Compositions containing anionic phosphoric ester and alkoxylated alcohol and uses thereof

Abstract

The invention relates to compositions containing an anionic phosphoric ester, a non-ionic surfactant and additives, intended for applications requiring good wetting, low-foaming, anti-seize, anti-corrosion properties, among others in cleaning agents, rinse-aid agents, metalworking fluids, lubricants, anti-seize and flame-retardant HFC hydraulic fluids.

Description

[0001] Compositions containing anionic phosphoric ester and alkoxylated alcohol and uses thereof

[0002] The invention relates to the use of compositions containing an anionic phosphoric ester, a nonionic surfactant and additives. This composition has good wetting properties and reduced foaming, after neutralization also anti-corrosive, is dedicated for use in cleaning, shine-enhancing, lubricating, anti-seize and / or anti-corrosion compositions and for metal treatment.

[0003] Anionic phosphate esters contain a phosphorus atom in the molecule. Due to its presence in the molecule, these compounds exhibit lubricating properties and are effective AW / EP (antiwear / extreme pressure) additives, providing surface protection under extreme friction. This property is of particular importance in applications where high loads occur. An additional advantage of anionic phosphate esters and an advantage over many other surface-active compounds is their outstanding resistance to alkaline compounds. This product also improves wetting and cleaning properties in applications related to metal cleaning. Phosphoric esters, after neutralization with amines, additionally gain anti-corrosion properties, primarily with respect to: steel, copper and aluminum. The above-mentioned advantages enable the effective use of anionic phosphate esters as an additive in the production of lubricants, metalworking fluids, semi-synthetic and synthetic fluids and hard surface cleaners. Products with low foaming properties can be successfully used as an auxiliary agent for textile processing, cleaning in closed systems and in many other applications.

[0004] Phosphoric esters have a wide range of applications: as emulsifiers, corrosion inhibitors and anti-wear additives in metalworking fluids, wetting agents, antistatics and hydrotropes.

[0005] Patent US8728990B2 relates to a fracturing fluid composition comprising about 0.25% to about 3.0% by weight, based on the weight of the hydrocarbon fluid, of a mixture of phosphoric esters selected from the group comprising: a monoester PO(OR1 )(OH)2, PO(OR2)(OH)2; a diester PO(OH)(OR1 )m(OR2)2-m, where m =0, 1 , or 2; a triester PO(OR1 )n(OR2)3-n, where n =0, 1 , 2, or 3; and a phosphoric acid H3PO4, where R1 and R2 each have 2 to 18 carbon atoms; and about 0.2% by weight of a phosphoric acid, H3PO4, where R1 and R2 each have 2 to 18 carbon atoms; up to about 1.0 wt.%, based on the weight of the hydrocarbon fluid, of an acidic polynuclear aluminum compound having an AI:CI molar ratio of from about 1.40:1 to about 2.2:1 , wherein the fracturing fluid composition is characterized by a substantially constant viscosity value, and fracturing the subterranean formation with the hydrocarbon fluid.

[0006] US7241724B2 claims a personal care product composition which comprises 5 to 85 wt.% of a surfactant system comprising an alkyl phosphate surfactant or a mixture of alkyl phosphate surfactants and a secondary surfactant selected from the group comprising alkyl carboxylates, alkyl polyether carboxylates, alkyl amino carboxylates, polyhydroxy surfactants, alkyl phenyl alkoxylates and mixtures thereof; wherein the secondary surfactant has a pKathat is higher (weaker acid) than the average pK a of the first H+ionization in said phosphorus surfactant or mixture thereof, the pH of the composition being about 4.5 to 6.5. The phosphorus surfactant and / or mixture and the auxiliary surfactant together constitute 40% or more of the surfactant system, and the molar ratio of alkyl phosphonic ester to auxiliary surfactant is about 55:45 to 65:35, and the composition also includes an amino acid counterion.

[0007] Also claimed is a composition wherein the phosphate surfactant and / or mixture and the secondary surfactant comprise 50% or more of a surfactant system, the chain length of the secondary surfactant is within ±4 carbons of the alkyl phosphate chain length, the molar ratio of alkyl phosphate ester to secondary surfactant is less than 90: 10 and the molar ratio is less than 80:20, the pH is from 4.5 to 6.

[0008] Patent EP1765968B1 relates to the use of phosphated 2-propylheptanol or phosphated 2-propylheptanol alkoxylate as a hydrotrope in aqueous alkaline solutions for a C8-C18 alcohol alkoxylate containing 1 -20 ethylene oxide units. It also relates to a phosphated 2-propylheptanol alkoxylate ester and an alkaline cleaning composition comprising a C8-C18 alcohol alkoxylate containing 1 -20 EO (ethylene oxide) units and a phosphate 2-propylheptanol ester and / or phosphated 2-propylheptanol alkoxylate containing 0-3 PO (propylene oxide) units as a hydrotrope. The cleaning compositions can be used for industrial cleaning of hard surfaces, for example for vehicle washing or machine dishwashing. The use of the compositions is limited to alkaline environments. Patent US1 1274261 B2 describes a method for improving lubricating properties in metalworking processes by using propoxylated and ethoxylated alcohol phosphate esters of the formula: wherein R is the residue of one or more C12-C18 linear or branched aliphatic alcohols and at least 70% by weight of said aliphatic alcohols consists of one or more C14-C16 linear or branched aliphatic alcohols; x is the average number of propoxyl groups and is from 3 to 6.5; y is the average number of ethoxyl groups and is from 3 to 8; R1 is hydrogen, an ammonium ion, a protonated amine, a quaternary organic ammonium or an alkaline earth metal. R2 is the same as R1 or

[0009] CHj

[0010] R (OCHCI-R)v— (OCHCH2)r

[0011] R, x, and y have the same meanings as given above, with the proviso that R1 and R2 are not hydrogen. The composition is used for a metal working fluid in a process selected from: cutting, drilling, grinding, turning, milling, tapping, and broaching or metal forming processes.

