WATER-DISPERSIBLE COMPOSITIONS HAVING A DETERGENT OR PROTECTIVE ACTION ON STEEL SHEETS AND A PROCESS FOR THEIR PREPARATION

Abstract: There are disclosed water-dispersible compositions having a cleaning action when they are used at a 3-5% concentration and a protective action when they are used at a concentration of 40% or higher. Said compositions are especially useful in forming steel sheets. Also disclosed is a process for their preparation. The composition consists of four components: 1) The reaction product of an ester of phosphoric acid and an amine 2) The reaction product of two carboxylic acids with an alkanolamine. 3) water 4) a co-solvent.

Description: The present invention relates to water-dispersible compositions having a detergent and/or protective action on steel sheets, and a process for their preparation. More specifically, the present invention relates to water-dispersible compositions that, when used in a diluted (3-5%) state, have a (temporary) detergent and protective action, and, when used at higher concentration (≧ 40%), have a longer-lasting protective action, in a similar way as the so-called slushing oils used up to now, and a process for their preparation. As is well known to the persons skilled in the art, the die-forming steel-sheets are sheets that are obtained from low-carbon steel (0.15%, extra-mild steel; 0.15 - 0.30%, mild steel); the steel grades that are employed can be of the rimmed type, semi-killed type, or of the killed type. Said steel sheets are obtained by cold rolling. After this process, the steel sheet is subjected to annealing and then to "temper milling" (milling in a mill that usually exhibits a reversible quarter arrangement). The purpose of this treatment is to rise the steel sheet yield point by means of a slight thickness reduction, thus imparting to the steel sheet good forming characteristics. As is known to the persons skilled in art, the steel sheet strip from the annealing furnace is to be cleaned of "metal fines" formed during the rolling step and/or of the carbonaceous particles from cracking of the lubricating agents employed in the cold rolling process. This cleaning operation is usually performed by spraying a water solution, said solution containing surface active agents, rust preventive additives (such as, for example, boric amide, boron, nitrites, benzoates, carbonates, sulphonamides, and so on) and small amounts of anionic compounds, such as soaps, amine salts, and so on. The application site for these detergent compositions is at the separation line between the back-up rolls and the working rolls and/or at the separation line between the working roll and the strip. Said cleaning solution should not stain the steel sheet (that is they should be inert towards it), while preventing the surface of the steel sheet from being oxidized within the time span elapsing between their application and the following application of the protective agent (this is the reason why these detergent compositions also contain rust preventing additives as summarily stated above). Said detergent compositions should also provide a lubricating action to remove wear of working rolls and preserving for a longer time the roughness of the rolls themselves. The detergent composition must have dried, before the protective agent is applied, for the protective composition, which is an oil-or wax-base composition, to be easily applied, as well as to prevent the water contained in the detergent composition from giving rise to a rust layer under the oil/wax layer of the protective agent. The known previous protective compositions usually consist of water-dispersions of waxes, or they are based on paraffinic and/or naphthenic petroleum hydrocarbons. In said protective compositions, dispersant amides, anionic oleophylic additives (such as e.g. petroleum sulphonates, said sulphonates corresponding to the formula R SO₃X, wherein R is an alkyl-aryl group with 20 to 30 carbon atoms, and X is usually a sodium atom, or an amine or alkanolamine group) are usually compounded with petroleum hydrocarbons. The main function of said protective compositions is to prevent the steel strip from being oxidized within the time period, that can even last several months, between the manufacture of steel sheets and their final use, e.g. in the car industry or in the electrical household applicance industry. Combinations of emulsifying agents for oil-in-water type emulsions are known e.g. from DD-A-159 434. Said oil-in-water emulsions are said to be suitable for water cooling systems and as metal-working fluids. They are made up of 20-80% ethoxylated (C₅-C₂₅)alkylphenols, 5-50% oleic acid mono-, di-, or tri-(C₁-C₄)alkanolamides, and 5-50% of an amine salt of a mono-, or di-(C₈-C₂₀)alkylphosphoric ester. This patent concerns combinations of emulsifying agents, not the corrosion inhibiting composition which is said to be a water-in-oil emulsion, whereas the water-dispersible composition of the instant invention does not contain any oil. Moreover, also the end-use of the said oil-in-water emulsion is quite different. A water-based rust inhibitor suitable for protecting steel sheet products is disclosed in US-A-4 379 072. The non-petroleum based composition comprises 