WO2010057976A1

WO2010057976A1 - Liquid surface treatment composition with phosphonic acid derivatives neutralized with a binary amine system

Info

Publication number: WO2010057976A1
Application number: PCT/EP2009/065553
Authority: WO
Inventors: Patrick NOTTÉ
Original assignee: Thermphos Trading Gmbh
Priority date: 2008-11-21
Filing date: 2009-11-20
Publication date: 2010-05-27

Abstract

Liquid surface treatment compositions are disclosed containing a surface-active agent, an amine neutralized phosphonic acid and water. The amine neutralizing agent is represented by a combination of two structurally different amine species, a first more hydrophobic species and a second more hydrophilic species having distinct HLB values. The HLB value of the hydrophobic species is smaller, by several units on the HLB scale, compared to the HLB value of the hydrophobic species. The compositions are found to be particularly beneficial in relation to the removal of stubborn greasy stains.

Description

LIQUID SURFACE TREATMENT COMPOSITION WITH PHOSPHONIC ACID DERIVATIVES NEUTRALIZED WITH A BINARY AMINE SYSTEM

This invention pertains to liquid treatment compositions containing surface-active agents, conventional additives and optional components comprising a surface-active agent and an amine neutralized phosphonic acid compound. In more detail, the treatment compositions herein comprise a major level of surface-active agent and a relatively minor level of an amine neutralized phosphonic acid. The liquid compositions herein comprise, at least 10 % of water. The surfactant component can be represented by known surfactants including non- ionic, anionic, amphotheric, zwitterionic and cationic species. The phosphonic acid group can be represented by specific aminoalkylene phosphonic acids, narrowly defined alkylene phosphonic acid species and by phosphono-alkane-polycarboxylic acids. The amine neutralizing agent is represented by a combination of, at least, two structurally different amine species, one more hydrophobic species and one more hydrophilic species.

The domain of liquid detergent compositions is crowded and multiple combinations have been advocated for use and/or have found effective application. The art is crowded accordingly.

US 3,527,608 describes a bottle washing process based on conventional alkaline cleansers complemented by a liquid non-ionic detergent/foam depressant concentrate and also water- soluble organic acids which are capable of forming complexes with hardness causing agents. Examples of suitable hardness sequestrants are represented by conventional phosphonates such as amino tri(methylene phosphonic acid) and ethylene diamino tetra(methylene phosphonic acid). EP 0 517 605 discloses liquid detergent compositions containing major levels of anionic and non- ionic surfactants and a saturated fatty acid salt whereby the anionic and fatty acid species are neutralized in situ with amines and from 0.5 to 6 % of a polyphosphonate sequestrant salt. The amine salts can be represented by C2-8 alkanolamines or C2-8 alkaneamines. FR 2 677 370 concerns sequestrants suitable for use in liquid detergents containing at least 20 % of water. The sequestrant can be represented by a mixed salt of: an earth-alkaline metal; an alkali metal, ammonium, alkanolamine or alkane amine of hydroxyethane 1,1- diphosphonic acid. US 4,717,507 pertains to liquid builder- free detergent concentrates having fabric-softening properties containing alkyl benzene sulfonates, ethoxylated non- ionics, water-soluble soaps, fatty acid amide, sequestrants, alcohols and water. The sequestrants can be represented by polyphosphonic acids such as amino tri(methylene phosphonic acid), ethylene diamine tetra(methylene phosphonic acid)and diethylene triamine penta(methylene phosphonic acid).

EP 0 157 605 discloses liquid detergent compositions containing major levels of surfactants, more than about 50 %, and fatty acids, more than about 30 %, in combination with a quasi builder level of a polyphosphonic acid sequestrant. The phosphonic acid can be present as a salt of potassium, ammonium, C2-8 alkanolamine or C2-8 alkylamine or a mixed salt of ammonium, alkaline metal, alkanolamine or alkylamine in combination with an earth alkaline metal. The composition contains up to 10 %, preferably less than 5 % of water.

Substantial efforts have been invested, over extended periods of time, for the purpose of improving cleaning efficiency in relation to a broad range of surfaces. However, greasy stains have always and continue to present removal difficulties, particularly upon treatment with liquid product formulations. Sequestrants can facilitate stain removal efficacy by sequestering cations e.g. metal ions which can be, and frequently are, bound to greasy stains. However, the sequestrant action is known to be substandard and insufficient because the embedding of the stains to the surface can be based on cations and, in addition, on locked up polymeric, difficultly detachable structures.

It is therefore a main object of this invention to make available liquid surface treatment compositions capable of providing markedly improved cleaning performance in relation to a vast range of stains including greasy stains. It is another object of this invention to generate greasy stain removal technology capable of substantially concurrently and in uninterrupted sequence detaching locked up greasy bonds and solubilizing/dispersing the greasy components from the surface. Yet another object of this invention aims at synergistically combining, what had been shown to be difficultly compatible treatments, metal sequestration without enhancing the resistance of grease stains towards removal. Still a further object of this invention aims at providing liquid treatment compositions capable of delivering greasy stain removal comparable to top of the line granular detergents. An additional important object of the invention aims at using functionality enhancers, i.e. a binary amine system, to thus promote guiding the phosphonic component towards hydrophobic concentrations/stains and also at using such a binary amine system for increasing the effectiveness of the bleach analogous performance in the laundry liquor.

The term "percent" or "%" as used throughout this application stands, unless defined differently, for "percent by weight" or "% by weight". The terms "phosphonic acid" and "phosphonate" are also used interchangeably depending, of course, upon medium prevailing alkalinity/acidity conditions. The term "ppm" stands for "parts per million".