[0012] Patent EP2020214198 relates to a lubricant composition comprising: from 70 to 99.99% of at least one base oil; from 0.01 to 30% of at least one ethoxylated phosphate ester alcohol of the formula: wherein: R is a linear or branched alkyl group having from 10 to 14 carbon atoms; m is an integer from 1 to 3, preferably from 1 to 2; n is an integer greater than or equal to 6. The invention also relates to the use of this compound for preventing and / or reducing and / or limiting and / or delaying corrosion and / or tribocorrosion of metal parts of an internal combustion engine.

[0013] Currently, solutions in the form of single phosphoric esters (chemically modified) are offered on the market, the disadvantage of which is the lack of universality. A given ester shows specific utility properties, i.e. it shows excellent EP properties, but it can foam a lot, which disqualifies it in some applications where high foam is undesirable. The proposed solution allows for increasing the universality of use of such compositions.

[0014] In a first aspect, the invention relates to a low-foaming composition characterized in that it comprises: a) at least one anionic phosphoric ester, wherein said anionic phosphoric ester is a phosphate ester of an ethoxylated alcohol or a non-ethoxylated fatty alcohol, wherein the ethoxylated alcohol is selected from the group comprising alcohols having a chain length of C4-C18 and 0-8 ethylene oxide units and the nonethoxylated fatty alcohol is selected from the group comprising isotridecyl alcohol and / or 2-ethylhexyl alcohol; b) at least one non-ionic surfactant being an alkoxylated fatty alcohol and / or a mixture thereof; c) at least one glycol; d) water; wherein

[0015] - the weight ratio of phosphoric ester to non-ionic surfactant is from 7:1 to 9:1 and

[0016] - the weight ratio of water to glycol is 1 :1 and

[0017] - the weight ratio of phosphoric ester to water or glycol is from 40:1 to 45:1 . Preferably in the composition the ethoxylated alcohol a) is selected from the group comprising alcohols having a chain length of C8-C14 and 3-6 ethylene oxide units. Preferably in the composition the alkoxylated fatty alcohol from b) is selected from the group comprising alcohols having a chain length of C9-C18 and containing 2-20 ethylene oxide units and / or 4-25 propylene oxide units.

[0018] Preferably, in the composition the glycol is selected from the group comprising alkylene glycols, alkylene glycol ethers and polyalkylene glycol ethers, derivatives of these compounds and / or mixtures thereof.

[0019] Preferably in the composition the glycol is selected from the group comprising propylene glycol, butyl glycol, glycerine and / or mixtures thereof.

[0020] Preferably, the anionic phosphoric ester a) is present in the composition in an amount of 80-90% by weight relative to the total weight of the low-foaming composition. In a further aspect, the invention relates to a method for producing a low-foaming composition as defined above, characterized in that the components of the composition are mixed together at a temperature not exceeding 50°C until a homogeneous composition is obtained.

[0021] In a further aspect, the invention relates to a use of the low-foaming composition as defined above as a component of cleaning, lubricating, anti-corrosion and / or metal treatment compositions.

[0022] Preferably, the use of a composition as defined above is characterized in that the addition of a low-foaming composition as defined above in an amount of 1 -5% by weight to the rapeseed oil increases the highest extreme pressure (EP) non-seizing load determined in accordance with the ASTM D2783 standard by at least 40% relative to pure rapeseed oil.

[0023] In a further aspect, the invention relates to an anti-corrosion composition characterized in that it comprises:

[0024] - a low-foaming composition as defined above, in an amount of 40-60% by weight relative to the total weight of the anti-corrosion composition, and f) water in the range of 15-25% by weight relative to the total weight of the anticorrosion composition; g) a base in an amount of 20-30% by weight based on the total weight of the anti-corrosion composition, preferably triethanolamine (TEA), monoethanolamine (MEA), triisopropanolamine (TIPA), NaOH or KOH.

[0025] Preferably, the anti-corrosion composition as defined above is a corrosion inhibitor of metal and / or metal alloys in aqueous solutions at a concentration of 1 -10% by weight relative to the total weight of the solution, preferably relative to steel, copper and aluminium.

