CZ20014507A3 - Cleansing compositions - Google Patents

Abstract

The present invention relates to a composition suitable for the cleaning of the exterior surface of a vehicle comprising an anionic surfactant, chelating agent and an anti-resoiling agent, soil suspending agent or mixtures thereof. The above composition provides excellent cleaning performance on contact with the surface to be cleaned.

Description

Technical field

The present invention relates to compositions suitable for cleaning the outer surface of vehicles, in particular automobiles.

BACKGROUND OF THE INVENTION

Means suitable for cleaning the exterior surface of vehicles are well known. Typically, the compositions are used in a diluted form and applied to the vehicle by means of a sponge or fabric. However, these products generally require the user to scrub or polish the vehicle. This necessary manual scrubbing is a problem especially when the surface is large, tall or of a shape that includes many relatively inaccessible places, such as a truck or aircraft. The biggest problem, however, is that manual scrubbing is time and labor intensive. It is therefore an object of the present invention to provide a cleaning agent for vehicles which does not require polishing or scrubbing the surface to be cleaned.

WO99 / 13036 relates to a hard surface cleaner which can be used for cleaning large surfaces and which does not need to be polished on the surface. The composition comprises a mixture of a nonionic alcohol ethoxylate and C ₈ to C _I6 alkyldimethylaminoxide in a weight ratio of 5: 1 to 15: 1 and nitrogen-containing chelating agent.

WO97 / 43372 relates to a hard surface cleaner which can be used to clean hard-to-reach surfaces, such as the exterior surface of windows or as a car protection. The composition comprises a silicate, a hydrophobic acrylate polymer and a surfactant and optionally a chelating agent.

• ♦ · • •

Applicants have found a combination of components in the form of a vehicle cleaner which cleans on contact with the vehicle and does not require polishing or scrubbing. In addition, the composition of the present invention also provides additional cleaning benefits. That is, the vehicle is not only easier to clean when compared to known vehicle cleaners when first used in the present composition, but also easier to clean in a second and subsequent cleaning using the present composition. It is believed that this additional advantage results from the use of a soil repellent polymer or soil suspending polymer or mixture thereof in the composition of the present invention. It is further contemplated that when using the composition of the present invention, the polymer settles and attaches to the surface of the vehicle. Between each cleaning of the vehicle, the polymer forms a protective layer on which dirt is deposited. The next time the vehicle is washed, the polymer layer is washed off along with the impurities deposited thereon and is replaced by a new polymer layer.

In a further aspect of the present invention, in addition to said advantages, the composition of the present invention also provides the possibility of not drying the surface to be cleaned, i.e., allowing it to dry naturally without leaving water stains on the surface.

SUMMARY OF THE INVENTION

Summary of the invention

The present invention provides a cleaning composition suitable for cleaning the exterior surface of vehicles comprising a chelating agent and an anionic surfactant in a ratio of 4: 1 to 1: 4 and a polymeric compound selected from the group consisting of a soil repellent polymer, a soil suspending polymer or mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

The composition of the present invention comprises a chelating agent, an anionic surfactant, and a soil-repellent polymer, a soil-suspending polymer, or mixtures thereof as essential components of the present composition.

Chelating agent

The composition of the present invention comprises a chelating agent. Typically, the composition of the present invention comprises up to 20% by weight, preferably 0.01% to 15% by weight of the total chelating agent composition.

Suitable chelating agents are any of those known to those skilled in the art, such as those selected from the group consisting of phosphonate chelating agents, aminocarboxylate chelating agents, other carboxylate chelating agents, polyfunctionally substituted aromatic chelating agents, ethylenediamine-N, Ν. disuccinic acids or mixtures thereof.

The presence of chelating agents contributes to further improving the chemical stability of the compositions.

Suitable phosphonate chelating agents for use in the present invention include alkali metal ethane-1-hydroxydiphosphonates (HEDP), alkylene polyes (alkylene phosphonates) as well as aminophosphonate compounds including aminoaminotri (methylene phosphonic acid) (ATMP), nitrilotrimethylene phosphonates ethylenediamintetram (ethylenediamintetram).

the compounds are present either in acid form or as salts with different cations on some or all of the acid groups.

(NTP), and

Phosphonate

Polyfunctionally substituted aromatic chelating agents can also be used in the compositions of the present invention. See U.S. Pat. U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine-N, N'-disuccinic acid or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts or mixtures thereof. Ethylenediamine-N, Ν'-disuccinic acids, especially the (S, S) isomer, have been extensively described in U.S. Patent 4,704,233, November 3, 1987 to Hartman and Perkins. Ethylenediamine-N, Ν'-disuccinic acid is, for example, commercially available under the trade name ssEDDS from Palmer Research Laboratories.

Suitable aminocarboxylates which may be used in the present invention include ethylenediaminetetraacetates, (ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid), or in the form of alkali metal, ammonium or substituted ammonium salts. Particularly suitable aminocarboxylates for use in the present invention are diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid (PDTA), which is commercially available from BASF under the trade name Trilon FS, and methylglycine diacetic acid (MGDA).

Other carboxylate chelating agents for use in the present invention include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid, or mixtures thereof.

Another chelating agent for use in the present invention is a compound of Formula I:

wherein R _1, R ₂ , R ₃ and R ₄ are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO ₂ , -C (O) R 'and -SO ₂ R '' wherein R 'is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl and aryloxy, R''is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy, and R ₅ , R ₆ R ₇ and R ₈ are independently selected from the group consisting of -H and alkyl.

Particularly preferred chelating agents that can be used according to the present invention are aminotri (methylenephosphonic acid), diethylenetriaminopentaacetic acid, diethylenetriaminopentamethylene phosphonate,

1-hydroxyethane diphosphonate, ethylenediamine-N, N'-disuccinic acid and mixtures thereof.

Other chelating agents include polycarboxylates, in particular citrate and complexes of formula II:

CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) -CH (B) (II) wherein A is H or OH, B is H or -O-CH (COOX) -CH ₂ (COOX) and X is H or a salt-forming cation. For example, when both A and B are H, the compound is oxydisuccinic acid and its water-soluble salts. When A is OH and B is H, the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. When A is H and B is -O-CH (COOX) -CH ₂ (COOX), then the compound is vinanedisuccinic acid (TDS) and its water-soluble salts. Mixtures of these chelating agents are particularly preferred for use in the present invention. Especially

TMS and TDS, these chelating agents are described in U.S. Patent 4,663,071, May 5, 1987, to Bush et al.

Still other polycarboxylates suitable for use in the present invention include copolymers of maleic anhydride with ethylene or 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid vinyl methyl ether.

Other useful polycarboxylate chelating agents include etherhydroxypolycarboxylates of formula III:

HO- [C (R) (COOM) -C (R) (COOM) -O] _n -H (III) wherein M is hydrogen or a cation that makes the resulting salt soluble in water, preferably an alkali metal, ammonium or substituted ammonium cation, n is 2 to 15 (preferably n is 12 to 10, more preferably n is 2 to 4) and each R is the same or different and is selected from hydrogen, C 1 -C ₄ alkyl or C 1 -C _{4 4} substituted alkyl (preferably R is hydrogen).

Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in U.S. Pat. patents 3,923,679, 3,835,163,

158,635, 4,120,874 and 4,102,903, all of which are incorporated herein by reference.

Of these cyclic compounds, dipicolinic acid and chelidanoic acid are preferred.

The polycarboxylates of the present invention are succinic acid, an acid suitable for use according to mellitic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, benzenepentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.