75-90% water, 2-8% linseed oil fatty acid, 1-10% of a (C₆-C₁₂) dibasic acid, 3-8% of an amine blend (comprising a 1:2 to 2:1 ratio of a cyclic amine such as cyclohexyl amine, morpholine and (C₂-C₄)alkanol amine), 0.5-3% of a water-soluble alkali metal base; It is clear that although the rust inhibitor disclosed in this patent is water-based and appears to be suitable for protecting steel sheet products, the composition thereof is quite different from that of the present invention. Corrosion inhibiting compositions useful for coating surfaces to provide temporary protection against corrosion are described in US-A-4 130 524. Said compositions contain (a) a salt of a carboxylic acid and an organic amine,(b) a salt of a phosphoric acid and an organic amine or a salt of an alkyl acid phosphate and an organic amine, and (c) a water-dispersible polymer. Also the composition of this patent differs substantially from that of the compositions of the instant case. Finally, a metallic surface cleansing agent is described in FR-A-1 602 731. The detergent liquid contains in particular (a) a monoethanolamine soap and/or a potassium soap, (b) a tri-, and/or di-, and/or mono-ethanolamine, (c) a non-organic wetting and emulsifying agent, and (d) an organic solvent and/or a mineral oil. As it is immediately apparent, this cleansing agent is not a water-based composition. In fact, although it can be diluted with water, it does not contain, per se , water whereas it contains not less than 12% of an organic solvent and/or of a mineral oil. As it can be seen, none of such patents, however, describes the novel compositions of the instant invention. To Applicant's best knowledge there has never been disclosed or even suggested a water-dispersible composition that, when used in a diluted state, has a detergent and temporary protective action, whereas when used at higher concentrations has a longer-lasting protective action. As the detergent compositions, e.g. are aqueous, they are little, if at all, compatible with the wax-base or oil-base protective compositions. Therefore, if the detergent composition is not thoroughly dried before the protective composition is applied, there is a serious risk that the residual water causes the steel sheet to be rust- stained, notwithstanding the presence of the protective agent. Moreover, also the known protective compositions exhibit various drawbacks: they are not easily distributed, especially the oil-based compositions, onto the steel strip surface, especially at room temperature, thus making it necessary to apply heat; the conventional protective compositions tend to cause the formation of depositions onto the distribution rolls and to clog the nozzles of the devices that are used for the application thereof, with the consequence that further maintenance work is needed; the protective film formed by the known protective compositions is sometimes non-homogeneous or non-continuous; the protective agents that are commercially available can form stable aerosols by spray application; the known protective agents are sometimes not completely inert towards the steel surface, thus causing stains on it; if the steel surface is handled shortly after said oil- or wax-based protective agents have been applied, the protective agent becomes partly removed; when several steel plates are stacked, protective oil accumulates along the borders due to pressure or gravity; moreover when plate reams are stacked onto joists, central pockets of a fatty nature are formed internally thus giving rise to more or less evident surface halos; the unsaturation or aromatic nature of the oily vehicle of the known protective compositions can give rise to stains on the surface of the steel sheets; the known protective compositions are inflammable, thus giving rise to fire hazard; the presence of an oily or waxy film of the conventional protective agents imparts to the steel sheets greasiness and/or tackiness, thereby making it more difficult to operate on them by mechanical means and, further, the adherence between plates makes their manipulation with suction cups problematic; the galvanization or phosphate-coating treatments require that the oily or waxy protective film be completely removed, such a removal being difficult, if not impossible , to be carried out with a cold process; the same problem occurs if the steel sheet is to be lithographed. It is therefore an object of the present invention to provide a detergent composition and a protective composition for forming steel sheets not having the draw-backs of the known compositions. It has now been discovered a water-dispersible composition that exhibits a long-term protective action when employed at a concentration of at least 40% or higher, said water-dispersible composition exhibiting a detergent and a short term protective action when employed at a concentration of 3-5%. The compositions of the present invention consist substantially of four components: 1) base A, 2) base B, 3) dispersant, 4) co-solvent. Base A serves mainly to impart detergency to the composition of the present invention when this is employed in the diluted state (concentration 3-5%); said base can consist of a mixture of different bases A. Base B, on the contrary, serves