[0026] In a further aspect, the subject of the invention is a composition of a flame-retardant HFC hydraulic fluid characterized in that it comprises

[0027] - an anti-corrosion composition as defined above in an amount of 1 -5% by weight based on the total weight of the flame retardant composition, whereby according to the ISO 6743-4 classification: HFC is a polymer solution in water containing more than 35% w / w of water, and also includes: c) glycol in an amount of 30-40% by weight based on the total weight of the flame-retardant composition, selected from the group comprising alkylene glycols, alkylene glycol and polyalkylene glycol ethers, derivatives of these compounds and / or mixtures thereof; d) water in the range of 35-50% by weight relative to the total weight of the flame retardant composition; e) glycerine in an amount of 5-15% by weight based on the total weight of the flame retardant composition; f) polyacrylamide with a molecular weight of 2 to 4 million in an amount of 5- 15% by weight relative to the total weight of the composition; g) a neutralizing agent in an amount of 1 -3% by weight based on the total weight of the composition, preferably triethanolamine.

[0028] In a further aspect, the invention relates to a cleaning composition characterized by the fact that it contains

[0029] - a low-foaming composition as defined above in an amount of 5-20% by weight of the cleaning composition, and h) a glycol in an amount of 1 -10% by weight based on the total weight of the cleaning composition, selected from the group comprising alkylene glycols, alkylene glycol and polyalkylene glycol ethers, derivatives of these compounds and / or mixtures thereof; i) cocam idopropyl betaine in the range of 1 -10% by weight based on the total weight of the cleaning composition; and optionally j) an alcohol in the range of 0-5% by weight based on the total weight of the cleaning composition selected from the group comprising C10-C18 alcohols having 1 -10 ethylene oxide units, preferably C12-C15 alcohols and 6-9 ethylene oxide units or mixtures thereof.

[0030] In a further aspect, the invention relates to the use of a cleaning composition as defined above for the treatment of metals and / or for industrial cleaning, preferably of hard surfaces, preferably made of metal, even more preferably made of aluminium and stainless steel.

[0031] In a further aspect, the subject of the invention is a rinse-aid composition characterized in that it comprises:

[0032] - a low-foaming composition as defined above in an amount of 1 -10% by weight relative to the total weight of the rinse-aid composition, and k) water in the range of 80-85% by weight relative to the total weight of the composition; l) an alcohol in the range of 5-15% by weight based on the total weight of the composition selected from the group comprising C12-C14 alcohols and having 3-10 ethylene oxide units and / or 3-10 propylene oxide units or mixtures thereof; m) carboxylic acid in the range of 1 -5% by weight based on the total weight of the composition, preferably citric acid.

[0033] Due to their properties, the compositions according to the invention are a particularly useful alternative to single anionic phosphoric esters available on the market due to the synergy effect that is obtained by preparing a mixture of anionic phosphoric ester and nonionic surfactant. These compositions are used in cleaning formulas, metalworking fluids, wetting, anticorrosive (after neutralization) among others in cleaning agents, lubricants, anti-seize and flame retardant hydraulic fluids, for single anionic phosphoric esters available on the market due to the synergy effect that is obtained by preparing a mixture of anionic phosphoric ester and nonionic surfactant and additional substances.

[0034] Phosphoric esters are available on the market, which are a mixture of monoester, diester, free phosphoric acid and free alcohol or its ethoxylate. Depending on the choice of phosphating agent, different contents and ratios of individual components are obtained, and therefore different properties of the finished product.

[0035] The solution according to the invention is based on the modification of the properties of the phosphoric ester by creating a physical mixture of the phosphoric ester and alkoxylated alcohol and additives. The composition shows high resistance to alkaline compounds, after neutralization it is completely soluble in water, it shows a freezing point below -30°C. The phosphorus atom in the phosphoric ester molecule gives lubricating and anti-seize (EP) properties to this composition. In addition, the advantages of using a composition based on the phosphoric ester on the ethoxylated alcohol and alkoxylated alcohol in a system with additives in relation to the use of a single phosphoric ester are: increased stability, improved wetting properties, reduced foaming and increased solubility.

[0036] The advantages of the composition according to the invention are shown in the drawing, in which Fig. 1 shows a graph of the dependence of foam height as a function of time for two solutions: 1 ) a composition as in Table 14 (square) and 2) pure phosphoric ester of alcohol C10, 3 EO (rhombus).

[0037] - Fig. 2 shows the test results of the anti-corrosion properties of the inhibitor solution with the composition as in Table 20;

[0038] - Fig. 3 shows the cleaning effectiveness of the composition for cleaning aluminum and steel according to the invention from Table 28 on the surface of a dirty plate in relation to a plate cleaned with water only;

[0039] - Fig. 4 shows the effectiveness of shine-enhancing with a rinse-aid composition by comparing the appearance of glasses after 6 washing cycles in an automatic dishwasher (washing program: pre-wash, washing at 50°C, intermediate rinse, rinse at 65°C, shine-enhancing, drying) using the rinse-aid composition according to the invention from Table 29 in relation to dishes rinsed only with water.

[0040] Examples - preparation of a composition

[0041] Example 1

[0042] Phosphoric ester of alcohol C10, 3 EO + ethoxylated fatty alcohols a) A clear phosphoric ester of alcohol C10, 3 EO (if it is not clear, it must be heated to 40°C and stirred to homogenize) was weighed into a 1 I beaker in a given amount (Table 1 ) relative to the total weight of the composition, b) an ethoxylated fatty alcohol (non-ionic surfactant) with the composition given in point 2 was added (if it is not clear, it should be heated to 40 °C and mixed to homogenize) in a given amount relative to the total weight of the composition, c) all ingredients were mixed for 30 minutes at a temperature of 20 ± 2°C using a mechanical stirrer with a propeller tip, d) If the composition is not clear, it should be heated to a temperature not exceeding 50°C and mixed again using a mechanical mixer with a propeller tip for about 30 minutes to obtain a homogeneous composition. Table 1. Composition in % by weight.