Other suitable carboxylate chelating agents of the present invention include the carboxylated carbohydrates described in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, which is incorporated herein by reference.

Other suitable carboxylates for use in the present invention, but less preferred because they do not meet the above criteria, are alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acids. Examples of polyacetic acid chelating agent salts are sodium, potassium, lithium, ammonium, and substituted ammonium salts of ethylenediamine tetraacetic acid and nitrilotriacetic acid.

Other suitable, but less preferred, polycarboxylates are those known as alkyl iminoacetic chelating agents such as methyl imino diacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxypropylene imino diacetic acid, and other alkyl imino acetic acid chelating agents.

Also suitable in the compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds described in U.S. Patent 4,566,984, Bush, issued Jan. 28, 1986, which is incorporated herein by reference. Useful succinic acid chelating agents include C ₅ to C ₂ alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecylsuccinic acid. Alkyl succinic acids typically are of the R-CH (COOH) _CH2 (COOH) i.e. derivatives of succinic acid, wherein R is hydrocarbon, e.g. C _X o to C ₂₀ alkyl or alkenyl, preferably C12-CI6 or wherein R is substituted with hydroxyl, sulfo, sulfoxyl or sulfone as described in the above patents.

Succinic acid chelating agents are preferably used in the form of water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinic acid chelating agents include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. Lauryl succinates are preferred chelating agents from this group and are described in polymerization. European Patent Application 86200690.5 / 0 200 263, issued November 5, 1986.

Examples of useful chelating agents include sodium and potassium carboxymethyl malonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentantetracarboxylate, water-soluble polyacrylates, and copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates described in U.S. Patent 4,144,226, Crutchfield et al., Issued March 13, 1979, which is incorporated herein by reference. These polyacetal carboxylates can be prepared by mixing, under conditions of glyoxylic ester and initiator. The resulting polyacetal carboxylate ester is then chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in an alkaline medium, converted to the corresponding salt and added to a surfactant.

Polycarboxylate chelating agents are also described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, which is incorporated herein by reference. Such substances include the water-soluble salts of the homo- and copolymer of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Suitable polyphosphonates for use in the present invention are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (examples of which are tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates) or phosphonates.

The most preferred chelating agents that can be used in the present invention are selected from diethylenetriaminepentamethylene phosphonate ethane-1-hydroxy diphosphonate (HEDP).

(DTPMP) or

Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST.

«· ·· ·· ··· · · · ···

Anionic surfactant

The composition of the present invention also contains an anionic surfactant as an essential component. The anionic surfactant is present in an amount of 0.01% to 40% by weight, preferably 0.1% to 20% by weight, and even more preferably less than 10% by weight, and most preferably 0.2% to 10% by weight of the composition.

Suitable anionic surfactants for use in the compositions of the present invention include water-soluble salts or ROSO ₃ M acids, wherein R is preferably a C ₇ to C ₂₄ hydrocarbon, preferably an alkyl or hydroxyalkyl containing a C ₇ to C ₂₄ alkyl component, more preferably C ₁₂ to C _1-8 alkyl or hydroxyalkyl, and M is H or a cation, eg, an alkali metal (eg, sodium, potassium, lithium) or ammonium or substituted ammonium (eg, methyl, dimethyl and trimethylammonium cations, and quaternary ammonium cations, such as tetramethylammonium cation and dimethylpiperidinium cation and quaternary ammonium cations derived from alkylamines (such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like).

Other suitable anionic surfactants for use in the present invention are water-soluble salts or acids of RO (A) _m SO ₃ M, wherein R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl comprising a C ₁₀ -C ₂₄ alkyl component, preferably C12 to _C20 alkyl or hydroxyalkyl, more preferably _C12 to C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy group, m is greater than zero, typically 0.5 to 6, more preferably 0.5 to 3, and M is H or a cation such as is, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. This includes alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are _C12-C18 alkyl polyethoxylate (1.0) sulfate, _C12-C18E (1.0) M, _C12-C18 alkyl polyethoxylate (2.25) sulfate, C _i2 to C ₁₈ E (2 25) M, C ₃₂ to C ₁₈ alkyl polyethoxylate (3.0) sulfate, C _i2 to C ₁₈ E (3.0), and C ₂ to C ₈ alkyl polyethoxylate (4.0) sulfate, C ₂ to C ₁₈ E (4.0) M, wherein M is selected from sodium and potassium.

Other anionic surfactants particularly suitable for use in the present invention are the water-soluble salts or acids of RSO ₃ M, wherein R is a C ₆ -C ₂₂ straight or branched saturated or unsaturated alkyl, preferably C ₁₀ -C ₁₆ alkyl, and more preferably C ₃₂ to C _1-6 alkyl, and M is H or a cation, eg, an alkali metal cation (eg, sodium, potassium, lithium) or ammonium or substituted ammonium (eg, methyl, dimethyl and trimethylammonium cations, and quaternary ammonium cations, such as tetramethylammonium cation and dimethylpiperidinium cation and quaternary ammonium cations derived from alkylamines (such as ethylamine, diethylamine, triethylamine and mixtures thereof and the like).

Alkylarylsulfonates suitable for use in the present invention are water-soluble salts or acids of RSO ₃ M, wherein R is aryl, preferably benzyl, substituted with a C ₆ -C ₂₂ straight or branched saturated or unsaturated alkyl, preferably C ₁₀ -C ₁₈ alkyl and more preferably _C12 alkyl _1G, and M is H or a cation, e.g. an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium cation and dimethylpiperidinium cation and quaternary ammonium cations derived from alkylamines (such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like).

Alkyl sulfonates and alkylarylsulfonates suitable for use in the present invention include primary and secondary alkylarylsulfonates. Secondary C ₆ -C 22 alkyl or C ₆ -C 22 alkylarylsulfonates indicate in the present invention that the SO ₃ M or aryl-SO ₃ M group is attached to the carbon atom of the alkyl chain, which is located between two other carbons of the alkyl chain (secondary carbon atom) ).

For example C14-C _alkyl sul phosphonate salt is commercially available under the name Hostapur SAS from Hoechst and _C8 sodium alkyl sulphonate is commercially available under the name Witconate NAS 8 ° from Witco SA. An example of a commercially available alkylarylsulfonate is Suuryl laurylarylsulfonate. Particularly preferred alkylarylsulfonates are alkylbenzene sulfonates commercially available under the trade name Nansa® from Albright & Wilson.

Other anionic surfactants useful for detergent purposes may also be used in the present invention. These include, for example, salts (e.g., sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolammonium salts) of soaps, C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonating pyrolyzed alkaline earth citrate products, e.g. . as described in British patent no. 1,082,179, C ₈ to C ₂ 4 alkylpolyglycolethersulfates (containing up to ethylene oxide); alkyl ester sulfonates such as C ₁₄ methyl ester sulfonates; acyl glycerol sulfonates, glycerol fatty acid esters, alkyl phenol, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C _i2 to C _I8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C C ₁₄ diesters), ethoxylated sulfosuccinates, alkylpolysaccharide sulfates, such as alkylpolyglucoside sulfates (non-ionic unsulfate moles up to C 18) will be described below) , branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as RO (CH ₂ CH ₂ O) _k CH ₂ COO'M ⁺ wherein R is a C ₈ to C ₂ 2 alkyl, k is an integer from 0 to 10 and M is a soluble salt-forming cation . Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present or derived from tall oil are also suitable. Further examples are given in Surface Active Agents and Detergents (Vol. I and II, Schwartz, Perry and Berch). Various such surfactants are also generally described in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin et al. in section 23, line 58 to section 29, line 23 (which is incorporated herein by reference).