The above and other objects of the invention can now be met with the aid of a liquid surface treatment composition comprising a major level of a surface active agent in combination with an amine neutralized phosphonic acid component. In more detail, this invention relates to liquid surface treatment composition containing surface-active agents, conventional additives and optional ingredients, comprising:

(a) from 89.6 to 58 % by weight of a surface-active agent;

(b) from 0.4 to 32 % by weight of an amine neutralized phosphonic acid component wherein the phosphonic acid radical is selected from the group of:

i: aminoalkylene phosphonic acid having the general formula:

wherein X is selected from C1-C200000, preferably C1-C50000, most preferably C1-C2000, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci -C 12 linear, branched, cyclic or aromatic groups (which radicals and/or which - A -

groups can be) optionally substituted by OH, COOH, COOG, F, Br, Cl, I, OG, SO₃H, SO₃G and SG moieties; ZPO₃M₂; [V-N(K)J_n-K; [V-N(Y)J_n-V or [V-O]_x-V; wherein V is selected from: a C2-50 linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more Ci_i₂ linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by OH, COOH, COOR', F/Br/Cl/I, OR', SO₃H, SO₃R' or SR' moieties; wherein R' is a Ci_i₂ linear, branched, cyclic or aromatic hydrocarbon radical, wherein G is selected from C1-C200000, preferably C1-C50000, most preferably C1-C2000, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more C1-C12 linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOR', F, Br, Cl, I, OR', SO₃H, SO₃R' and SR' moieties; ZPO₃M₂; [V-N(K)]_n-K; [V-N(Y)]_n-V or [V- O]_x-V; wherein Y is ZPO₃M₂, [V-N(K)]_n-K or [V-N(K)]_n-V; and x is an integer from 1- 50000; z is from 0-200000, whereby z is equal to or smaller than the number of carbon atoms in X, and a is O or 1; n is an integer from O to 50000; z=l when a=0; and X is [V- N(K)]_n-K or [V-N(Y)]_n-V when z=0 and a= 1 ;

Z is a Ci _6 alkylene chain;

M is H;

W is selected from H, X and ZPO₃M₂;

K is ZPO₃M₂ or H whereby K is ZPO₃M₂ when z=0 and a=l or when W is H or X;

with the proviso that the aminoalkylene phosphonic acid contains, at least, two phosphonic acid groups;

ii: an alkylene phosphonic acid having the formula:

D-[C (OH) (PO₃M₂)₂] _y

wherein D is selected from Ci_ioo linear, branched, cyclic or aromatic hydrocarbon chain, optionally substituted by a Ci_i₂ linear, branched, cyclic or aromatic group (which chain and/or which group can be) optionally substituted by SO₃H,SO₃J,COOJ,OJ and SJ moieties; or [V-O]_x-V wherein V is selected from a C2-C50 linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more C₁-C₁₂ linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by SO₃H, SO₃R' ,COOR' ,OR' or SR' moieties wherein J is selected from C₁- Cioo linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more C₁-C₁₂ linear, branched, cyclic or aromatic groups (which chain and/or group can be ) optionally substituted by SO₃H, SO₃R' ,COOR' OR' or SR' wherein R' is a d_₁₂ linear, branched, cyclic or aromatic hydrocarbon chain and x is an integer from 1-50000; y is an integer from 1-50 whereby y is equal or smaller then the number of carbon atoms in D; and M is H; and

iii: phosphono-alkane-polycarboxylic acid wherein the alkane moiety is a C₃_2o linear, branched, cyclic or aromatic hydrocarbon chain and wherein the molar ratio of phosphonic acid radical to carboxylic acid radical is in the range of from 2 : 3 to 1 : 7;

iv: linear or branched hydrocarbon chains having from 6 to 2.10⁶ carbon atoms containing amino groups substituted by ZPO₃M₂ , and/or -E-N(W)(Y), with respect to the hydrocarbon chain, in either terminal or branched positions whereby the molar ratio of the aminoalkylene phosphonic acid substituents to the number of carbon atoms in the hydrocarbon chain is in the range of from 2 : 1 to 1 : 40 whereby at least 30 % of the available NH/NH₂ functionalities have been converted into the corresponding aminoalkylene phosphonic acid and/or into -E-N(W)(Y) substituted groups and wherein the alkylene moiety is selected from Ci_-6; wherein E is selected from C1-C2000, preferably C1-C500, most preferably C1-C200, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more C1-C12 linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOL, F, Br, Cl, I, OL, SO₃H, SO₃L and SL moieties; [V-N(Y)J_n-V or [V-O]_x-V wherein V is selected from: a C2-50 linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more C_1-12 linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by OH, COOH, COOR', F/Br/Cl/I, OR', SO₃H, SO₃ROr SR' moieties wherein R' is a d_₁₂ linear, branched, cyclic or aromatic hydrocarbon radical; wherein L is selected from C1-C2000, preferably C1-C500, most preferably C1-C200, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more C1-C12 linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOR', F, Br, Cl, I, OR', SO₃H, SO₃R' and SR' moieties; ZPO₃M₂; [V-N(K)J_n-K; [V- N(Y)]_n-V or [V-O]_x-V; wherein Y is ZPO₃M₂, [V-N(IQ]_n-K or [V-N(IQ]_n-V; and x is an integer from 1-50000; n is an integer from 0 to 50000;

M is H;

W is selected from H, E and ZPO₃M₂; preferentially W is ZPO₃M₂;

K is ZPO₃M₂ or H whereby K is ZPO₃M₂ when W is H or E;

in combination with an amine neutralizing agent having the formula:

(X)_b[N(W)(H)₂._b]_z

wherein X is selected from Ci-C₂ooooo, preferably Ci_soooo, most preferably Ci_₂ooo, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci-Ci₂ linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOG, F, Br, Cl, I, OG, SO₃H, SO₃G and SG moieties; H; [V-N(H)]_X-H or [V-N(Y)]_n-V or [V-O]_x-V; wherein V is selected from: a C_2-50 linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more Ci_i₂ linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by OH, COOH, COOR', F/Br/Cl/I, OR', SO₃H, SO₃R' or SR' moieties wherein R' is a Ci_i₂ linear, branched, cyclic or aromatic hydrocarbon radical,; wherein G is selected from Ci-C₂ooooo, preferably C1-C50000, most preferably Ci-C₂ooo, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci-Ci₂ linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOR', F, Br, Cl, I, OR', SO₃H, SO₃R' and SR' moieties; H; [V-N(H)]_n-H; [V-N(Y)]_n-V or [V-O]_x-V; wherein Y is H, [V- N(H)]_n-H or [V-N(H)]_n-V and x is an integer from 1-50000; n is an integer from 0 to 50000; z is from 0-200000 whereby z is equal to or smaller than the number of carbon atoms in X, and b is 0, 1 or 2; z=l when b=0; and X is [V-N(H)]_X-H or [V-N(Y)]_n-V when z=0 and b=l; with W different from H when X=H;

W is selected from H and X; whereby the molar ratio of the phosphonic acid multiplied by the number of phosphonic acid moieties in the phosphonic acid to the molar ratio of amine multiplied by the number of N in the amine is from:

1 : 0.25 to 1 : 1.

with the proviso that the amine neutralizing agent is represented by a combination of, at least, two structurally different amine species, the first one being more hydrophobic having a HLB value which is at least 2 units smaller than the HLB value of the second, and the second one being more hydrophilic than the first one, said first and said second amine species being used in equivalent ratios of first (more hydrophobic) : second (more hydrophilic) in the range of from 10 : 1 to 4 : 7 ; and

(c) at least 10 % by weight of water.

The HLB system and the calculation of the individual HLB values of amine neutralizing species are based on the criteria set forth in:

"The HLB System" "Presentation to the Midwest Chapter of the Society of Cosmetic Chemists, March 9^th 2004, UNIQUEMA".

The HLB scale goes from 0 to 20. The HLB value of a compound is derived from the water loving portion of the compound, on its molecular weight and then dividing that number by 5.

The term "structurally different" with respect to the amine neutralizing agent means that the individual amine species have different molecular weights.

The amine neutralizing agent is used in neutralizing levels, in relation to the phosphonic acid component, thereby considering the required pH of the detergent formulation, including the type of phosphonate. It goes without saying that detergent co -neutralizing agents such as alkaline and alkaline-earth metal hydroxides can be used. The degree of neutralizing activity of the essential amine component, in relation to the phosphonic acid group, can be expressed by means of the pH of a 1% aqueous solution at 20 °C of the neutralized product. For an amino alkylene phosphonic acid and also for an aminophosphonate in the meaning of iv, this value is at least 1, preferably from 1.5 to 8.5, in one particular execution from 2 to 8. For alkylene phosphonic acids and phosphonoalkane polycarboxylic acids, the pH of a 1 % aqueous solution at 20°C of the neutralized phosphonate being at least 2, preferably from 3 to 8.5, and in one particular execution from 3.5 to 8.0. The amine-neutralized phosphonate component can also be prepared individually and as such i.e. as a solution or as a solid added to the claimed arrangement.

The first and second amine species are preferably used in equivalent ratios (more hydrophobic: more hydrophilic) of from:

10 : 1 to 4 : 7; particularly from

10 : 3 to 1 : 1.

The term "equivalent ratio" represents the number of moles of the more hydrophobic amine multiplied by the number of amino groups present in that molecule divided by the number of moles of the more hydrophilic amine multiplied by the number of amino groups present in that molecule.

The terms "more hydrophilic" and "more hydrophobic" can, inter alia, also be defined by means of the chemical structures. Alkylene amines, alkylamines and arylamines used in combination with the second species, in the ponderal proportions set forth above, are more hydrophobic, in the meaning of the invention herein, than species from the group of alkoxyamines, and alkanolamines.

Examples of the HLB values of amine neutralizing agents for use herein are as follows:

-isopropylamine 5.41

-di-n-butylamine 2.47 -tri-n-butylamine 1.72

-cyclohexylamine 3.22

-1,2-diaminocyclohexane 5.60

-stearylamine 1.18

-tridecaneoxyethylethanolamine 7.24

-nonylphenyldodeca(oxyethyl)ethanolamine 14.47

-laurylamine 1.73

In one particular execution herein, the first, more hydrophobic, amine neutralizing species has a HLB value which is, at least, 4 units, smaller than the HLB value of the second more hydrophilic species. In one preferred aspect herein, the HLB value of the first (more hydrophobic) species is smaller than 6. The HLB values of mixtures or of either one of the first or the second species can be determined in accordance with the UNIQUEMA paper.

The iii phosphonocarboxylic acid is preferably represented by 2-phosphonobutane 1,2,4- tricarboxylic acid. The ii alkylene phosphonic acid can, in one preference, be represented by species of the formula 1-hydroxyalkylene 1,1-diphosphonic acid wherein the alkyl group is selected from C_2-10, more preferably C_2-6, in one particular execution 1- hydroxyethylene 1,1-diphosphonic acid. In another preference, D in the ii alkylenephosphonic acid is [V-O]_x-V with V being C_2-10 and with x being from 1-50.