mainly to impart film-forming properties to the composition of the present invention when this is used in a concentrated state (≧ 40%); also base B can consist of a mixture of different bases B. The dispersant is water. The cosolvent consists of one or a plurality of glycols. According to the present invention, base A is obtained by reacting a water-dispersible acid reagent Aa with a water-soluble basic reagent Ab; the product of said reaction can be a salt, a soap and/or a condensation product. The reaction conditions normally promote the condensation, but the quality of the final product will not be very different if, instead of a condensation, a salt forming reaction between Aa and Ab occurs. According to the present invention, any polycarboxylic and / or monocarboxylic acid having more than 8 carbon atoms can be used as the acid reagent Aa to be used for the preparation of base A, provided it is water-dispersible. Preferred are the water-soluble polycarboxylic acids ; otherwise, the acidic reagent Aa can also be a phosphoric ester that is obtained by reacting phosphoric anhydride (P₂O₅) with a fatty alcohol having at least 8 carbon atoms in the molecule, or with a monosubstituted and/or disubstituted phenol compound, oxo-alcohol compound, said compounds being condensed or non-condensed with ethylene oxide and / or ethylene oxide / propylene oxide mixtures. The term "oxo-alcohol" stands for an alcohol prepared by means of the oxo-process from a polyolefine having at least 7 carbon atoms. Said alcohols are obtained by adding one mole of carbon oxide and two moles of hydrogen to polyolefins, such as tri-, tetra-, penta-propylene, di-, tri-, tetra-isobutylene, propylene-isobutylene, tributene, and so on, with a Fischer-Tropsch catalyst (e.g. cobalt carbonyls, Raney cobalt): see for example The Merck Index 10th edition, ONR-65 and references therein. Illustrative examples of phosphoric esters that can be used for the preparation of base A according to the present invention are described in US patent 3,004,056, the disclosure of which is incorporated herein by reference. Among the various alcohols that are described in said US patent, those having the following formula: R₁-(OCH₂CHR₂) x -OH, (I) wherein R₁ is an alkylene or aralkyl group having 8 to 24 carbon atoms, and R₂ is a hydrogen atom or a methyl group, x is an integer of from 0 to 20, included, are especially preferred for the preparation of the phosphoric esters useful for the present invention. The esters according to the above-mentioned US patent can contain in their molecule non-esterified phosphoric groups that impart acid properties the reto; in this case they will be available for further reaction with any water-soluble, organic and/or inorganic base. Among the various types of the above-mentioned acid reagent Aa that can be used for the preparation of base A accordingly to the present invention, the arylalkyl-ethoxyphosphate - type esters , commercially available under the trade mark GAFEN, (GAF Corporation, New York, N.Y. ) or the organic, water-soluble polycarboxylic acid with an oleic acid equivalent of 0.83, manufactured by Ciba-Geigy and sold under trade mark REOCOR 190, or mixtures thereof are presently preferred. As the based reagent Ab useful for the preparation of base A of the present invention, an organic basic compound can be used, such as an amine, a diamine and/or a polyamide, having 1 to 24 carbon atoms in their molecule and corresponding to the following formula: H₂N-(RNH) n -H (II) wherein R stands for an alkylene group having 1 to 4 carbon atoms and n is an integer of ≦ 6; Preferably, the basic reagent Ab will consist of a propylene diamine having a primary amine group and a secondary amine group, and corresponding to formula (II), with or without oxyethylene groups. According to the present invention, as the basic reagent Ab also a compound of formula can be advantageously used. A product according to the above-mentioned formula, wherein R stands for the alkyl residues of the tallow fatty acids, in the following proportions: C₁₂: 1%; C₁₄:4%; C₁₆:31%; C₁₈:64%; C₂₀: trace amounts, is sold by AKZO CHEMIE Italia S.p.A.,Via Vismara 80, 20020 Arese, under the tradename ETHODUOMEEN T 13. As the Ab reagent, the mixture of diethanolamine and a diamine of formula (IIIa) , that is ETHODUOMEEN T 13, is presently preferred. Moreover, also the alkanolamines, preferably the dialkanolamines of the formula HN(ROH)₂ (IV) wherein R is an aliphatic residue containing 2 to 6 alkylene groups, are useful basic reagents Ab according to the present invention, depending on the reaction conditions, the number and the nature of the functional groups, the alkylamines, the alkanolamines and the low and / or high molecular weight organic acids can give rise to different compounds. If the reaction is carried out at room temperature, merely a neutralization and /or saponification will occur. For example, if a monoalkanolamine of formula HOCHRCH₂NH₂ is reacted with oleic acid at room temperature ( or any temperature much lower then 100°C), an addition compound of formula HOCHRCH₂NH₂.HOOCC₁₇H₃₅ (V) will be obtained, said compound being usually called a soap. This compound has a waxy appearance, is non-crystalline and usually is