Other anionic surfactants very suitable for use in the present invention are alkyl carboxylates and alkoxycarboxylates of 4 to 24 carbon atoms in the alkyl chain, preferably 8 to 18, and even more preferably 8 to 16, wherein the alkoxy is propoxy and / or ethoxy and is preferably ethoxy in the alkoxylation step, 0.5 to 20, preferably 5 to 12 carboxylate Preferred for use herein is sodium laureth 11 carboxylate (i.e. RO (C ₂ H ₄ O) ₀ and -CH ₂ COONa, with R = C _i2 to C _i4) commercially available under the tradename Akyposoft® 100NV from Kao Chemical Gbmh.

Particularly preferred surfactants are those selected from the group consisting of alkyl sulfate, alkyl sulfonate, alkyl ethoxy sulfate, alkyl benzene sulfonate, alkyl carboxylate, alkyl ethoxy carboxylate, alkyl sulfosuccinate, and mixtures thereof. In a preferred aspect of the present invention, the anionic surfactant is a system consisting of at least two anionic surfactants. Particularly preferred anionic surfactants are linear alkyl or alkylbenzene sulfonate and sulfosuccinate surfactants. More particularly preferred are anionic surfactants of the surfactant system, where present, C _i2 linear alkylbenzene sulphonate (LAS) and dioctyl sulphosuccinate.

The chelating agent and anionic surfactant of the present invention are present in a ratio of 4: 1 to 1: 4.

Reagents to prevent dirt re-settling

The compositions of the present invention optionally include a polymer to prevent re-settling of impurities. If present, the soil-repellent polymers are present in an amount of up to 20% by weight, more preferably 0.001% by weight to 10% by weight, even more preferably 0.01% by weight to 5% by weight and most preferably 0.1% by weight to 2% by weight. % by weight.

Suitable anti-redeposition agents include those well known to those skilled in the art, including, for example, a polyalkoxylene glycol ester, a vinylpyrrolidone homopolymer or a copolymer other than those described above, a polysaccharide polymer, a polyalkylene glycol, a mono- or di-terminated polyalkoxylene glycol that will as defined below, or a mixture thereof.

Vinylpyrrolidone homopolymers suitable for use in the present invention are N-vinylpyrrolidone homopolymers containing a repeating monomer of structural formula IV:

HC ² I h ₂ C - CH - I ²

TO

C = 0

AND

-CH.

(IV) wherein n (degree of polymerization) is an integer of 10 to 1,000,000, preferably 20 to 100,000, and even more preferably 20 to 10,000.

Vinylpyrrolidone homopolymers (PVP) suitable for use in the present invention have an average molecular weight of from 1000 to 100,000,000, preferably from 2000 to 10,000,000, even more preferably from 5,000 to 1,000,000, and most preferably from 50,000 to 500,000.

• · •

• *

9 * »9

Suitable vinylpyrrolidone homopolymers are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP ^K-15 (viscosity molecular weight of 10,000), PVP K-30 DEG (average molecular weight of 40,000), PVP K -60 ° (average molecular weight 160,000) and PVP K-90 ® (average molecular weight 360,000). Other suitable vinylpyrrolidone homopolymers which are commercially available from BASF Cooperation include Sokalan HP 165 ° and Sokalan HP 12 °; vinylpyrrolinone homopolymers known to those skilled in the detergent art (see for example EP-A-262 897 and EP-A-256,696).

Copolymers of vinylpyrrolidones suitable for use in the present invention include N-vinylpyrrolidone and alkylenically unsaturated monomers or a mixture thereof.

Alkylenically unsaturated monomers of the copolymers of the present invention include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid and vinyl acetate. Any of the unsaturated acid anhydrides can be used, for example acrylate, methacrylate. Aromatic monomers such as styrene, sulfonated styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene and similar well known monomers may be used.

The molecular weight of the vinylpyrrolidone copolymer is not particularly important when the polymer is water-soluble, has some surface activity and is adsorbed to a solid surface from a liquid composition or solution (i.e., when used at dilution) in which it is included to increase surface hydrophilicity. However, preferred copolymers of N-vinylpyrrolidones and alkylenically unsaturated monomers or mixtures thereof have a molecular weight of 1000 to 1,000,000, preferably 10,000 to 500,000, and most preferably 10,000 to 200,000.

Such copolymers of Ν'-vinylpyrrolidones and alkylenically unsaturated monomers, such as PVP / vinyl acetate copolymers, such as PVP / vinyl acetate copolymers.

9 are commercially available under the trade name Luviskol® from BASF.

Other polymers suitable for use in the present invention are polysaccharide polymers including substituted cellulosic materials such as carboxymethylcellulose ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, succinoglycan, and natural polysaccharide polymers such as xanthan gum, guar gum, carbonic acid derivatives, or a gum thereof or .

Particular polysaccharide polymers that can be used in the present invention are xanthan resin and derivatives thereof. Xanthan resin and derivatives thereof are commercially available, for example, from Kelco under the tradename Keltrol RD °, Kelzan S ° or Kelzan T °.

Additional soil retardant components suitable for use in the present invention further include polyoxyalkylene glycol, mono- and di-terminated polyoxyalkylene glycol, or a mixture thereof, as defined below.

Polyalkoxylene glycols suitable for use in the present invention are H-O- (CH ₂ -CHR ₂ O) _n -H.

Mono-terminated polyalkoxylene glycols suitable for use in the present invention are R _x -O- (CH ₂ -CHR ₂ O) _n -H.

The di-terminated polyalkoxylene glycols suitable for use in the present invention are R 1 -O- (CH ₂ -CHR ₂ O) _n -R ₃ .

In these substances, R 1 and R _{3 are} each independently a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain of 1 to 30 carbon atoms or an amine bearing a linear or branched hydrocarbon chain of 1 to 30 carbon atoms, R ₂ is hydrogen or a linear or branched hydrocarbon chain consisting of 1 to 30 carbon atoms and n is an integer greater than 0.

···· ·· • ·

In fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc ··> »

Preferably, R ₁ and R _{3 are} each independently substituted or unsubstituted, linear or branched alkyl, alkenyl or aryl consisting of 1 to 30 carbon atoms, preferably 1 to 16, more preferably 1 to 8 and most preferably 1 to 4 carbon atoms. or an amine bearing a linear or branched, substituted or unsubstituted alkyl, alkenyl or aryl group having 1 to 30 carbon atoms, preferably 1 to 16, more preferably 1 to 8 and most preferably 1 to 4. Preferably R ₂ is hydrogen or a linear or branched alkyl, alkenyl or aryl of 1 to 30 carbon atoms, preferably 1 to 16, more preferably 1 to 8, and most preferably R ₂ is methyl or hydrogen. Preferably n is an integer greater than 1, more preferably 5 to 1000, even more preferably 10 to 100, even more preferably 20 to 60, and most preferably 30 to 50.

Preferred polyoxyalkylene glycols, mono and di-terminated polyoxyalkylene glycols for use in the present invention have a molecular weight of at least 200, more preferably 400 to 5000 and most preferably 800 to 3000.

Mono-terminated polyoxyalkylene glycols suitable for use in the present invention include 2-aminopropylpolyethylene glycol (molecular weight 2000), methylpolyethylene glycol (molecular weight 1800) and the like. Such polyalkoxylene glycols are commercially available from Hoechst in a series of polyglycols or from Huntsman under the trade name XTJ °. Polyalkoxylene glycols suitable for use in the present invention are polyethylene glycols such as polyethylene glycol (molecular weight 2000).