[0043] Results

[0044] Assessment of appearance

[0045] The samples were subjected to stability tests consisting in testing temperature resistance. The sample was stored in the temperature range from 20 to 25°C and at 6 °C, in both cases for 24 hours, and after that time the external appearance of the sample was visually assessed. The results of the observations are described in Table 2.

[0046] Table 2. Assessment of appearance

[0047] Legend

[0048] K-clear

[0049] 0- opalescent

[0050] M- cloudy

[0051] R- stratified

[0052] Z- solidified

[0053] ML - Milky

[0054] Conclusions: After preparation of the E1 -E9 composition and visual evaluation of the external appearance of the samples stored at 20 to 25°C and at 6°C None of the samples were found to be stable when stored under the given conditions.

[0055] The addition of ethoxylated alcohol does not improve the appearance or stability of Phosphoric ester of alcohol C10, 3 EO when stored at reduced temperature.

[0056] Example 2

[0057] Phosphoric ester of alcohol CIO, 3 EO + block copolymers a) A clear phosphoric ester with the composition given in point 1 of Table 3 (if it is not clear, it must be heated to 40°C and stirred to homogenize) was weighed into a 1 I beaker in a given amount (Table 3) relative to the total weight of the composition, b) a block copolymer (non-ionic surfactant) with the composition given in point 2 (if it is not clear, it must be heated to 40 °C and stirred to homogenize) was added in a given amount (Table 3) relative to the total weight of the composition, c) All ingredients were mixed for 30 minutes at 20±2°C using a mechanical stirrer with a propeller tip. d) If the composition is not clear, it should be heated to a temperature not exceeding 50°C and mixed again using a mechanical mixer with a propeller tip for 30 minutes to obtain a homogeneous composition.

[0058] Table 3. Composition in % by weight:

[0059] Results

[0060] Assessment of appearance The samples were subjected to stability tests consisting in testing temperature resistance. The sample was stored in the temperature range from 20 to 25 °C and at 6 °C, in both cases for 24 hours, and after that time the external appearance of the sample was visually assessed. Table 4 describes the results of the observations.

[0061] Table 4. Appearance assessment

[0062] Conclusions:

[0063] After preparing the E10-E15 composition and visually assessing the external appearance of the samples stored at 20-25°C and at 6°C It was found that none of the samples passed the stability tests at temperatures reduced to 6°C.

[0064] The addition of block copolymers does not improve the external appearance of the phosphoric ester of alcohol C10, 3 EO stored at reduced temperature.

[0065] Example 3

[0066] Phosphoric ester of alcohol C10s3 EO + ethoxylated and propoxylated fatty alcohols a) A clear phosphoric ester with the composition given in point 1 of Table 5 (if it is not clear, it must be heated to 40°C and stirred to homogenize) was weighed into a 1 I beaker in the specified quantity (Table 5) relative to the total weight of the composition, b) ethoxylated and propoxylated fatty alcohol (non-ionic surfactant) with the composition given in point 2 was added (if it is not clear, it must be heated to 40 °C and mixed to homogenize) in the given amount (Table 5) relative to the total weight of the composition, c) All ingredients were mixed for 30 minutes at 20±2°C using a mechanical stirrer with a propeller tip. d) If the composition is not clear, it should be heated to a temperature not exceeding 50°C and mixed again using a mechanical mixer with a propeller tip for 30 minutes to obtain a homogeneous composition. Table 5. Composition in % by weight:

[0067] Results

[0068] Assessment of appearance

[0069] The samples were subjected to stability tests consisting in testing temperature resistance. The sample was stored in the temperature range from 20 to 25°C and at 6 °C, in both cases for 24 hours, and after that time the external appearance of the sample was visually assessed. The results of the observations are described in Table 6. Table 6. Appearance assessment Conclusions:

[0070] After preparing the composition and visually assessing the external appearance of the samples stored at 20-25°C and at 6°C Only sample E22 was found to be clear during storage, both at 20-25°C and at 6°C for 24 hours. This sample was selected for further stability tests.

[0071] Further testing of sample E22 at low temperatures:

[0072] Further stability tests were performed on the selected sample. The sample was stored at 6°C for 7 days, during which time its appearance was assessed visually. Table 7 describes the results of the observations.

[0073] Table 7. Appearance assessment

[0074] Results:

[0075] After storage at 6°C the sample is homogeneous and clear for 3 days.

[0076] Example 5

[0077] Phosphoric ester of alcohol C10, 3 EO + C12-14 alcohols, 4-8 EO, 4-8 PO + additives a) a clear phosphoric ester with the composition given in point 1 (Table 8) was weighed into a 1 L beaker (if necessary, heat to 40 °C and mix to homogenize) in an amount of 86.4% to the total weight of the composition, b) a non-ionic surfactant was added with the composition given in point 2 (Table 8) in the given amount of 9.6% in relation to the total weight of the composition, c) a solvent with the composition given in point 3 (Table 8) was added in a given amount relative to the total weight of the composition, d) All ingredients were mixed for 30 minutes at 20±2°C using a mechanical stirrer with a propeller tip. e) If the composition is not clear, it should be heated to a temperature not exceeding 50°C and mixed again using a mechanical mixer with a propeller tip for 30 minutes to obtain a homogeneous composition.