thixotropic. On the contrary if fatty acids or carboxylic acids are reacted with the above-mentioned mono- alkanolamines and dialkanolamines in a molar ratio of 1:1, at a much higher temperature (140-160°C), non-water-soluble N-alkylol amides will mainly be obtained. If a mono-alkanolamine is reacted at 160°C with a carboxylic acid, the corresponding monoalkanolamide will be obtained. However, in the course of said reaction perceptible amounts of aminoesters and amidoesters will be formed due to the reaction of the OH group of the monoalkanolamine with the carboxylic acid. Moreover, also small amounts of amino-diesters and amido-diesters will possibly be formed in the case the monoalkanolamine contains also dialkanolamines. If, on the contrary, the alkanolamine /carboxylic acid molar ratio is 2:1, the reaction at 140-160°C, yields a dialkanolamide that, contrary to the product obtained with a molar ratio of 1:1, is water soluble. This product is actually a complex mixture comprising N-alkylolamide, amino-ester, amino-diester, amido-ester, amido-diester, free dialkanolamine and a major amount of dialkanolamide. It is believed that the water-solubility is mainly due to the free alkanolamine. In case the alkanolamine/carboxylic acid molar ratio is 1.4:1, a product is obtained that is dispersible instead of being soluble. However, if the water contains glycols (co-solvents) or dialkanolamine the dispersion is solubilized. According to the present invention, base B is mainly a product or a mixture of products of condensation or salification possibly containing free components resulting from the reaction at a temperature of from 150°C to 190°C of a mono-carboxylic acid with 8-18 carbon atoms (reagent Ba), in mixture with a dicarboxylic acid having a maximum of 36 carbon atoms (reagent Bb), with an alkanolamine, preferably a dialkanolamine (reagent Bc) in a molar ratio of Bc: (Ba+Bb) ≦ 1.5:1. The reagent Ba according to the present invention preferably consists of a monocarboxylic aliphatic acid containing 10 to 20 carbon atoms, or a mixture of preponderantly unsaturated fatty acids and 2-3% of rosin acids, said rosid acids consisting of abietic and neo-abietic acid, such as, e.g., the tall oil fatty acid. The reagent Bb useful for preparing base B according to the present invention is preferably a dimer acid, said dimer acid being obtained from the polymerization of an unsaturated fatty acid with 18 carbon atoms, containing about 80-97% of dimer acid, about 20-3% of trimer acid and a maximum of about 1% of monomer acid. The reagent Bb tipically consists of a dimer acid containing about 95% of dioleic acid, about 4% of trimer acid and about 1% of monomer acid. Said acid has an acid number of about 191, an equivalent weight of about 293 and a molecolar weight of about 365. Dimer acids exhibiting said features are commercially available e.g. under the trade name PRIPOL, UNICHEMA International. The reagent Bb according to the present invention can also be a hydrogenated dimer acid having an acid number of about 193, an equivalent weight of about 290 and an iodine number of about 30. The reagent Bc is preferably a dialkanolamine , said dialkanolamine being obtained from a mixture of diethanolamine and diisopropylamine in the molar ratio of 2:1. The co-solvent that can be used for the preparation of the composition of the present invention can be a monoalkyl ether of an alkyleneglycol of the formula R₁O[CH₂C(R₂)OH] y -OH (VI) wherein R₁ stands for 1 to 4 alkyl groups R₂ stands for an H atom or a methyl group and y is an integer of from 1 to 3. Preferred glycol ethers are, e.g. 2-ethyl-1,3-hexanediol and ethylene glycol in a molar ratio of 3:1. It must be taken into account that the present invention is practiced using commercially available materials that consist of a mixture of compounds, not a single compound. Therefore, even though in the course of the present disclosure reference is made to single compounds, they are actually, in most cases, mixtures of compounds, said mixtures containing the main compound in a preponderant amount, together with other compounds. Thus, e.g. the fatty acid actually consists of a mixture of acids, such as, e.g., the tall oil acids. The mono-alkanolamine can actually contain various monoalkanolamines and dialkanolamines. Same can be said of alcohols. Therefore, also the reaction products obtained from said reagent will obviously consist of more or less complexe mixture, as illustrated herein above for the alkanolamines. The following examples serve to better illustrate the present invention. They have not to be construed restrictively, because, as it is evident for the man skilled in the art, the way the present invention is implemented can be varied within rather large limits, due to the fact that many are the useful starting materials which normally consist of mixtures rather then a single pure compound. However, the man skilled in the art, based on the above disclosure, will meet no difficulties in adapting the reaction conditions to the actual circumstances, thereby always being able to obtain the desired product. Unless otherwise stated, parts and percentages are on a weight basis. Preparation of base A As already stated above, base A has the main