Di-terminated polyoxyalkylene glycols suitable for use in the present invention include O, O'-bis- (2-aminopropyl) polyethylene glycol (molecular weight 2000),

O, O'-bis- (2-aminopropyl) polyethylene glycol (molecular weight 400), O, O'-dimethylpolyethylene glycol (molecular weight 2000), dimethylpolyalkylene glycol (molecular weight 2000), dimethylpolyethylene glycol (molecular weight 2000) or a mixture thereof. The di-terminated polyoxyalkylene glycol suitable for at least one of the metal (a) ethoxylations of (a) to prepare the product of use according to the present invention is dimethylpolyethylene glycol (molecular weight 2000).

For example, dimethylpolyethylene glycol is commercially available from Hoechst in a series of polyglycols, such as PEG DME-2000, or from ® ® from Huntsman under the tradename Jeffamine and XJT.

Preferred impurity retardants include oligomeric terephthalate esters, typically prepared by a process involving transesterification / oligomerization, with a catalyst such as titanium lacoxide. Such esters can be made using other monomers that can be incorporated into the ester structure at one, two, three, four or more positions, without forming a densely crosslinked overall structure.

Suitable anti-redeposition agents include sulfonated products of substantially linear ester oligomers containing an oligomeric ester backbone of terephthaloyl and oxyalkylene repeating units and allyl derived sulfonated end groups covalently bonded to the backbone, such as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990, J.J. Scheibel and E.P. Gosselink.

Such ester oligomers may be allyl alcohol; (b) reaction with dimethyl terephthalate (DMT) and 1,2-propylene glycol (PG) in a two-step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other anti-redeposition agents include nonionic terminated 1,2-propylene / polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4,711,730, December 8, 1987 to Gosselink et al., For example, products resulting from transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG, and poly (ethylene glycol) (PEG). Other examples of soil release agents include; partially and fully anionic terminated oligomeric esters of U.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as ethylene glycol (EG), PG, DMT, and oligomers of ethylene glycol (EG);

Na-3,6-dioxa-8-hydroxyoctane sulfonate; non-ionically terminated block oligomeric compounds US 4,072,857, Oct. 27, 1987, Gosselin, for example made of DMT, methyl (Me) terminated PEG and EG and / or PG or a combination of DMT, EG and / or PG, ME-terminated PEG and Na -dimethyl-5-sulfoisophthalate; and anionic, especially sulfoaryl-terminated terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31, 1989 to Maldonato, Gosselink et al., Exemplified by an ester compound made from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably containing added PEG, e.g., PEG 3400.

Anti-redeposition agents also include simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US 3,959,230, Hays, May 25, 1976, and US 3,893,929, Basadur, July 8, 1975; cellulose derivatives such as hydroxyethyl cellulose polymers available as METHOCEL from Dow; Ci to C ₄ alkyl celluloses and C ₄ hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al .; and methylcellulose ethers having a mean degree of substitution (methyl) per anhydroglucose unit of 1.6 to 2.3 and a solution viscosity of 80 to 120 centipoise, measured at 20 ° C in a 2% aqueous solution. Such materials are available as METOLOSE SM 100 and METOLOSE SM 200, which under the trade names methyl cellulose ethers are manufactured by Shin-etsu Kagaku Kogyo KK.

Suitable anti-redeposition agents containing poles (vinyl ester) hydrophobic moieties include graft copolymers poles (vinyl ester), e.g., C 1 to C ₆ vinyl esters, preferably poles (vinyl acetate) grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, issued April 22, 1987 to Kud et al. Commercially available examples include SOKALAN impurity resistants such as SOKALAN HP-22 available from BASF, Germany. Anti-redeposition agents are polyesters with repeating units containing 10 to 15% by weight of ethylene terephthalate together with 80 to 90% by weight of polyoxyethylene terephthalate derived from polyoxyethylene glycol with an average molecular weight of 300 to 5000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Another preferred anti-redeposition agent is the (CAP) ₂ (EG / PG) ₅ (T) ₅ (SIP) 1 oligomer, which contains terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene ( EP / PG) units and which is preferably capped, preferably capped with isethionates, such as in an oligomer containing one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably 0.5: 1 to 10: 1 and two end caps derived from 2- (2-hydroxyethoxy) ethanesulfonate. Preferably, these soil re-settling agents further comprise from 0.5% to 20% by weight of an oligomer of a crystallinity-reducing stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzene sulfonate or a member of the xylene-, cumene- and toluene-sulfonates group or mixtures thereof; wherein these stabilizers or modifiers are placed in synthetic containers as described in US 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for said soil re-settling agent include Na-2- (2). -hydroxyethoxy) ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.

Another group of preferred soil release agents are oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, a unit that is at least three functional, wherein the ester linkers result in the formation of a branched oligomeric backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl unit; and (c) at least one 1,2-oxyalkylenoxy unsulfonated unit which is a group; and (2) one or more terminating units selected from non-ionic terminating units, anionic terminating units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propane disulfonates, alkoxylated mixtures.

phenolsulfonates, Preferred and their esters wherein CAP, sulfoaroyl derivatives are {(CAP) χ (EG / PG) y '(DEG) _y - (PEG) _y >> (T) _z (SIP) ₂ > (SEG) _q (B) _m },

EG / PG, PEG, T and SIP are as defined above, (DEG) represents di (oxyethylene) oxyl units, (SEG) represents units derived from sulfoethyletheruglycerin and related units, (B) represents branched units that are at least three functional, wherein the ester linkages give rise to a branched oligomeric backbone, x is 1 to 12, y 'is 0.5 to 25, y' 'is 0 to 12, y' '' is 0 to 10, y '+ y' '+ y '' 'is a total of 0.5 to 25, z is 1.5 to 25, z' is 0 to 12, z + z 'is a total of 1.5 to 25, q is 0.05 to 12, m is 0 The 011 to 10 ax, y ', y' ', y' '', z, z ', q and m represent the average number of moles of the corresponding units per mole of ester and the ester has an average molecular weight of 500 to 5000.

Preferred SEG and CAP monomers for said esters include Na-2- (2-, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3) and homologues thereof, and mixtures thereof and products of ethoxylation and sulphonation of allyl alcohol. Preferred ester resistants in this group include the transesterification and oligomerization product of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate and / or 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} ethanesulfonate sodium, 9, 9, 9, 9, 9, 9, 9

DMT, 2 - (2,3-dihydroxy-propoxy) sodium ethanesulfonate, EG, and PG using an appropriate titanium catalyst and can be designated as (CAP) ₂ (T) ₅ (EG / PG) _{1 4} (SEG) _{2, 5} (B 10, where CAP is [Na ⁺ -O ₃ S (CH ₂ CH ₂ O) ₃ , ₅ ] - and B is a unit of glycerin and the molar ratio of EG / PG is 1.7: 1 measured by conventional gas chromatography after complete hydrolysis.