In preferred phosphonic acids i herein, X or Y are different from ZPO3M2 when W is ZPO₃M₂. In another preferred execution X is [V-N(K)J_x-K or [V-N(Y)J_n-V, with V being a C2-4 linear or branched hydrocarbon radical when z=0 and a=l . In yet another preference, W and K are ZPO3M2 when X is [V-O]_x-V. In other preferred executions, z is equal to or smaller than half the number of carbon atoms in X. In another preference W and Y are [V- N(K)]_X-K or [V-N(Y)J_n-V when X is a Ci to C₅₀ alkyl chain substituted by COOH, COOG, SO₃H, SO₃G, OG, SG, OH, F, Br, Cl or I groups.

The i and iv aminoalkylene phosphonic acid group can preferably be selected from the group of: ethylene diamine tetra(methylene phosphonic acid); diethylenetriamine penta(methylene phosphonic acid); 1,3-propane diamine-N,N'-bis(2- aminoethyl)hexa(methylene phosphonic acid); L-lysine-N,N,N',N'-tetra(methylene phosphonic acid); L-alanine-N,N- di(methylene phosphonic acid); poly((propyl or ethyl) imino bis(methylene phosphonic acid)) substituted polyethylene imine; glycine N₅N- bis(propyl or ethyl imino bis(methylene phosphonic acid)); alanine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); β-alanine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); glutamic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 4-aminomethyl 1,8-octane diamino hexa(methylene phosphonic acid); 6-amino hexanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 9-amino nonanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 11 -amino undecanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 12-amino dodecanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); poly(vinylamino bis(methylene phosphonic acid)); and poly(vinylamino N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid))).

In another approach preferred i and IV aminoalkylene phosphonic acid groups can be selected from the group of: 4-amino butanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); methionine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); L-lysine N,N,N',N'-tetra(propyl or ethyl imino bis(methylene phosphonic acid)); aspartic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); phenylalanine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); threonine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 2-ethanol amine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 6-hexanol amine N₅N- bis(propyl or ethyl imino bis(methylene phosphonic acid)); 4-butanol amine N₅N- bis(propyl or ethyl imino bis(methylene phosphonic acid)); di(2-ethanol)amine(propyl or ethyl imino bis(methylene phosphonic acid)); dipropanol amine(propyl or ethyl imino bis(methylene phosphonic acid)); 2-(2-aminoethoxy)ethanol bis(propyl or ethyl imino bis(methylene phosphonic acid)); 3-propanol amine bis(propyl or ethyl imino bis(methylene phosphonic acid)); toluene diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); 1 ,6-hexamethylene diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); 1 ,4-butane diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); 1 ,2-ethylene diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); linear or branched polyethylene imine poly(propyl or ethyl imino bis(methylene phosphonic acid)); methyl or ethyl or propyl or butyl or hexyl or heptyl or octyl or nonyl or decyl or dodecyl amine bis(propyl or ethyl imino bis(methylene phosphonic acid)); aniline bis(propyl or ethyl imino bis(methylene phosphonic acid)); C_12- 22 fatty amine bis(propyl or ethyl imino bis(methylene phosphonic acid)); thioglycolic acid S-(propyl or ethyl imino bis(methylene phosphonic acid)); cysteine S,N,N-tri(ethyl or propyl imino bis(methylene phosphonic acid)); methyl(propyl or ethyl imino bis(methylene phosphonic acid)) thioether; ethyl or propyl or pentyl or hexyl or octyl or phenyl or naphthyl or decyl or dodecyl(propyl or ethyl imino bis(methylene phosphonic acid)) thioether; propanoic acid 3-oxy(propyl or ethyl imino bis (methylene phosphonic acid)); butanoic acid 4-oxy(propyl or ethyl imino bis(methylene phosphonic acid)); pentanoic acid 5-oxy(propyl or ethyl imino bis(methylene phosphonic acid)); acetic acid 2- oxy(propyl or ethyl imino bis(methylene phosphonic acid)); tartaric acid O,O'-bis(propyl or ethyl imino bis(methylene phosphonic acid)); hydroxysuccinic acid O-(propyl or ethyl imino bis(methylene phosphonic acid)); butyric acid α-oxy-(propyl or ethyl imino bis(methylene phosphonic acid)).

The essential amine component needed to neutralize the phosphonic acids can be represented by a wide variety of known species. Examples of preferred amines include: alkylene amines; alkoxy amines; halogen substituted alkyl amines; alkyl amines; aryl amines; and alkanol amines. It is understood that poly species are embraced. As an example, the term "alkyl amines" also includes -polyalkyl amines-, -alkyl polyamines- and -polyalkyl polyamines-.

Individual species of amines of interest include: ethylene diamine; diethylene triamine; triethylene tetramine; tetraethylene pentamine; hexamethylene diamine; dihexamethylene triamine; 1,3-propane diamine N,N'-bis (2-amino ethyl); polyether amine; polyether polyamines; amine and poly amine alkoxylates or polyalkoxylates like cocodiamine ethoxylate; 2-chloroethyl amine; 3-chloropropyl amine; 4-chlorobutyl amine; primary, secondary and tertiary amines, and the corresponding poly-amines with C1-C50 linear or branched or cyclic hydrocarbon chains, in particular morpholine, n-butylamine; isopropyl amine; diisopropyl amine; di-n-butylamine; tri-n-butylamine; tri-isobutyl amine; cyclohexyl amine; cycloheptylamine; cyclododecylamine; or substituted amino cycloalkanes, for example 4-methylcyclohexylamine, N,N-dimethylcyclohexylamine; 1,2- cyclohexyl diamine and isophoron diamine; laurylamine; stearyl amine and oleyl amine; polyvinyl amines; polyethylene imine, branched or linear or mixtures thereof; ethanolamine; diethanolamine; propanolamine; and dipropanol amine. Aromatic amines can be represented by aniline; diaminotoluenes; diphenylalanine; N-phenylbenzamine. Commercially available fatty amines with a chain length from C₆-C₂₂ such as hydrogenated tallow alkyl amine; cocoalkyl amine and soyaalkylamine are also examples of preferred species.