purpose of imparting to the composition of the present invention detergency when used in a diluted state (concentration of 3-5%). Example 1 (Base A1; condensation reaction) Into a four-necked two- liter glass reactor provided with vertex thermometer, stirrer, reflux condenser and connection to the vacuum pump and a trap for measuring the reaction water, 5.5 GAFEN LM 400 and 49.4 g REOCOR 190 are charged. The mixture is heated under stirring, to 65 °C. After stirring for 10 minutes, 41.17 g diethanolamine and 41.7 g ETHODUEMEEN T 13 are added under continuous stirring. To the heterogeneous mixture, having a molar ratio of 1:2, 100 g xylene is added. The reflux condenser with trap is connected, and the temperature is raised to 150°C - 160°C. The azeotrope is refluxed while maintaining the temperature for 14 hours or until 14 ml of water is collected. This means that also a small amount of ester has been formed besides the diethanolamide and, therefore, the base will exhibit also a film-forming property, that however will not affect its detergent property. After cooling to 60 °C, 10 g of diethanolamine or diisopropanolamine is added for the purpose of increasing the water solubility. The reflux condenser with trap is removed and the vacuun pump is connected. At a pressure of 1 mmHg at a maximum temperature of 60°C, the xylene is distilled off. This operation is rather long and requires the temperature to be thoroughly controlled to avoid the further formation of ester. To avoid this draw-back, the diethanolamine can be substituted with the same amount of diisopropylamine, but this involves a partial loss of the latter through distillation. The end product has a weight of about 132 g and a clear appearance, viscous consistency and amber colour; it is completely soluble at any ratio in water of 50°HF (french hardeness degrees). A 10% solution in distilled water (pH about 8.8) passes a load of 2800 pounds and does not give rise to corrosion on a mild steel foil after 5 cycles in the climatic chamber (8 hours in a saturated ambient at 40°C plus 16 hours in a saturated ambient at 25°C = 1 cycle). Draves test, average: 23 seconds (1% solution in distilled water). Base A1 has the following initial percent composition: Example 2 (base A2; salification reaction) Into a 1-liter glass vessel provided with an electromagnetic stirrer, 11 g GAFEN LE 500, and 100 g REOCOR 190, are added in said order, followed by 10 g water, and the mixture is sturred, with optional heating to 40/45°C, for 30 ÷ 45 minutes, at the most. The solution is not clear. Under steady stirring and with the heater off, 82 g diethanolamine and 82 g ETHODUOMEEN T 13 are slowly and very cautiously added. Stirring is continued until the solution is completely clear, adding more REOCOR 190 in case the solution remains turbid. A clear appearance and complete solubility in water indicate that the salification is sufficient. About 280 g salified product is obtained. The thus formed soap is a free flowing, pale straw-colored mass and is completely water-dispersible in any ratio; it is rather sensitive to water hardeness. The percent composition of the starting materials for base A2 is: Aa: 39.0 g (GAFEN LE 500 + REOCOR 190) Ab: 57.5 g (diethanolamine + ETHODUOMEEN T 13) Water: 3.5 g A 10% solution in distilled water (pH about 9) passes a Falex load of 1700 pounds. The protective power passes 12 cycles in the climatic chamber. A 1% solution in distilled water provides an average of 18 seconds at the Draves test. Example 3 (base A3; condensation reaction) A two-liter glass reactor provided with at least 3 necks and equipped with vertex thermometer, reflux condenser, and magnetic bar stirrer is used, said reflux condenser being connectable to a vacuum pump and provided with a trap for collecting the water evolving from the reaction. 187.5 g REOCOR 190 and 350 g xylene are chatged into the reactor. The mixture is heated to 105 °C after connection of the vacuum pump to the reflux condenser. The temperature is gradually raised to 120°C under continuous stirring; this condition is maintained until water is collected in the trap. The vacuum is disconnected. Stirring is continued for about half an hour and 168.75 g diethanolamine is added. Further 25-30 g xylene is added and the reflux condenser with trap is connected. The temperature is raused to 160 ÷ 165°C under stirring . The temperature is controlled at 165°C. Stirring is continued and the temperature is kept constant for 12 hours, while noting the level of the reaction water reached in the trap. When 32 ml of water has been collected, the reaction mass will have the desired dialkanolamide/ester ratio. After cooling to 150°C, the reflux condenser is removed and xylene is distilled off at 1 mmHg. The operation can also be carried out in a rotary evaporator connected to a vacuum pump. After removing the xylene, the reaction product is cooled down to 60°C. 143 g of diethanolamine is added under stirring to fluidize and clear the product. Yield: 370 g. The appearance of the mass is clear, non thixotropic, viscous but sufficiently flowing and its color is markedly lighter than that of the product of example 1. It is completely water dispersible, even into medium hardness water (pH ≧ 