Other classes of soil retardant agents include (1) nonionic terephthalates bonded by diisocyanate coupling agents to polymeric ester structures, see U.S. Pat. No. 4,101,824, Violland et al., And U.S. Pat. And (2) carboxylate end group impurity retarding agents made by adding trimellitic anhydride to known impurity retardants to convert the terminal hydroxyl groups to trimellitate esters. With appropriate selection of the catalyst, trimellitic anhydride forms a linker to the ends of the polymer via an isolated carboxylic acid ester of trimellitic anhydride rather than opening the anhydride linker. Nonionic or anionic anti-redeposition agents can be used as starting materials as long as they have hydroxyl end groups that can be esterified. See U.S. Pat. No. 4,525,524, Tung et al. Other groups include (3) anionic agents that prevent the re-settling of impurities of terephthalate with a variable urethane linker, see U.S. Pat. 4,101,824, Violland et al .; (4) polyesters (vinylcaprolactam) and related copolymers with monomers such as vinylpyrrolinod and / or dimethylaminoethyl methacrylate, including both non-ionic and cationic polymers, see U.S. Pat. 4,579,681 to Ruppert et al .; (5) graft copolymers added to BASF types of SOKALAN produced by grafting acrylic monomers onto sulfonated polyesters. These anti-redeposition agents have the same soil release and anti-redeposition activity as the known cellulose ethers: see EP 279 134 A, 1988,

Rhone-Poulenc Chemistry. Still other groups include (6) graft vinyl monomers, such as acrylic acid and vinyl acetate, to proteins such as casein, see EP 457 205 A, BASF (1991), and (7) polyester antipollution agents prepared by condensing adipic acid , caprolactam and polyethylene glycol, see Bevan et al., DE 2 335 044, Unilever NV, 1974. Other agents preventing soil re-settling are described in U.S. Pat. patents

240,918, 4,787,989 and 4,525,524.

Other suitable soil release agents include hydrophobically modified cellulose polymers. The cellulose-based polymers to be used according to the present invention are preferably compounds of formula V:

R (V) wherein each R is selected from the group consisting of R ₂ , R _c and ^r 2 wherein

each R ₂ is independently selected from the group consisting of H and C 1 -C ₄ alkyl

- each R _c is

O

II

- (CH 3 -C 2) wherein each Z is independently selected from the group consisting of M, R ₂ , R _c and R _h ;

each R _h is independently selected from the group consisting of C ₅ to C ₂ alkyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₂ alkylaryl, C ₇ to C ₂ arylalkyl, substituted alkyl, hydroxyalkyl, C _x to C ₇ alkyl; • · · · ·

C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ to C ₂ alkylaryloxy-2-hydroxyalkyl, (R ₄ ) ₂ N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, ( R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ to C ₁₂ aryloxy-2-hydroxyalkyl,

R _r 0 R _q OR, O

⁵ II I II I II I ^{5 5} II

-c-CH-C-CH ₂ c-CH-CH-C-OM a

-C-CH-CH-C-OM

each R ₄ is independently selected from the group consisting of H, C 1 to C ₂₀ alkyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₂₀ alkylaryl, C ₇ to C ₂ arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl , cycloalkylaminoalkyl and hydroxyalkyl;

- each R ₅ is independently selected from the group consisting of H, C 1 to C ₂₀ alkyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₂₀ alkylaryl, C ₇ to C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, (R ₄ ) ₂ N-alkyl and (R ₄ ) ₃ N-alkyl;

where

M is a suitable cation selected from the group consisting of Na, K, 1 / 2Ca and 1 / 2Mg;

each x is 0 to 5, each y is 1 to 5, and provided that:

the degree of substitution of the group _RH is 0.001 to 0.1, more preferably 0.005 to 0.5 and most preferably 0.01 to 0.05;

the degree of substitution of R _c where Z is H or M is 0.2 to 2.0, more preferably 0.3 to 1.0, and most preferably 0.4 to 0.7;

if any R _H carries a positive charge, it is counterbalanced by a suitable anion a

- two R ₄ on the same nitrogen atom together form a cyclic structure selected from the group consisting of piperidine and morpholine.

The degree of substitution of the group R _H , sometimes shortened to "DS _RH " in the present invention, refers to the number of moles of the group R _H which are substituted per anhydrous glucose unit, where the anhydrous glucose unit is a six-membered cycle of the above general formula V.

"The degree of substitution of the group R _c , sometimes shortened to" DS _Rc in the present invention, refers to the number of moles of the group R _c in which Z is H or M which are substituted per anhydrous glucose unit, where the anhydrous glucose unit is a six-membered cycle, The requirement that Z be H or M is necessary to ensure a sufficient number of carboxymethyl groups such that the resulting polymer is soluble. It will be understood that in addition to the required amount of R _c in which Z is H or M, other R _c components in which Z is other than H or M are optionally present, and most preferably are present.

For example, these polymers can be obtained using the procedures described in co-pending application PCT / US98 / 19139 and PCT / US98 / 19142.

Particularly preferred polymers to prevent re-settling of the impurities are selected from the group consisting of homo or copolymers of vinylpyrrolidone, polysaccharide polymers, polyoxyalkylene glycols, and mixtures thereof.

Dirt-suspending polymer

The compositions of the present invention optionally comprise a soil-suspending polymer. If such soil-suspending polymers are present, they are preferably present in an amount of 0.001% by weight to 10% by weight, more preferably 0.01% by weight to 5% by weight, and most preferably 0.1% to 3% by weight.

Any polyamine soil-suspending polyamine polymer known to those skilled in the art can be used herein. Polyamine polymers particularly suitable for use in the present invention are polyalkoxylated polyamines. Such materials can commonly be described as molecules of empirical structures with repeating units:

^{R '} -1' - (alkoxy) _ylamine form

R ¹ (alkoxy) _y quaternized form wherein R is a hydrocarbon, usually consisting of 2 to 6 carbon atoms; R ¹ is a C ₁ to C ₂₀ hydrocarbon; alkoxy groups are ethoxy groups, propoxy groups and the like and y is 2 to 30, most preferably 10 to 20; n is an integer of at least 2, preferably 2 to 20, most preferably 3 to 5; and X 'is an anion such as a halide or methyl sulfate added in a quaternization reaction.

The polyamines most preferred for use in the present invention are the so-called ethoxylated polyethylene amines, i. the product of the polymerization reaction of ethylene oxide and ethyleneimine of formula VI:

(EtO) -) - N - CH - CH 2 -N - (EtO) _y (EtO) _y (EtO) _y (VI) wherein y = 2 to 30. For use according to the present invention, ethoxylated polyethylene amine is particularly preferred, especially ethoxylated tetraethylenepentamine; and quaternized ethoxylated hexamethylenediamine.

Particularly preferred soil-suspending polymers are polyalkoxylated polyamine polymers, more preferably ethoxylated polyethylene amines.

Folders (if any)

The compositions of the present invention optionally comprise various optional ingredients depending on the requirements for the surface being cleaned.

Optional ingredients suitable for use in the present invention may be selected from the group consisting of surface-retaining polymers, additional surfactants, enzymes, hydrotropic ions, suds control agents, buffers, thickeners, radical scavengers, pigments, dye preservatives and / or fragrances.

Polymer remaining on the surface

The composition of the present invention comprises a surface-retaining polymer as an optional but preferred component. Surface-retaining polymer means a polymer that is capable of treating the surface by adhering to or attaching to the surface that needs to be cleaned so that it remains on the surface during and after cleaning. Such adherence or attachment is, for example: covalent interaction; electroatatic interaction; hydrogen bond or Van der Waals forces. The polymer treats the surface to render it hydrophilic, which means that the angle between the water and the surface after treatment of the surface with the polymer-containing composition is less than 50 °, more preferably less than 40 °, even more preferably less than 30 ° and most preferably less than 20 °. ° or less. Contact angle is measured according to the US standard contact angle test procedure, identification number D5725-95 using an instrument commercially marketed under the trade name Contact Angle Measuring System G10 by Kruss.