The treatment compositions can be used, in a conventional manner, for application in relation to all kind of surfaces. The like applications can be represented by: textile laundry; textile softening, textile bleaching; hard surface treatment; dishwasher use; glass and other surface treatment/cleaning applications well known in the domain of the technology.

The treatment compositions herein comprise, as a major constituent, of from 89.6% to 58% of a surface active agent; from 0.4% to 32% of a selected amine neutralized phosphonic acid; and at least 10 % of water, although mixtures of water and suitable well known solvents including aliphatic alcohols can preferably be used. In one such preference, the water can represents at least 20 % and can be used together with up to 20 % of a solvent selected from C_1-10 aliphatic alcohol, monopropylene glycol, ethers of glycol e.g. ethylene glycol and butylglycol, benzyl alcohol and mixtures thereof. In a particular execution, the aliphatic alcohol is represented by C2-4 species and is used in levels of about 10 %. The treatment compositions of this invention frequently contain, expressed in relation to the total composition, surfactant ingredients in the range of from 2 to 50 %, more preferably of from 2 to 40 % in specific executions from 3 to 15%. The phosphonate ingredient herein can be used, in the actual treatment compositions, in sub additive levels in the range of from 0.001 to 5 %, preferably from 0.002 to 3 %. The phosphonate exhibits, within the context of the actual treatment composition, conventional phosphonate functionalities such as chelant, sequestrant, threshold scale inhibition, dispersant and oxygen bleach analogous properties. In addition, the essential phosphonate can provide, in part due to its structural particularities in combination with the amine neutralizing properties, additional synergistic functionalities in relation to e.g. optional ingredients, such as aesthetics e.g. perfumes, optical brighteners, dyes, and catalytic enhancers for enzymes, and also provide improved storage stability to e.g. bactericides. The essential phosphonate amine salt was also found to seek the promiscuity of hydrophobic concentrations/stains in the laundry liquor thereby providing desirable performance benefits non achievable by means of art technologies. The binary amine phosphonate salt also, quite unexpectedly and against expectations, reinforces the effectiveness of bleach analogous performance during the laundry operation. The inventive compositions are particularly beneficial in relation to greasy stains which are known to be particularly stubborn and adversely resistant to, for example, actual liquid treatment technology. The essential phosphonate constituent, very importantly, can greatly facilitate the environmental and regulatory acceptability of the cleaning compositions herein. The use of selected amine neutralizing agents for the phosphonate component were found to deliver unusual grease removal from all kinds of surfaces, such as greasy stains having been subject to heat deterioration and thus can be present as difficultly removable stains. The use of specific proportions of hydrophobic and hydrophilic amines was found to yield unexpected removal benefits. Without being bound by any hypothesis or theory, it is established that using a majority of the hydrophobic amine species, together with a relatively lesser portion of the hydrophilic species, facilitates the polymeric stain disintegration and subsequently facilitates the dispersion of the disintegrated greasy stain.

The treatment compositions herein can also comprise conventional additives and optional components which are used in art established levels and for their known functionalities. The surface active agents herein can be represented by conventional species selected from e.g. cationic, anionic, non-ionic, ampholytic and zwitterionic surfactants and mixtures thereof. Typical examples of the like conventional detergent components are eminently well known and have been used extensively. Useful surfactants include C_11-20 alkyl benzene sulfonates, Cio-20 alkyl sulfates, C12-20 alkyl alkoxy sulfates containing e.g. 1-6 ethoxy groups and C 10-20 soaps. Suitable non- ionic surfactants can also be represented by amine oxides having the formula R,R',R' 'N→O wherein R, R' R" can be alkyl having from 10 to 18 carbon atoms. Cationic surfactants include quaternary ammonium surfactants such as C_6-16 N-alkyl or alkenyl ammonium surfactants. Treatment compositions generally are well known and have found commercial application for a long time. The ingredients of such compositions are eminently well known, including quantitative and qualitative parameters. We wish to exemplify, in a summary manner, some of the matrixes of treatment compositions to which the essential phosphonate ingredient can be added.

Heavy Duty Liquid Laundry Detergent.

Parts by weight.

C 10-22 fatty acids 10

Nonionic surfactant 10

Anionic surfactant 15

Potassium hydroxide (50%) 3

1,2-Propanediol 5

Sodium citrate 5

Ethanol 5

Enzymes 0.2-2

Phosphonate, amine neutralized 1-3

Minors and water balance to 100

Fabric softener.

Parts by weight.

Phosphoric acid 1

Distearyl dimethyl ammonium chloride 10-20 Stearyl amine ethoxylate 1-3 Magnesium chloride ( 10%) 3 Perfume; dye 0.5

Phosphonate, amine neutralized 0.1-2 Water balance to 100 Hard surface cleaner (Industrial).

Parts by weight.

Sodium hydroxide (50%) 40 Low foaming non-ionic surfactant 5-20 Sodium carbonate 2-5 Phosphonate, amine neutralized 0.1-3 Water balance to 100

Multi Purpose Kitchen Cleaner

Parts by weight.

Low foaming non-ionic surfactant 2-5 Potassium hydroxide (50%) 1-3 Fatty C 10-20 Acid 2-5 1,2-Propanediol 3-5 Sodium metasilicate 1-2 Phosphonate, amine neutralized 0.1-2 Color and Perfume 0.1-0.5 Water balance to 100

Bottle Washing.