9). The initial percent composition of base A3 is as follows: Molar ratio: Aa : Ab = 1 : 2 A 10% solution in distilled water passes a Falex load of 2500 pounds. It causes no corrosion on a mild steel plate after 10 cycles in the climatic chamber. The wetting power referred to a 1% water solution, according to the Draves test, shows an average value of 20 seconds. According to the present invention in order to obtain a water-dispersible composition of good quality it is necessary that base A exhibits, in a proper amount, the following characteristics (listed in decreasing order of importance): As) Degreasing and moistening-soaking properties; Af) Film forming, polar and protecting properties; Al) Lubricating properties. In table I the evaluation of each of the above characteristics relative to bases A prepared in the examples are reported. Base As Af Al Average evaluation A1 I I O I A2 O O I O A3 S B B B Legend: I = insufficient S = sufficient B = good O = very good Based on these evaluation, base A2 is the best. Base A3 is a good alternative, especially if the water-dispersible composition needs to have a good lubricating power (in the case of great elongations at the temper mill). Preparation of base B As stated above, base B is preponderantly used to confer film forming power to the composition of the present invention, when it is used in a concentrated state (conc. ≧ 40%). Example 4 (base B1, condensation reaction) . Into a similar glass reactor as used for the preparation of base A3, 350 g tall oil fatty acids and 150 g PRIPOL 1022 are added. The mixture is homogenized at a temperature of 60 ÷ 70°C, with 300 g xylene added thereto. The reflux condenser with water trap is connected and vertex thermometer is adjusted at 160 ±5°C the magnetic stirrer, is introduced. Through the neck for the reflux condenser, 224 g diethanolamine and 112 g diisopropanolamine are introduced. The reflux condenser is inserted, followed by heating for 12 hours at 160 ± 5°C. When 52 ml reaction water has been collected in the trap, base B1 can be considered to have achieved the desired composition. The reflux condenser is removed and vacuum is connected then cooling to 120°C, or the reaction mixture is poured into a rotary evaporator connected to the vacuum pump for removing the azeotrope. The mixture is allowed to cool to 60 ÷ 50°C. A sample is then taken for the determination of the acid number, that must be ≦ 2 mg KOH/g. The viscous compound thus obtained is poured off at room temperature. The weight of the compound that is poured off is 780 g. The original composition for base B1 is: Ba: 41.86 g (tall oil fatty acids with a low content of rosin acids), Bb: 17.9 g (dimer and trimer fatty acids: "PRIPOL 1022"), Bc: 40 g (diethanolamine/diisopropanolamine, ratio 2:1; molar ratio: Bc:(Ba+Bb) = 1.4:1. The colour of base B1 is amber; base B1 can be dispersed into hard water (50 HF) yielding a dispersion having a pH = 9.2 A 10% dispersion in distilled water provides the following results: maximum Falex load passed: 2950 pound; Draves test, average value (1% average solution): 28 seconds. protective power: 14 cycles in the climatic chamber. Example 5 (base B2; condensation) Into a similar reactor as that used in example 4, and following the same procedure, the following reagents are charged: 350 g PRIPOL 1022, 150 g tall-oil fatty acids, 292.5 g diethanolamine, 146.5 g diisopropanolamine. The condensation is continued at 160 ± 5°C until 68 ml of reaction water is collected. The very viscous liquid thus obtained is poured off at 60°C. The weight of poured off product is 868 g. The product does not flow at room temperature because it sets to a non-clear, slightly thixotropic mass. To ease the cold-water dispersibility, a little amount of PRIPOL 1022 is to be added. The product is much more readily dispersed in hot water, indipendently of whether it is soft or hard water. The pH of the dispersion is about 9. A 10 % dispersion in distilled water at 60°C has provided the following results: maximum Falex load passed: 3350 pounds; protective power: 22 cycles in the climatic chamber. Draves Test (1% dispersion in distilled water): non determinable. The starting percent composition of base B2 is the following : Bb: 15.95 (dimer and trimer fatty acids: "PRIPOL 1022"), Ba: 37.23 (tall oil fatty acids with 2% content of rosin acids), Bc: 46.80 (diethanolamine/diisopropanolamine, ratio 2:1; molar ratio: Bc:(Ba+Bb) = 1.4:1. Example 6 (base B3; condensation reaction) As for the preceeding example following the same procedure, the following reagents are charged into the reactor: 250 g PRIPOL 1022, 250 g talloil fatty acids, 253.3 g diethanolamine, 126.7 g diisopropanolamine. The condensation is continued at 160 ± 5°C until 60 ml of reaction water is collected. A viscous product is obtained, said product being flowable at room temperature and having an acid number of ≦ 1 mg KOH/g. The weight of the obtained product is 877 g. Base B3 is not readily dispersible into a water room temperature, irrespective of its hardness. A 10% water dispersion of base B3 in distilled water at 60°C has provided the following results: maximum Falex load passed: 3050 pounds; protective power: 22 cycles in the climatic chamber. The Draves