[0078] Table 8. Composition, % by weight:

[0079] Results

[0080] Assessment of appearance

[0081] The samples were subjected to stability tests consisting in examining temperature resistance. The sample was stored in the temperature range of 20 to 25°C and at 6 °C for 30 days, during which time the external appearance of the sample was visually assessed several times. Table 9 describes the results of the observations.

[0082] Table 9. Appearance assessment

[0083] Conclusions :

[0084] After preparation of the composition and visual evaluation of the external appearance of the samples stored at 6°C Sample D1, D4 and D5 are found to be clear when stored under the given conditions. Surprisingly, the compositions of the invention have been found to be exceptionally stable at specific waterglycol and phosphate:alcohol:water ratios.

[0085] To improve the appearance at low temperatures of compositions with the following compositions: phosphoric ester of alcohol C10, 3 EO and alcohols, C12-14, 4-8 EO, 4-8 PO, water and / or glycerine and / or glycerine and / or butyl glycol and / or glycerine and / or propylene glycol should be used.

[0086] Example 6

[0087] Phosphoric ester of alcohol C10, 3 EO + ethoxylated alcohol, propox hted + additives a) a clear phosphoric ester of composition D1 (Table 10), which is identical to D1 from Table 8 and hereinafter referred to as D1 , was weighed into a 1 L beaker (if necessary, it should be heated to 40 °C and mixed to homogenize) in an amount in the ratio of 86.4% to the total weight of the composition, b) a non-ionic surfactant was added with the composition given in point 2 (Table 10) in the given amount of 9.6% in relation to the total weight of the composition, c) a solvent with the composition given in points 3 and 4 (Table 10) was added in an amount of 2% of the total composition weight, d) all ingredients were mixed for 30 minutes at 20±2°C using a mechanical stirrer with a propeller tip. e) If the composition is not clear, it should be heated to a temperature not exceeding 50°C and mixed again using a mechanical mixer with a propeller tip for 30 minutes to obtain a homogeneous composition.

[0088] Table 10. Composition, % by weight: Results

[0089] Assessment of appearance

[0090] The samples were subjected to stability tests consisting in examining the temperature resistance. The sample was stored at a temperature ranging from 20 to 25 °C and 6 °C for 24, 72 hours and 7 and 30 days, respectively, and after a specified time the visual appearance of the sample was assessed. Table 11 describes the results of the observations.

[0091] Table 11 . Appearance assessment

[0092] Conclusions :

[0093] After preparing the composition and visually assessing the external appearance of the samples stored at 6°C for 30 days, it has been found that samples D1, A2, A3 and A4 are clear when stored under the given conditions. It was therefore unexpected that the specified proportions of anionic phosphoric ester: alcohol: water: glycol allow obtaining stable compositions for various alcohols.

[0094] Example 7 a) a clear phosphoric ester with the composition given in point 1 (Table 12) was weighed into a 1 L beaker (if necessary, heat to 40 °C and mix to homogenize) in an amount of 86.4% to the total weight of the composition, b) a non-ionic surfactant was added with the composition given in point 2 (Table 12) in the given amount of 9.6% in relation to the total weight of the composition, c) a solvent with the composition given in point 3 (Table 12) was added in a given amount relative to the total weight of the composition, d) all ingredients were mixed for 30 minutes at 20±2°C using a mechanical stirrer with a propeller tip. e) If the composition is not clear, it should be heated to a temperature not exceeding 50°C and mixed again using a mechanical mixer with a propeller tip for 30 minutes to obtain a homogeneous composition. Products from the series anionic phosphoric esters + C12-14 alcohol ethoxylate, propoxylate and solvents.

[0095] Table 12. Composition, % by weight.

[0096] Results

[0097] Assessment of appearance

[0098] The samples were subjected to stability tests consisting in examining the temperature resistance. The sample was stored at 6 °C for 24, 72 hours and 7 and 30 days, respectively, and after that time the external appearance of the sample was visually assessed. The results of the observations are described in Table 13.

[0099] Table 13. Appearance assessment after heating

[0100] Conclusions :

[0101] After preparing the composition and visually assessing the external appearance of the samples stored at 20-25°C and at 6°C Samples D1, A5, A8, A9, A13 and A14 are found to be clear when stored under the given conditions for 30 days. It was therefore unexpected that the specific proportions of the components: anionic phosphoric ester: alcohol: water: glycol allowed obtaining stable compositions for various phosphates.

[0102] The use of appropriate amounts of water and glycerine improves the appearance of compositions containing 4-8 EO, 4-8 PO and one of the phosphoric esters : phosphoric ester of alcohol C8-C10, 3-6 EO, phosphoric ester of alcohol C6-C10, 4-8 EO, phosphoric ester of alcohol C4, 3-6 EO, phosphoric ester of alcohol C8 , 3- 6 EO, phosphoric ester of isotridecyl alcohol, phosphoric ester of 2-ethylhexyl alcohol.