Parts by weight.

Low-foaming non-ionic surfactant 5-15 Phosphoric acid (85 %) 30-40 Isopropanol 2-5 Phosphonate, amine neutralized 0.5-5 Water balance to 100

Suitable examples of amine combinations for use in the illustrated treatment compositions are listed hereinafter. N° Amines Mole(s) Equivalent Ratio

i: isopropylamine 3 tri-n-butylamine 2.0 0.66

ii: 1 ,2-diaminocyclohexane 0.95 stearylamine 1.10 0.58

iii: diethanolamine 2 dodecylamine 5.5 2.75

iv: cyclohexyl amine 3 tridecaneoxyethanolamine 2.5 1.2

v: ethanolamine 2 laurylamin 4 2

vi: triethanolamine 2 tri-n-butylamine 10

Claims

1. Liquid surface treatment composition containing surface-active agents, conventional additives and optional ingredients, comprising:

(a) from 89.6 to 58 % by weight of a surface-active agent;

i: aminoalkylene phosphonic acid having the general formula:

wherein X is selected from C1-C200000, preferably C1-C50000, most preferably C1-C2000, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci -C 12 linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOG, F, Br, Cl, I, OG, SO₃H, SO₃G and SG moieties; ZPO₃M₂; [V-N(IQ]_n-K; [V-N(Y)J_n-V or [V-O]_x-V wherein V is selected from: a C2-50 linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more C_1-12 linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by OH, COOH, COOR', F/Br/Cl/I, OR', SO₃H, SO₃R' or SR' moieties, wherein R' is a C_1-12 linear, branched, cyclic or aromatic hydrocarbon radical, wherein G is selected from C1-C200000, preferably C1-C50000, most preferably C1-C2000, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci -C 12 linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOR', F, Br, Cl, I, OR', SO₃H, SO₃R' and SR' moieties; ZPO₃M₂; [V-N(IQ]_n-K; [V-N(Y)]_n-V or [V- O]_x-V; wherein Y is ZPO₃M₂, [V-N(K)]_n-K or [V-N(K)]_n-V and x is an integer from 1- 50000; z is from 0-200000, whereby z is equal to or smaller than the number of carbon atoms in X, and a is 0 or 1; n is an integer from 0 to 50000; z=l when a=0; and X is [V- N(K)]_n-K or [V-N(Y)]_n-V when z=0 and a=l;

Z is a Ci _6 alkylene chain;

M is H; W is selected from H, X and ZPO₃M₂;

ii: an alkylene phosphonic acid having the formula:

D-[C(OH)(PO₃M₂)₂]_y

wherein D is selected from Ci_ioo linear, branched, cyclic or aromatic hydrocarbon chain, optionally substituted by a C_1-12 linear, branched, cyclic or aromatic group (which chain and/or which group can be) optionally substituted by SO₃H, SO₃J, COOJ, OJ and SJ moieties; or [V-O]_x-V wherein V is selected from a C₂-Cso linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more Ci-Ci₂ linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by SO₃H, SO₃R', COOR', OR' or SR' moieties wherein J is selected from Ci- Cioo linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci-Ci₂ linear, branched, cyclic or aromatic groups (which chain and/or group can be ) optionally substituted by SO₃H, SO₃R', COOR' OR' or SR' wherein R' is a d_₁₂ linear, branched, cyclic or aromatic hydrocarbon chain and x is an integer from 1-50000; y is an integer from 1-50 whereby y is equal or smaller then the number of carbon atoms in D; and M is H; and

iii: phosphono-alkane-polycarboxylic acid wherein the alkane moiety is a C₃_₂o linear, branched, cyclic or aromatic hydrocarbon chain and wherein the molar ratio of phosphonic acid radical to carboxylic acid radical is in the range of from 2 : 3 to 1 : 7;

iv: linear or branched hydrocarbon chains having from 6 to 2.10⁶ carbon atoms containing amino groups substituted by ZPO₃M₂ , and/or -E-N(W)(Y), with respect to the hydrocarbon chain, in either terminal or branched positions whereby the molar ratio of the aminoalkylene phosphonic acid substituents to the number of carbon atoms in the hydrocarbon chain is in the range of from 2 : 1 to 1 : 40 whereby at least 30 % of the available NH/NH2 functionalities have been converted into the corresponding aminoalkylene phosphonic acid and/or into -E-N(W)(Y) substituted groups and wherein the alkylene moiety is selected from Ci_-6; wherein E is selected from C1-C2000, preferably C1-C500, most preferably C1-C200, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more C₁-C₁₂ linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOL, F, Br, Cl, I, OL, SO₃H, SO₃L and SL moieties; [V-N(Y)J_n-V or [V-O]_x-V wherein V is selected from: a C2-50 linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more Ci_i2 linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by OH, COOH, COOR', F/Br/Cl/I, OR', SO₃H, SO₃ROr SR' moieties wherein R' is a C_1-12 linear, branched, cyclic or aromatic hydrocarbon radical; wherein L is selected from C1-C2000, preferably C1-C500, most preferably C1-C200, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more C₁-C₁₂ linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOR', F, Br, Cl, I, OR', SO₃H, SO₃R' and SR' moieties, ZPO₃M₂; [V-N(IQ]_n-K; [V- N(Y)]_n-V or [V-O]_x-V; wherein Y is ZPO₃M₂, [V-N(K)J_n-K or [V-N(K)]_n-V and x is an integer from 1-50000; n is an integer from O to 50000;

M is H;

W is selected from H, E and ZPO₃M₂; preferentially W is ZPO₃M₂;