test on a 1% dispersion in distilled water is not evaluable. The original percent composition for base B3 is as follows: Bb: 28.42 (PRIPOL 1022) Ba: 28.42 (tall oil fatty acids) Bc: 43.15 (diethanolamine/diisopropanolamine). For good quality water-dispersible compositions according to the present invention to be obtained, it is necessary that base B exhibits, to a proper degree, the following characteristics (listed in decreasing order of importance: Bf) film-forming and protective power Bp) polarity Bs) degreasing power. In table II the evaluation of each of the above characteristics relative to the bases B prepared in the examples are reported. Base Bf Bp Bs Average evaluation B1 B S I I B2 O O N.V. O B3 O B N.V. O legend: I = insufficient S = sufficient B = good O = very good N.V. = non evaluable. As already stated in the introductory clauses, the water-dispersible compositions of the present invention consist of four components, that are: base A, base B, dispersant and co-solvent. For the formulation of said water-dispersible composition, the man skilled in the art must above all keep in mind which among the various characteristics, should be enhanced in view of the specific end-use of the composition. Therefore, the various components will be chosen as needs be, keeping well in mind the particular intended use. The evaluations that have been reported in table I for bases A and in table II for bases B, only have a relative, non absolute value, that means that also a base such as, for example, base A1, the total (average) evaluation of which has been considered as insufficient, can nevertheless be usefully employed where it is important to impart the water-dispersible composition especially good lubricating properties. For example, if base A1 is mixed with base B2 a water dispersible composition will be obtained that, besides having good lubricating properties, will also exhibit film-forming and polar properties. Not only but, as stated above, the water-dispersible compositions of the present invention can be employed both in a diluted state (conc. 3-5%) and in a concentrated state (conc. ≧ 40%). In the first case (conc. 3-5%) the composition will predominantly exhibit degreasing and detergent properties. The water-dispersible composition should however show sufficient film-forming properties too, because a protection, even though for a short time, of the steel sheet is necessary (in this case a continuous film of monomolecular thickness will suffice). In the second case (conc. ≧ 40%) the water-dispersible composition will predominantly exhibit protective properties (that is, in this case it is preferable that the composition be able to form a continuous film having a multimolecular thickness). In some cases, it is necessary that the protective film be able to last many months (at least 4-5 months). This double function requires a compromise solution since a high detergent power is not compatible with a high film-forming power. There are also, further, less important factors that must sometimes be taken into account. As a guideline we will show hereinbelow some of the most common cases and suggest the corresponding formulations for water-dispersible compositions. 1) The treatment of steel sheet with a very soiled surface is required, for which a short time protection is necessary , or 2) A steel sheet having not a very soiled surface is to be treated, for which a long-lasting protection is necessary, or 3) a steel sheet, the surface of which has not been temper milled for which a long-lasting protection is required, or, finally, 4) a steel sheet with a very soiled surface for which a good detergent power, and a temporary protection (diluted composition) and subsequently a durable protection (concentrated composition) are required; this is the most frequent situation. Having in mind the characteristics shown in tables I and II above, the following conclusions can be drawn: for the first case a composition of formula A at a concentration of 3-5% is suited; for the second case the suitable composition will be formula B at a concentration of 40-50%; for the third case on the other hand a composition of formula C at a concentration higher then 60% is more appropriate; Finally, for the fourth case it will be useful to employ a composition of formula D, first at a concentration of 3-5% and, then, the same composition at a concentration higher then 40%; as far as the formulation those four compositions is concerned, Table III can be referred to. FORM. A % FORM. B % FORM.C % FORM. D % Base A2 50 28 7 38 Base B2 8 30 38 25 Base B3 - 5 18 18 Ethyleneglycol 7 - 10 - Glycol ether 21 10 - 5 Water 14 27 27 14 It is to be recalled that no difficulty is involved in the preparation of the various water-dispersible compositions of the present invention, in that the various above-mentioned components simply have to be mixed, preferably, but not necessarily, in the given order (viz. base A, base B, dispersant, co-solvent), at a temperature of 40-50°C under stirring until the mixture is completely homogeneous or clear. As already stated above, if it is not possible to obtain a clear dispersion by simply mixing the components, it will suffice to yet add a small quantity (0.5-1%) of co-solvent.