[0103] It is clear from Tables 8 and 9 that only with fixed proportions of water and glycol relative to phosphoric ester and alkoxylated alcohol as non-ionic surfactant are the compositions stable and at the same time have other advantageous properties, this stability being demonstrated for different alcohols (Table 10) and different phosphoric esters (Table 12). A number of compositions with other compositions, e.g. containing more water / glycol relative to ester, do not show such good stability. These proportions were obtained after long and laborious laboratory tests, as is evident from the comparisons in Tables 1 -13, which means that the invention is not obvious in the context of the prior art.

[0104] Examples of properties of the compositions according to the invention

[0105] Properties of composition D1 in the composition of Table 14 containing phosphoric ester of alcohol C10, 3 EO.

[0106] Table 14. Composition of composition D1.

[0107] Foaming properties (DFA-100 foam analyzer)

[0108] Two solutions were prepared: 1 ) a 1 % aqueous solution of the composition D1 as in Table 14 (hereinafter referred to as D1 ), and 2) a 1 % aqueous solution of the phosphoric ester of a alcohol C10, 3 EO by dissolving it in demineralized water. The obtained solutions were foamed by adding 150 ml of air at a rate of 0.5 l / min and tested using a Kruss DFA100 foam analyzer. The measurement was carried out at a temperature of 20±2°C for 10 minutes.

[0109] Table 15. Foaming properties and foam stability results for composition D1 and phosphoric ester of alcohol C10, 3 EO.

[0110] Legend f FLS 75% [s] - 25% drainage time: time in which the FLS decreased to 75% of its initial value, t FLS 50% [s] - 50% drainage time: time in which the FLS decreased to 50% of its initial value, t FLS 25% [s] - 75% drainage time: time at which FLS decreased to 25% of its initial value

[0111] The study of foaming properties showed that upon foaming solutions of composition D1 and phosphoric ester of alcohol C10, 3 EO, the same volume of foam is obtained, but the foam of composition D1 is unstable and condenses quickly compared to the foam of phosphoric ester of alcohol C10, 3 EO.

[0112] Wetting ability

[0113] The wetting capacity of cotton fabric was determined in accordance with the PN-EN 1772:2001 standard. The wetting time was determined, i.e. the time in seconds required to wet the textile material, measured in a solution of composition D1 prepared at a concentration of: 0.5, 1 .0 and 1 .5 g / l in demineralized water at 25°C.

[0114] Table 16. Wetting ability results determined as for composition D1 . Table 17. Explanation of wetting ability

[0115] Composition D1 solutions have good or excellent wetting properties, as confirmed by tests to determine the wetting capacity of cotton fabric performed in accordance with the PN-EN 1772:2001 standard.

[0116] Anti-seize properties (extreme pressure, EP) determined according to ASTM D2783

[0117] Table 18. EP properties

[0118] Extreme Pressure (EP) anti-seize properties according to ASTM D2783: Composition D1 at a concentration of 3% by weight dissolved in rapeseed oil shows EP properties (maximum non-seizing load 126 kg) better than pure rapeseed oil (maximum non-seizing load 80 kg) by approx. 58%.

[0119] Composition D1 has more applications than just the phosphoric ester itself, as illustrated in Table 19. Table 19. Applications of D1 composition and phosphoric ester of alcohol C-10, 3 EO

[0120] The composition according to the invention D1 , in relation to the phosphoric ester of alcohol C-10, 3 EO itself, additionally shows solubility in rapeseed oil methyl esters (EMOR) and also shows cleaning and low-foaming properties.

[0121] Anti-corrosion properties:

[0122] Preparation of corrosion inhibitor solution: Table 20. Composition of corrosion inhibitor - T20:

[0123] The D1 composition and water are placed in the reactor, the batch is heated to about 60°C and triethanolamine is added. The pH should be checked, if it is in the range of 7-8, if it is lower, another portion of TEA should be added and the pH value checked again. After the correct pH value was established, the reactor batch was stirred for 1 hour at a temperature of about 60°C.

[0124] Cast Iron Chip corrosion testing based on DIN 51360-2 The method consists in preparing a sample for testing by diluting it if the initial product is in the form of a concentrate, with particular attention paid to the hardness of the water used for the determination. Then, an appropriate amount of grey cast iron shavings is placed on filter paper. The whole is placed on a Petri dish and soaked with an appropriate amount of the tested sample. The system is left for 2 hours at room temperature. After this time, the degree of coverage of the filter paper with traces of corrosion products is assessed.

[0125] Table 21 . Description of the Cast Iron Chip corrosion test results based on the DIN 51360-2 standard

[0126] Table 22. Results of corrosion activity using the CAST IRON method for demineralized water and corrosion inhibitor solution with the composition as in Table 20.