K is ZPO₃M₂ or H whereby K is ZPO₃M₂ when W is H or E;

in combination with an amine neutralizing agent having the formula:

(X)_b[N(W)(H)₂._b]_z

wherein X is selected from C1-C200000, preferably Ci_soooo, most preferably Ci_₂ooo, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci -C 12 linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOG, F, Br, Cl, I, OG, SO₃H, SO₃G and SG moieties; H; [V-N(H)J_x-H or [V-N(Y)J_n-V or [V-O]_x-V wherein V is selected from: a C2-50 linear, branched, cyclic or aromatic hydrocarbon radical, optionally substituted by one or more Ci_i2 linear, branched, cyclic or aromatic groups (which radicals and/or groups are) optionally substituted by OH, COOH, COOR', F/Br/Cl/I, OR', SO₃H, SO₃R' or SR' moieties wherein R' is a Ci_i2 linear, branched, cyclic or aromatic hydrocarbon radical,; wherein G is selected from C1-C200000, preferably C1-C50000, most preferably C1-C2000, linear, branched, cyclic or aromatic hydrocarbon radicals, optionally substituted by one or more Ci -C 12 linear, branched, cyclic or aromatic groups (which radicals and/or which groups can be) optionally substituted by OH, COOH, COOR', F, Br, Cl, I, OR', SO₃H, SO₃R' and SR' moieties; H; [V-N(H)]_n-H; [V-N(Y)J_n-V or [V-O]_x-V; wherein Y is H, [V- N(H)]_n-H or [V-N(H)]_n-V and x is an integer from 1-50000; n is an integer from O to 50000; z is from 0-200000 whereby z is equal to or smaller than the number of carbon atoms in X, and b is 0, 1 or 2; z=l when b=0; and X is [V-N(H)]_X-H or [V-N(Y)]_n-V when z=0 and b= 1 ; with W different from H when X=H :

W is selected from H and X;

whereby the molar ratio of the aminoalkylene phosphonic acid multiplied by the number of phosphonic acid moieties in the phosphonic acid to the molar ratio of amine multiplied by the number of N in the amine is from:

1 : 0.25 to 1 : 1.

with the proviso that the amine neutralizing agent is represented by a combination of, at least, two structurally different amine species, the first one being more hydrophobic having a HLB value which is at least 2 units smaller than the HLB value of the second, and the second one being more hydrophilic than the first one, said first and said second amine species being used in equivalent proportions of first (more hydrophobic) : second (more hydrophilic) in the range of from 10 : 1 to 4 : 7; and

(c) at least 10 % by weight of water.

2. The composition in accordance with Claim 1 wherein the first species of the amine neutralizing agent has a HLB value which is at least 4 units smaller than the HLB value of the second species.

3. The composition in accordance with Claims 1 or 2 wherein the surfactant agent, selected from the group of cationic, non- ionic, anionic, ampho lytic and zwitterionic surfactants and mixtures thereof is present in a level of from 2 to 40 % by weight.

4. The composition in accordance with any one of Claims 1 to 3 wherein z is equal to or smaller than half the number of carbon atoms in X.

5. The composition in accordance with any one of Claims 1-4 wherein in the amino phosphonic acid i, X or Y are different from ZPO3M2 when W is ZPO3M2, and W and K are ZPO₃M₂ when X is [V-O]_x-

6. The composition in accordance with any one of Claims 1-5 wherein the amine neutralized phosphonic acid component represents from 0.001 to 5 % by weight.

7. The composition in accordance with any one of Claims 1-6 wherein the first (more hydrophobic) amine is selected from the group of alkylene amines, halogen substituted alkyl amines, alkyl amines and aryl amines and wherein the second (more hydrophilic) amine is selected from the group of alkoxy amines and alkanol amines.

8. The composition in accordance with any one of Claims 1-7 wherein the amine neutralized phosphonic acid component represents from 0.002 to 3 % by weight.

9. The composition in accordance with any one of Claims 1-8 wherein the equivalent ratio of first (more hydrophobic) to second (more hydrophilic) amine species is in the range from 10 : 3 to 1 : 1.

10. The composition in accordance with any one of Claims 1-6 or 8 wherein the binary amine species, expressed in mole(s), are selected from combinations as follows: isopropylamine/tri-n-butylamine 3/2;

1 ^-diaminocyclohexane/stearylamine 0.95/1.10; diethano lamine/dodecylamine 2/5.5 ; cyclohexylamine/tridecaneoxyethylethano lamine 3/2.5; ethanolamine/laurylamine 2/4; and triethano lamine/tri-n-buty lamine 2/10.

11. The composition in accordance with any one of Claims 1-10 containing, in addition, an aliphatic C_1-10 alcohol in an amount of up to 20 % by weight.

12. The composition in accordance with Claim 11 wherein the aliphatic alcohol is represented by C2-4 species and is present in a level of about 10 % by weight.

13. The composition in accordance with any one of Claims 1-12 wherein the aminoalkylene phosphonic acid moiety in the amine neutralized phosphonate is selected from the group of: ethylene diamine tetra(methylene phosphonic acid); diethylenetriamine penta(methylene phosphonic acid); 1,3-propane diamine-N,N'-bis(2- aminoethyl)hexa(methylene phosphonic acid); L-lysine-N,N,N',N'-tetra(methylene phosphonic acid); L-alanine-N,N-di(methylene phosphonic acid); poly((propyl or ethyl) imino bis(methylene phosphonic acid)) substituted polyethylene imine; glycine N₅N- bis(propyl or ethyl imino bis(methylene phosphonic acid)); alanine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); β-alanine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); glutamic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 4-aminomethyl 1,8-octane diamino hexa(methylene phosphonic acid); 6-amino hexanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 9-amino nonanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 11 -amino undecanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 12-amino dodecanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); poly(vinylamino bis(methylene phosphonic acid)); and polyvinylamino poly(N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid))).