In another aspect of the present invention, the polymer is capable of permanently treating a surface to be hydrophilic, provided that the surface contact angle between water and surface is less than 50 °, more preferably less than 40 °, even more preferably less than 30 ° and most preferably less than 50 °. 20 ° or less. “Permanently means that the hydrophilic surface treatment is maintained for at least one of the following periods: • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Rinsing, preferably at least three rinses, even more preferably at least five rinses, even more preferably at least seven rinses, and most preferably at least ten rinses or even at least thirty rinses performed by the rinse test procedure described in the present invention.

Test procedure for rinsing

The rinse test procedure used according to the present invention consists of spraying the surface with water having a hardness of 24 French degrees with a normal garden hose from a distance of 1.0 meters for 30 seconds. The water flow through the hose was 10 liters per minute.

The polymer of the present invention is a homo or copolymer and preferably comprises at least one hydrophobic or cationic group and at least one hydrophilic group. The hydrophobic group is preferably an aromatic C ₈ to C _x8 linear or branched carbon chain, vinyl imidazole or a propoxy group. Cationic groups include any group that is positively charged or has a positive dipole. The hydrophilic group may be selected from any group that forms a dipole capable of hydrogen bonding. Suitable examples of such hydrophilic groups include vinylpyrrolidone, a carboxylic acid such as acrylic acid, methacrylic acid, maleic acid and ethoxylates.

In a preferred aspect of the present invention, the polymer is selected from the group consisting of polyvinylpyrrolidone copolymers. A particularly preferred polyvinylpyrrolidone copolymer is N-vinyl imidazole N-vinylpyrrolidone (PVPVI) polymer available, for example, from BASF under the tradename Luvitec VP155K18P. Preferred PVPVI polymers have an average molecular weight of from 1000 to 5,000,000, more preferably from 5,000 to 2,000,000, even more preferably from 5,000 to 500,000, and most preferably from 5,000 to 15,000. Preferred PVPVI polymers contain at least 55% by weight, preferably at least 60% by weight N- vinylimidazole monomers. Alternatively, another suitable polymer is quaternized PVPVI, for example a compound sold under the tradename Luvitec Quat 73W by BASF.

Other vinylpyrrolidone copolymers suitable for use in the compositions of the present invention are quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers. Quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers suitable for use in the compositions of the present invention are compounds of formula VII:

'Ν' '0

AND

-CH-CH:

2 n

N-cfc = O) _y -R-N ⁺ (R ₃ ) ₂ R ₄ -X (VII) wherein n is 20 mol% to 99 mol% and preferably 40 mol% to 90 mol% and m is 1 mol% up to 80 mol% and preferably 5 mol% to 40 mol%; R x is H or CH ₃ ; y denotes 0 or 1; R ₂ is -CH ₂ -CHOH-CH ₂ - or C _x H _{2 x} , wherein x = 2 to 18; R ₃ represents lower alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl, or, ^CH 2

R ₄ denotes lower alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl; X 1 is selected from the group consisting of Cl, Br, I, 1 / 2SO ₄ , HSO _4, and CH ₃ SO ₃ . Polymers can be prepared as described in French Patent Nos. 2,077,143 and 2,393,573.

··································

Quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers preferred for use in the present invention have a molecular weight of 1000 to

000,000, preferably 10,000 to 500,000, and even more preferably 10,000 to 100,000.

Such vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers are commercially available as copolymer 845 ®, Gafquat 734 ® or Gafquat 755 ° from ISP Corporation, New York, NY and Montreal, Canada or from BASF under the trade name Luviquat °.

In the present invention, the most preferred quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate (polycarbonate-11) are available from BASF.

Another preferred polymer is a polyvinylpyridine-N-oxide (PVNO) polymer available, for example, from Reilly. Preferred PVNO polymers have an average molecular weight of 1000 to 1000

000 000, more preferably 5000 to 500 000, and most preferably 15 000 to 50 000.

The average molecular weight is determined by light scattering as described in Barth, H. G., Mays, J. W., Chemical Analysis Vol. 113, “Modern Methods of Polymer Characterization.

The polymer is preferably present in the composition in an amount of 0.001% by weight to 10% by weight, more preferably 0.01% by weight to 5% by weight, and most preferably 0.1% to 2% by weight of the composition.

Other surfactants

The compositions of the present invention also optionally contain an additional surfactant as an optional but preferred component. Such other surfactants include nonionic surfactants, cationic surfactants, zwitterionic surfactants and / or amphoteric surfactants.

Amphoteric surfactants suitable for use in the present invention include amine oxides R ₁ R ₂ R ₃ NO, wherein each of R 1, R ₂ and R ₃ is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chain of 1 to 30 carbon atoms. The amine oxide surfactants preferred for use in the present invention are the amine oxides R 1 -NO 2, wherein R 1 is a hydrocarbon chain consisting of 1 to 30 carbon atoms, preferably 6 to 20, more preferably 8 to 16, and most preferably 8 to 12, and R ₂ and R ₃ are independently substituted or unsubstituted, linear or branched hydrocarbon chains consisting of 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and most preferably methyl. R ₃ is a saturated, substituted or unsubstituted linear or branched hydrocarbon chain. Suitable amine oxides for use herein are for instance natural blend C ₈ to C ₀ amine oxides as well as C ₂ to C ₆ amine oxides commercially available from Hoechst.

Zwitterionic surfactants suitable for use in the present invention contain a cationic hydrophilic group, i. a quaternary ammonium group, and an anionic hydrophilic group in the same molecule over a relatively wide pH range. Typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups such as sulfates, phosphonates and the like can be used.

The generic formula of the zwitterionic surfactants useful in the present invention is a compound of formula VIII:

R 1 -N ⁺ (R ₂ ) R ₃ ) R ₄ X '(VIII) wherein R _x is a hydrophobic group; R ₂ is hydrogen, C ₃ -C ₆ alkyl, hydroxyalkyl or other substituted C 1 -C ₆ alkyl; R ₃ is C ₁ -C ₆ alkyl, hydroxyalkyl or other substituted C 1 -C ₆ alkyl, which is also optionally attached to R ₂ to form cyclic structures with N, or C ₃ -C ₆ carboxylic acids, or • · · · · ·

A C 1 -C ₆ sulfonate; R 4 is a group attaching a cationic nitrogen atom to a hydrophilic group and is typically an alkylene, hydroxyalkylene or polyalkoxy group of 1 to 10 carbon atoms; and X is a hydrophilic group such as a carboxylate or sulfonate.

Preferred hydrophobic groups R 1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains containing linking groups such as amide and ester. More preferably, R ₁ is alkyl of 1 to 24 carbon atoms, preferably of 8 to 18, and even more preferably of 10 to 16. These simple alkyls are preferred for reasons of cost and stability. However, the hydrophobic group R ₂ also optionally is an amide radical R _a -C (O) -NH- (C (R _b ) ₂ ) _m , wherein R _a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably alkyl of 8 to 20 carbon atoms, preferably up to 18, even more preferably up to 16, R _b is selected from the group consisting of hydrogen and hydroxyl and is 4, preferably 2 to 3, even more preferably 3, provided that in group (C ( R _b ) ₂ ) is not more than one hydroxyl.

Preferably R ₂ is hydrogen or C ₂ to C ₃ alkyl, and more preferably methyl. Preferred _R3 is a Ci to _C4 carboxylic _acid, or a Cl to _C4 sulfonate or C _b to C ₃ alkyl and more preferably methyl. Preferred R ₄ is (CH ₂ ) _n / wherein n is an integer from 1 to 10, preferably from 1 to 6 and even more preferably from 1 to 3.