Claims: A water-dispersible composition, characterized in that it consists of the following four components: i) a base A, said base being obtained by the reaction, at a temperature of from 20°C to 160°C, of an acid, organic, water-dispersible reagent Aa, selected from a water-soluble polycarboxylic acid or a phosphoric ester obtained by reacting phosphoric anhydride with a fatty alcohol having at least 8 carbon atoms in the molecule, or with a monosubstituted and /or disubstituted phenol compound, oxo-alcohol compound, said compounds being condensed or non-condensed with ethylene oxide and/or ethylene oxide/polypropylene oxide mixtures, and a basic, organic reagent Ab, consisting of an organic basic compound, selected from an amine, a diamine and/or a polyamine, having 1 to 24 carbon atoms in their molecule and corresponding to the following formula: H₂N-(RNH) n -H (II) wherein R stands for an alkylene group having 1 to 4 carbon atoms and n is an integer of ≦ 6, preferably of a propylene diamine having a primary amine group and a secondary amine group, and corresponding to formula II, with or without oxyethylene groups, or a compound of the formula wherein R stands for the residues of the tallow fatty acids, in a molar ratio of Aa : Ab = 1: 2, said reaction being carried out until about 0.65 - 1.95 moles of water has been collected, or up to complete water-solubility of the product of the salification reaction; ii) a base B, said base being mainly a product or a mixture of products of condensation or salification possibly containing free components resulting from the reaction at a temperature of from 150°C to 190°C of a monocarboxylic acid with 8 - 18 carbon atoms (reagent Ba),in admixture with a dicarboxylic acid having a maximum of 36 carbon atoms (reagent Bb), with an alkanolamine, preferably a dialkanolamine (reagent Bc) in a molar ratio of Bc : (Ba+Bb) ≦1.5:1. iii) water (dispersant) and iv) a co-solvent, said water-dispersible composition having the following percent make-up: i) base A : 7 - 50% ii) base B : 8 - 56% iii) co-solvent : 5 - 28% iv) water : 14 - 27%. A water-dispersible composition according to claim 1, characterized in that base A is obtained by the reaction of an organic water-dispersible acid reagent Aa that consists of a phosphoric acid ester, said phosphoric acid ester resulting from the reaction of 1 mole of P₂O₅ with 2 to 4.5 moles of alcohol R₁-(OCH₂CHR₂)-OH (I) wherein R1 is a (C₁-C₂₄) alkyl or aralkyl, R₂ is H or -CH₃ and x is an integer of from 0 to 20, and the basic reagent Ab is a mixture of a diamine of formula H₂N-(RNH) n -H (II) wherein R is a (C₁-C₄) alkylene group and n is an integer of from 1 to 6, with a compound of the formula wherein R is an alkyl residue of the tallow fatty acids. A water-dispersible composition according to claim 1, characterized in that base B is obtained from an organic carboxylic acid Ba that consists of the tall oil fatty acids, an organic carboxylic acid Bb that consists of a dimer acid, said dimer acid being obtained by polymerizing an unsaturated fatty acid having 18 carbon atoms containing 80-97% of dimer acid, about 20-3% of trimer acid and not more than about 1% of monomer acid, with an alkanolamine Bc, consisting of a dialkanolamine made of a 2:1 diethanolamine/diisopropylamine mixture, in the molar ratio of Bc :(Ba + Bb) less than or equal to 1.5: 1. A water-dispersible composition according to claim 3, characterized in that base B is obtained from a carboxylic organic acid Bb consisting of a dimer acid containing about 95% of dioleic acid, about 4% of trimer acid and about 1% of monomer acid, and having an acid number of from 185 to 195, an equivalent weight of 290-295 and a molecular weight of 360-370. A water-dispersible composition according to any of claims 1 to 4, characterized in that the cosolvent consists of one or more glycols. A water-dispersible composition having a detergent action, characterized in that it consists of 3-5% water dispersion of a water-dispersible composition according to anyone of claims 1 to 5. A water-dispersible composition having a protective action, characterized in that it consists of a dispersion of a water-dispersible composition according to anyone of claims 1 to 5, at a concentration of at least 40%. A process for preparing a water-dispersible composition according to claim 1, characterized in that the four components are mixed at a temperature of 40°C - 50°C, under stirring, until the mixture is completely homogenized or clear, possibly adding a small (0.5-1%) amount of co-solvent.

Inventors: BRUNI, ANTONIO, GIOVANE, GIUSEPPE, GRANATA, FRANCESCO, LATORRATA, ROCCO LUIGI
Applicants: LUBRITALIA S.P.A.
Application year: 1989
Main classification: C23F11
IPC codes: C23G5, C10M173, C23F11