14. The composition in accordance with any one of Claims 1-12 wherein the aminoalkylene phosphonic acid moiety in the amine neutralized phosphonate is selected from the group of: 4-amino butanoic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); methionine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); L-lysine N,N,N',N'-tetra(propyl or ethyl imino bis(methylene phosphonic acid)); aspartic acid N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); phenylalanine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); threonine N,N-bis(propyl or ethyl imino bis(methylene phosphonic acid)); 2-ethanol amine N₅N- bis(propyl or ethyl imino bis(methylene phosphonic acid)); 6-hexanol amine N₅N- bis(propyl or ethyl imino bis(methylene phosphonic acid)); 4-butanol amine N₅N- bis(propyl or ethyl imino bis(methylene phosphonic acid)); di(2-ethanol)amine(propyl or ethyl imino bis(methylene phosphonic acid)); dipropanol amine(propyl or ethyl imino bis(methylene phosphonic acid)); 2-(2-aminoethoxy)ethanol bis(propyl or ethyl imino bis(methylene phosphonic acid)); 3-propanol amine bis(propyl or ethyl imino bis(methylene phosphonic acid)); toluene diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); 1 ,6-hexamethylene diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); 1,4-butane diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); 1 ,2-ethylene diamine tetra(propyl or ethyl imino bis(methylene phosphonic acid)); linear or branched polyethylene imine poly(propyl or ethyl imino bis(methylene phosphonic acid)); methyl or ethyl or propyl or butyl or hexyl or heptyl or octyl or nonyl or decyl or dodecyl amine bis(propyl or ethyl imino bis(methylene phosphonic acid)); aniline bis(propyl or ethyl imino bis(methylene phosphonic acid)); C_12- 22 fatty amine bis(propyl or ethyl imino bis(methylene phosphonic acid)); thioglycolic acid S-(propyl or ethyl imino bis(methylene phosphonic acid)); cysteine S,N,N-tri(ethyl or propyl imino bis(methylene phosphonic acid)); methyl(propyl or ethyl imino bis(methylene phosphonic acid)) thioether; ethyl or propyl or pentyl or hexyl or octyl or phenyl or naphthyl or decyl or dodecyl(propyl or ethyl imino bis(methylene phosphonic acid)) thioether; propanoic acid 3-oxy(propyl or ethyl imino bis (methylene phosphonic acid)); butanoic acid 4-oxy(propyl or ethyl imino bis(methylene phosphonic acid)); pentanoic acid 5-oxy(propyl or ethyl imino bis(methylene phosphonic acid)); acetic acid 2- oxy(propyl or ethyl imino bis(methylene phosphonic acid)); tartaric acid O,O'-bis(propyl or ethyl imino bis(methylene phosphonic acid)); hydroxysuccinic acid O-(propyl or ethyl imino bis(methylene phosphonic acid)); butyric acid α-oxy-(propyl or ethyl imino bis(methylene phosphonic acid)).

15. The composition in accordance with any one of Claims 1-6 or 8-12 wherein the amine neutralizing species is selected from: ethylene diamine; diethylene triamine; triethylene tetramine; tetraethylene pentamine; hexamethylene diamine; dihexamethylene triamine; 1,3-propane diamine N,N'-bis (2-amino ethyl); polyether amine; polyether polyamines; amine alkoxylates; cocodiamine ethoxylate; 2-chloroethyl amine; 3- chloropropyl amine; 4-chlorobutyl amine; primary, secondary and tertiary amines; polyamines with C1-C50 linear or branched or cyclic hydrocarbon chains; morpholine; n- butylamine; isopropyl amine; diisopropyl amine; di-n-butylamine; tri-n-butylamine; tri- isobutyl amine; cyclohexyl amine; cycloheptylamine; cyclododecylamine; substituted amino cycloalkanes; 4-methylcyclohexylamine; N,N-dimethylcyclohexylamine; 1,2- cyclohexyl diamine; isophoron diamine; laurylamine; stearyl amine; oleyl amine; polyvinyl amine; branched or linear polyethylene imine; ethanolamine; diethanolamine; propanolamine; dipropanol amine; aniline; diaminotoluene; diphenylalanine; N- phenylbenzamine; hydrogenated tallow alkyl amine; cocoalkyl amine and soyaalkylamine.

16. The composition in accordance with any one of Claims 1-4 or 6-12 wherein the iii phosphono-alkane-polycarboxylic acid is represented by 2-phosphonobutane- 1,2,4- tricarboxylic acid.

17. The composition in accordance with any one of Claims 1-4 or 6-12 wherein the ii alkylene phosphonic acid is represented by l-hydroxyalkylene-l,l-diphosphonic acid wherein the alkyl group is selected from C2-6 or from [V-O]_x-V with V being C_2-10 and with x being 1-50.

18. The composition in accordance with any one of Claims 1-4 or 6-12 wherein X in the i aminoalkylene phosphonic acid is represented by [V-N(K)J_x-K or [V-N(Y)J_n-V, with V being a C2-4 linear or branched hydrocarbon radical when z=0 and a=l; or W and Y are selected from [V-N(K)J_x-K or [V-N(Y)J_n-V when X is a Ci_₅₀ alkyl chain substituted by: COOH, COOG, SO₃H, SO₃G, OG, SG, OH, F, Cl, Br or I groups.

19. The use of a composition in accordance with any one of Claims 1-18 in a method of surface treatment selected from textile laundering, textile softening, textile bleaching, hard surface cleaning, dishwasher cleaning and glass cleaning.