Some common examples of betaine / sulfobetaine are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, which are incorporated herein by reference.

Examples of particularly suitable alkyldimethyl betaines include coconut-dimethyl betaine, lauryldimethyl betaine, decyldimethyl betaine, 2- (N-decyl-N, N-dimethylammonium) acetate,

2- (N-coco- N, N-dimethylammonium) acetate, myristyldimethyl betaine, palmityldimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine. For example, coconut-dimethyl betaine is commercially available

It is Seppic under the trade name Amonyl 265. Laurylbetain is commercially available from Albright & Wilson under the trade name Empigen BB / L °.

Examples of amidobetaines include cocoamidoethyl betaine, cocoamidopropyl betaine or C ₁₀ to C ₁₄ fatty acylamidopropylene (hydropropylene) sulfobetaine. For example, C _0-C14 fatty acylamidopropylene (hydropropylene) sulfobetaine is commercially available from Sherex Company under the trade name "Varion CAS® sulfobetaine.

Another example of betaine is lauryl imino dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®.

Cationic surfactants suitable for use in the present invention include derivatives of quaternary ammonium, phosphonium, imidazolinium and sulfonium compounds. The cationic surfactants preferred for use in the present invention are quaternary ammonium compounds in which one or two hydrocarbon groups attached to the nitrogen are saturated, linear or branched alkyls having from 6 to 30 carbon atoms, preferably from 10 to 25 carbon atoms, and even more preferably The 12 to 20 carbon atoms and the remaining hydrocarbon groups (i.e., three when one hydrocarbon group is a long chain hydrocarbon as described above or two when two hydrocarbon groups are long chain hydrocarbons as described above) attached to the nitrogen are independently substituted or unsubstituted, linear or branched alkyls having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and most preferably methyl. Preferred quaternary ammonium compounds suitable for use in the present invention are non-chloride / non-halogen quaternary ammonium compounds.

Trimethyl quaternary ammonium compounds, such as myristyltrimethyl sulfate, are particularly preferred for use in the compositions of the present invention. And / or cetyltrimethylsulfate and / or (tallow-derived alkyl) trimethylsulfate. Such trimethyl quaternary ammonium compounds are commercially available from Hoechst or Albright & Wilson under the trade name EMPIGEN CM.

In one embodiment of the present invention, the compositions comprise, in addition to an anionic surfactant, a nonionic surfactant. Any nonionic surfactant known in the art is suitable for use in the present invention. Preferred nonionic surfactants include alkoxylated nonionic surfactants. Such alkoxylated nonionic surfactants are preferably alkoxylated alcohols containing a carbon chain consisting of 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, and most preferably 10 to 15 carbon atoms. Alkoxylation is provided by ethoxylate, propoxylate or butoxylate groups, preferably ethoxylate groups. In a preferred embodiment, the ethoxylated alcohol comprises 0.5 to 20, more preferably 2 to 10, and most preferably 4 to 6 ethoxy groups. Preferred alcohol ethoxylates are described in Example 1.

Terminated alkoxylated nonionic surfactants suitable for use in the present invention are compounds of Formula IX:

R _x (O-CH ₂ -CH ₂ ) _n - (OR ₂ ) _m -OR ₃ (ix) wherein R _x is C ₈ to C ₂₄ linear or branched alkyl or alkenyl, aryl, alkaryl, preferably R _x is C _{X8 8} to C alkyl or alkenyl, more preferably C ₁₀ to C ₁₅ alkyl or alkenyl, more preferably C _X o to C ₅ alkyl;

wherein R ₂ is C ₁ to C ₁₀ linear or branched alkyl, preferably C ₂ to C ₁₀ linear or branched alkyl;

wherein R ₃ is C ₁ -C ₁₀ alkyl or alkenyl, preferably C ₁ -C ₅ alkyl and more preferably methyl;

and wherein n and m are integers independently selected from the range of 1 to 20, preferably 1 to 10, more preferably 1 to 5; or mixtures thereof.

9 9 9 9 9 9 99 99 99 99 99 99

These surfactants are commercially available from BASF under the trade name Plurafac®, from Hoechst under the trade name Genapol® or from ICI under the trade name Symperonic®. Preferred terminated nonionic alkoxylated surfactants of formula (IX) are those commercially available under the tradename Genapol (R) 2.5 NR from Hoechst and Plurafac (R) from BASF.

Where the composition of the present invention also comprises a nonionic surfactant, it is preferably present such that the ratio of anionic surfactant to nonionic surfactant is 6: 1 to 1: 1, more preferably 5: 1 to 3: 1 and even more preferably 4: 1.

Other suitable surfactants include silicone surfactants such as organosilane or organosiloxane. Preferably, the silicone surfactants have a molecular weight of 600 to 10,000, more preferably 900 to 6000 and most preferably 3000. Such compounds are well known in the art, examples of which can be found, for example, in US 3 299 112, US 4 311 695, US 4 782 095, which are incorporated herein by reference. Suitable siloxane oligomers are described in US 4,005,028. Suitable silicone surfactants include polysiloxane polyethylene glycol copolymers, polyalkylene oxide treated polydimethylsiloxane copolymers.

Other suitable surfactants include fluorotensides that contain a hydrophilic and hydrophobic moiety. The hydrophilic moiety comprises an alkyl of 2 to 12 carbon atoms and an ester, sulfonate or carboxylate. The hydrophobic portion is fluorinated. Preferred fluorotensides include alkyl fluorocarboxylates such as ammonium perfluorocarboxylate and potassium fluoroalkylcarboxylate. Particularly suitable fluorotensides are aqueous mixtures of potassium fluoroalkylcarboxylate containing from about 40% to about 44% by weight of an alkyl chain of 8 carbon atoms, from about 1% to about 5% by weight of an alkyl chain of 6 carbon atoms, from about 1% to about 5% by weight of fluoroalkylcarboxylate. 4 carbon atoms in the alkyl chain, 1% fluoroalkylcarboxylate chain and 0.1% fluoroalkylcarboxylate chain.

% by weight of up to 7 atoms% by weight of up to 5 atoms% by weight of carbon in the alkyl% by weight of carbon in the alkyl

Enzyme

The enzyme or a mixture thereof is present in the composition of the present invention as an optional ingredient.

Preferred enzymatic materials are commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases commonly used in detergent builders or compositions. Suitable enzymes are discussed in U.S. Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazy and Esperase by Novo Industries A / S (Denmark), those sold under the trade names Maxatase, Maxacal and Maxap by Gist-Brocades , those sold under the trade names Opticlean and Optimase by Solvay Enzymes. The protease enzyme may be used in the compositions of the present invention in an amount of 0.0001% to 4% by weight of the active enzyme per weight of the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A / S. Highly preferred amylase enzymes are those described in PCT / US 9,703,635 and in WO95 / 26,397 and WO96 / 23,873.

· * · * * 4 ··

The amylase enzyme may be used in the compositions of the present invention in an amount of 0.0001% by weight to 2% by weight of the active enzyme per weight of the composition.

The lipolytic enzyme is optionally present in an amount (expressed as active lipolytic enzyme) of 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, and most preferably 0.001% to 0.5% by weight of the compositions.

Lipase is derived from fungi or bacteria obtained, for example, from Humicola sp. , Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically according to the present invention also lipase is obtained from Pseudomonas pseudoalcaligenes, which is described in the granted European patent EP-B-0 218 272.