[0127] Demineralised water causes corrosion of steel chips and a value of 3 was obtained, determined using the CAST IRON method, and the addition of just one 1 % corrosion inhibitor according to the composition in Table 20 (T20) prevents corrosion and allows to obtain a result of 1 based on the DIN 51360-2 standard. Corrosion action on copper based on ASTM D130-18

[0128] The method is designed to assess the interaction of lubricants with copper surfaces. This method involves placing a previously prepared copper plate in the sample being analyzed, then leaving it at a suitable temperature for a specified time. Then, a visual assessment of the changes in the plate's appearance is made according to the standard. Table 23. Description of the results of the corrosion action on copper based on the

[0129] ASTM D130-18 standard Table 24. Copper corrosion results using ASTM D130-18 method determined for 20 dH hard water and T20 corrosion inhibitor solution prepared with 20 dH hard water

[0130] Hard water with a hardness of 20 dH has a strong corrosive effect on the copper plate 3a, while the addition of 3% of the corrosion inhibitor composition according to the composition T20 (from Table 20) to water with the same hardness prevents corrosion of the copper plate and a result of 1 a is obtained.

[0131] Own method on aluminum:

[0132] A PA9 aluminum alloy plate was placed in the composition according to the invention T20, so that part of the plate was immersed in the liquid and the remaining part in the gas phase. The sample with a closed glass vessel was left for 2 weeks at 40°C, after which the appearance of the plate was assessed.

[0133] Table 25. Results of corrosion action on aluminum.

[0134] Based on the test of the corrosive effect on aluminium, it was found that demineralised water causes severe corrosion in both the gas and liquid phases, and the addition of 5% corrosion inhibitor according to the composition in Table 20 significantly prevents corrosion, under the experimental conditions, the effect of gentle corrosion is obtained. The results of anti-corrosion tests are shown in Figure 2. Composition T20 shows corrosion inhibition activity against steel, copper and aluminum.

[0135] The composition, after neutralization with TEA, can be used as a corrosion inhibitor in a flame-retardant hydraulic fluid of the HFC type, i.e. of the water-polymer (ethylene glycol) type.

[0136] Flame retardant HFC hydraulic fluid is used to eliminate fire hazards, especially in the machinery and mining industry and as a lubricant in actuators. It is perfect for: filling power hydraulics devices, testing, transporting and maintaining hydraulic devices. Fluid operating temperature range from - 20 °C to + 60 °C. Table 26. Composition of flame retardant HFC hydraulic fluid (according to ISO 6743-4 classification: HFC - polymer solution in water containing more than 35% w / w water), the control composition does not contain a corrosion inhibitor, while composition T26 contains a corrosion inhibitor of the composition T20, as in Table 20: Table 27. Corrosion test results for the composition of a flame retardant HFC hydraulic fluid containing a corrosion inhibitor - T26 and without a corrosion inhibitor as a control composition : Composition T20 (corrosion inhibitor with the composition as in Table 20), which is a component of the flame-retardant hydraulic fluid with the composition T26 (according to Table 26) shows an anti-corrosion effect on steel (result 0 according to DIN 51360-2) and copper (result 1 a ASTM D130-18). On the other hand, the composition with the control composition, not containing the corrosion inhibitor composition according to the invention, shows a strong corrosive effect on copper (result 2c - ASTM D130-18) and steel (result 4 according to DIN 51360-2).

[0137] Examples of use of the cleaning composition:

[0138] Cleaning compositions - starter recipes

[0139] Table 28. Composition T28 for cleaning aluminum and stainless steel. Surface cleaning efficiency was measured based on the ASTM D3050-07 method. A scrubbability tester was used for this purpose, on which a plate was placed, soiled with standard dirt, and cellulose sponges soaked in 15 g of the test solution were used. The sponge performed 5 cleaning cycles at a speed of 30 strokes / m inute. The cleaning efficiency of the aluminum and steel cleaning fluid on a hard surface is illustrated in Figure 3.

[0140] The inventive composition for cleaning aluminum and stainless steel of composition T28, as in Table 28, exhibits cleaning properties on hard surfaces soiled with standard dirt relative to cleaning the same surface with water, as evidenced by less soiling of the surface.

[0141] Table 29. T29 rinse-aid composition for dishwashers.

[0142] Figure 4 shows the appearance of glasses after 6 washing cycles in an automatic dishwasher (washing program: pre-wash, wash at 50°C, intermediate rinse, rinse at 65°C, shine-enhancing, drying), using the rinse-aid composition according to the invention T29, with the composition as in Table 29, and compared with dishes rinsed only with water.

[0143] During washing, a glass to which the rinse-aid composition according to the invention was not applied shows numerous limescale streaks after washing, resulting from the quality of the tap water, whereas a glass to which the rinse-aid composition according to the invention for dishwashers was applied does not have any streaks. Composition D1 can be used as a component of hard surface cleaning products, particularly strong alkaline cleaning agents and textile treatment aids. It exhibits hydrotropic properties in an alkaline environment. The composition in question, in a form neutralized with triethanolamine, is an additive for the production of: lubricants, metalworking fluids, semisynthetic and synthetic fluids, particularly as a corrosion inhibitor for: steel, copper and aluminum.

Claims

AMENDED CLAIMS received by the International Bureau on 14 August 2025 (14.08.2025)1. A low-foaming composition characterized in that it comprises: a) at least one anionic phosphoric ester, wherein said anionic phosphoric ester is a phosphate ester of an ethoxylated alcohol or a non-ethoxylated fatty alcohol, wherein the ethoxylated alcohol is selected from the group comprising alcohols having a chain length of C4-C18 and 0-8 ethylene oxide units and the non-ethoxylated fatty alcohol is selected from the group comprising isotridecyl alcohol and / or 2-ethylhexyl alcohol; b) at least one non-ionic surfactant being an alkoxylated fatty alcohol and / or a mixture thereof; c) at least one glycol; d) water; wherein- the weight ratio of phosphoric ester to non-ionic surfactant is from 7:1 to 9:1 and- the weight ratio of water to glycol is 1 :1 and- the weight ratio of phosphoric ester to water or glycol is from 40:1 to 45:1 .

