergently-dispersingly acting additive with different base number and different metal content.
12. A lubricating oil composition as claimed in any of claims 7 to 11, characterized by a content of 0.6-26% by weight of component "A", 03-18.6% by weight of component "B" and 0-25% by weight of compound "C".
13. An additive pack that is useable for lubricating oil compositions, preferably for motor oil compositions, characterized in that it contains in an amount of 15-100% by weight components "A", "B" and, if desired, "C", consisting of one or more additives each, and in an amount of 0-85% by weight a diluent, wherein the components have the following composition:

    component "A"

    - in an amount of 10-100% by weight a polyfunctional ashless additive mixture acting detergently-dispersingly or an oily solution thereof, where the polyfunctional ashless additive mixture acting detergently-dispersingly consists of polymeric components of identical or different numerical average molecular weight that were prepared by reacting a polyolefine derivative of a numerical average molecular weight of at least 800, preferably a PIB-derivative, that was grafted with one or more dicarboxylic acids and/or dicarboxylic anhydrides and one or more comonomers with olefinic double bond but without any free acid group, and compounds containing an amino and/or imino and/or hydroxyl group, where in the polymeric components the polyolefine chain carries in average more than 6-20 acid derivatives, and the amount of the molecules carrying more than one acid derivative is at least 25% by weight, where the derivative may be an imide and/or amide and/or ester amide derivative, and

    - in an amount of 0-90% by weight a usual alkenyl succinyl acid derivative like an imide and/or ester and/or ester amide derivative;

    component "B"

    - one or more usual additives such as detergently-dispersingly acting additives with different base number and different metal content, antioxidants, materials decreasing friction and abrasion, corrosion-inhibiting agents, anti-foam additives and flow-point decreasing agents;

    component "C"

    - one or more usual polymers increasing viscosity and viscosity index; wherein the weight ratio of components "A", "B" and "C" amounts to 15-85:15-85:0-70.
14. An additive pack as claimed in claim 13, characterized by a content of polymer components that are grafted with maleic anhydride in component "A".
15. An additive pack as claimed in claim 13 or 14, characterized in component "A" by a content of polymeric polyolefine components that were prepared by reacting polyisobutylene having a numerical average molecular weight of 1300-30,000.
16. An additive pack as claimed in any of claims 13 to 15,
    characterized in component "A" by a content of at least two polymeric components that have different - a lower (M_n1) and a higher (M_n11) - numerical average molecular weight, wherein the numerical average molecular weight of the polymeric component with lower numerical average molecular weight is smaller than the sixfold value of the average molecular weight of the starting polyolefine, the ratio of the average molecular weight of the polymeric component with lower numerical average molecular weight to that of the polymeric component with higher numerical average molecular weight amounts to 3-50:1, preferably 10-20:1, and the weight ratio of the polymeric component with lower numerical average molecular weight to the component with higher numerical average molecular weight amounts to 0.01-5:1.
17. An additive pack as claimed in any of claims 13 to 16, characterized by a content in component "B" of organic calcium or magnesium salts like sulfonates, phenates, salicylates or their mixture as detergently-dispersingly acting additive with different base number and different metal content.
18. An additive pack as claimed in any of claims 13 to 17, characterized by a content of 0.6-26% by weight of component "A", 03-18.6% by weight of component "B" and 0-25% by weight of compound "C".