2. The composition according to claim 1 , wherein the ethoxylated alcohol a) is selected from the group comprising alcohols having a chain length of C8-C14 and 3-6 ethylene oxide units.

3. The composition according to claim 1 or 2, wherein the alkoxylated fatty alcohol from b) is selected from the group comprising alcohols having a chain length of C9-C18 and containing 2-20 ethylene oxide units and / or 4-25 propylene oxide units.

4. The composition according to any one of claims 1 -3, characterized in that the glycol is selected from the group comprising alkylene glycols, alkylene glycol ethers and polyalkylene glycol ethers and / or mixtures thereof.

5. The composition according to any one of claims 1 -4, characterized in that the glycol is selected from the group comprising propylene glycol, butyl glycol, glycerine and / or mixtures thereof.

6. The composition according to any one of claims 1 -5, characterized in that the anionic phosphoric ester a) is in an amount of 80-90 wt.% based on the total weight of the low-foaming composition.

7. A method for producing a low-foaming composition according to any one of claims 1 -6, characterized in that the components of the composition are mixed together at a temperature not exceeding 50°C until a homogeneous composition is obtained.

8. Use of a low-foaming composition according to claims 1 -6 as a component of cleaning, lubricating, anti-corrosion and / or metal treatment compositions.

9. The use of a composition according to claim 8, characterized in that the addition of a low-foaming composition as defined in any one of claims 1 -6 in an amount of 1 -5% by weight to the rapeseed oil increases the highest extreme pressure (EP) non-seizing load determined in accordance with ASTM D2783 compared to neat rapeseed oil by at least 40%.

10. An anti-corrosion composition characterized in that it comprises:- a low-foaming composition according to any one of claims 1 -6 in an amount of 40-60 wt.% based on the total weight of the anti-corrosion composition, and f) water in the range of 15-25% by weight relative to the total weight of the anticorrosion composition; g) a base in an amount of 20-30% by weight based on the total weight of the anti-corrosion composition, preferably triethanolamine (TEA), monoethanolamine (MEA), triisopropanolamine (TIPA), NaOH or KOH.

11. The anti-corrosion composition according to claim 10, characterized in that it is an inhibitor of corrosion of metal and / or metal alloys in aqueous solutions at a concentration of 1 -10% by weight relative to the total weight of the solution, preferably relative to steel, copper and aluminum.12.A flame retardant HFC hydraulic fluid composition characterized in that it contains- an anti-corrosion composition according to claim 10 or 11 in an amount of 1 - 5% by weight relative to the total weight of the flame retardant composition, whereby according to the ISO 6743-4 classification: HFC is a polymer solution in water containing more than 35% w / w of water, and also includes:c) glycol in an amount of 30-40% by weight based on the total weight of the flame-retardant composition, selected from the group comprising alkylene glycols, alkylene glycol and polyalkylene glycol ethers and / or mixtures thereof; d) water in the range of 35-50% by weight relative to the total weight of the flame retardant composition; e) glycerine in an amount of 5-15% by weight based on the total weight of the flame retardant composition; f) polyacrylamide with a molecular weight of 2 to 4 million in an amount of 5- 15% by weight relative to the total weight of the composition; g) a neutralizing agent in an amount of 1 -3% by weight based on the total weight of the composition, preferably triethanolamine.

13. A cleaning composition characterized in that it contains- a low-foaming composition according to any one of claims 1 -6 in an amount of 5-20% by weight of the cleaning composition, and h) a glycol in an amount of 1 -10% by weight based on the total weight of the cleaning composition, selected from the group comprising alkylene glycols, alkylene glycol and polyalkylene glycol ethers, derivatives of these compounds and / or mixtures thereof; i) cocam idopropyl betaine in the range of 1 -10% by weight based on the total weight of the cleaning composition; and optionally j) an alcohol in the range of 0-5% by weight based on the total weight of the cleaning composition selected from the group comprising C10-C18 alcohols having 1 -10 ethylene oxide units, preferably C12-C15 alcohols and 6-9 ethylene oxide units or mixtures thereof.

14. Use of the cleaning composition according to claim 13 for metal treatment and / or industrial cleaning, preferably of hard surfaces, preferably made of metal, even more preferably made of aluminium and stainless steel.15.A rinse-aid composition characterized in that it contains:- a low-foaming composition according to any one of claims 1 -6 in an amount of 1 -10% by weight relative to the total weight of the rinse-aid composition, and k) water in the range of 80-85% by weight relative to the total weight of the composition;l) an alcohol in the range of 5-15% by weight based on the total weight of the composition selected from the group comprising C12-C14 alcohols and having 3-10 ethylene oxide units and / or 3-10 propylene oxide units or mixtures thereof; m) carboxylic acid in the range of 1 -5% by weight based on the total weight of the composition, preferably citric acid.