Another preferred lipase of the present invention is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillius oryza as a host as described in European Patent Application EP-A-0 258 068, and is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Pat. No. 4,810,414, Huge-Jensen et al., issued Mar. 7, 1989.

customizable.

mutants is preferred

Hydrotropy

The compositions of the present invention comprise a hydrotrope as an optional ingredient.

Suitable hydrotropes of the present invention include sulfonated hydrotropes. Any sulfonated hydrotropes known to those skilled in the art can be used according to the present invention. In a preferred embodiment, alkylarylsulfonates or alkylarylsulfonic acids are used. Preferred alkylarylsulfonates include sodium, potassium, calcium and ammonium xylene sulfonates, sodium, potassium, calcium, and ammonium toluenesulfonates, sodium, potassium, calcium and ammonium. ammonium cumene sulfonates, sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalenesulfonates and mixtures thereof. Preferred alkylarylsulfonic acids include xylenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and mixtures thereof. Even more preferably, xylenesulfonic acid or p-toluenesulfonate or mixtures thereof are used.

Typically, the composition of the present invention comprises 0.01% to 20% by weight, preferably 0.05% to 10% by weight and even more preferably 0.1% to 5% by weight of the total sulfonated hydrotrope composition.

A sulfonated hydrotrope, if present, contributes to the physical and chemical stability of the compositions described in the present invention.

Ions

The compositions of the present invention further comprise ions, preferably added to the composition in the form of a salt. Preferred ions that can be used according to the present invention are sodium, ammonium, zinc, cadmium, nickel, copper, cobalt, zirconium, chromium and / or magnesium, and even more preferably calcium, zinc and / or magnesium. These ions may be added in the form of salts, for example chloride, acetate, sulfate, formate, carbonate and / or nitrate, or as a metal salt complex. For example, calcium in the form of calcium chloride, magnesium in the form of magnesium acetate or magnesium sulfate, zinc such as zinc chloride and ammonium ion such as ammonium carbonate can be added. Typically, such ions are present in an amount of up to 20% by weight, preferably 0.001% by weight to 10% by weight of the total composition.

Foaming control agents

The compositions of the present invention further optionally comprise a suds control agent such as a 2-alkyl alkanol or a mixture thereof as an optional ingredient. Particularly suitable for use in the present invention are 2-alkyl alkanols having an alkyl chain of 6 to 16 carbon atoms, preferably 8 to 12, and a terminal hydroxyl group, wherein the alkyl chain is substituted in position with an alkyl chain of 1 Such suitable compounds are commercially available, for example, in the Isofol® series, such as Isofol®12 (2-butyloctanol) or Isofol®16 (2-hexyldecanol).

Other suds control agents optionally include alkali metal salts (e.g., sodium or potassium) of fatty acids or their soaps, consisting of 8 to 24, preferably 10 to 20 carbon atoms.

Fatty acids, including those used in the production of soaps, can be obtained from natural sources such as glycerides derived from animals or plants (eg palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, lard, fat and mixtures thereof). Fatty acids can also be prepared synthetically (eg by oxidation of petroleum fractions or by the Fischer-Tropsch process). Alkali metal soaps can be made by direct saponification of fats and oils or by neutralizing free fatty acids, which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps. The term "suet in the present invention is used in connection with fatty acid mixtures which typically has a distribution of average carbon chain length of 2.5 wt% C _14, 2, 9 wt% C ₆ 23 wt% _C18, 2% palmitoleic acid, 41.5% by weight of acid

oleic acid and 3% by weight of linoleic acid (the first three fatty acids are saturated). Other mixtures with a similar distribution, with fatty acids being derived from various animal tallow and lard, also come under the term tallow. The tallow is also optionally solidified (ie, hydrogenated) thereby converting some or all of the unsaturated fatty acid residues into saturated fatty acid residues. As used herein, the term "coconut" refers to a fatty acid mixture that typically has an average carbon chain length distribution of 8% C ₈ , 7% C ₀ , 48% C ₁₂ , 17% C ₁₄ , 9% ₆ C, 2 wt% Cie, 7% oleic and 2% linoleic (the first six fatty acids listed being saturated). Other sources with a similar carbon chain length distribution such as palm kernel oil and babassu oil also fall under the term coconut oil.

Examples of other suitable suds control agents are silicones and silicon dioxide-silicone mixtures. Silicones can generally be described as alkylated polysiloxane materials, while silica is normally used in finely divided form, such as silica and silica xerogels and hydrophobic silicas of various types. These materials are used as particles in which the suds control agents are preferably releasably incorporated in a water-soluble or water-dispersible carrier substantially impermeable to the non-surfactant detergent. Alternatively, the suds control agent may be dissolved or dispersed in a liquid carrier and applied by spraying on one or more other ingredients.

A preferred silicone suds controlling agent is described in Bartollota et al., U.S. Pat. Other particularly suitable suds control agents are the self-emulsifying silicone suds control agents described in German patent application DTOS 2,646,126, issued on September 2, 2002. • »· · · · ·

An example of such a compound is DC-544, commercially available from Dow Corning which is a siloxane-glycol copolymer.

Particularly preferred suds control agents are described in co-pending European Patent Application No. 92 201 649.2. These compositions optionally comprise a silicone / silica mixture in combination with a non-porous silica such as Aerosil.

A particularly preferred suds control agent is a suds control agent system or a mixture of silicone oils and 2-alkyl alkanols.

Typically, the compositions of the present invention contain up to 4% by weight of the total suds control agent composition or mixtures thereof, preferably 0.1% to 1.5% by weight, and most preferably 0.1% to 0.8% by weight.

Solvents

The compositions of the present invention further optionally comprise a solvent or a mixture thereof. Solvents for use in the present invention include all those known to those skilled in the art. Suitable solvents for use in the present invention include ethers and diethers consisting of 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms, glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C 1 -C ₅ alcohols, linear C 1 -C ₅ alcohols, C ₈ -C ₁₄ alkyl, and cycloalkyl hydrocarbons and halogen hydrocarbons, C ₆ -C ₁₆ glycol ethers and mixtures thereof.

Suitable glycols which can be used according to the present invention are HO-CR ₁ R ₂ -OH, wherein R ₄ and R ₂ are independently H or C ₂ which can be used methoxyoctadecanol according to and / or up to C 10 saturated or unsaturated aliphatic hydrocarbon chain and / or cycle. Suitable glycols which can be used according to the present invention are dodecanglycol and / or propanediol.

Suitable alkoxylated glycols which can be used according to the present invention are R- (A) _n -R 1 -OH, wherein R is H, OH, linear saturated or unsaturated alkyl having 1 to 20 carbon atoms, preferably 2 to 15, and even more preferably from 2 to 10, wherein R 3. is H or a linear saturated or unsaturated alkyl of 1 to 20 carbon atoms, preferably 2 to 15 and even more preferably 2 to 10, and A is alkoxy, preferably ethoxy, methoxy or propoxyl, and preferably 5, preferably 1 to 2 Suitable alkoxylated glycols of the present invention are ethoxyethoxyethanol.

Suitable alkoxylated aromatic alcohols which can be used according to the present invention are R (A) _n -OH, wherein R is an alkyl substituted or non-alkyl substituted aryl having 1 to 20 carbon atoms, preferably 2 to 15 and even more preferably 2 to 15 carbon atoms. 10, wherein A is alkoxy, preferably butoxyl, propoxyl and / or ethoxy, and n is an integer of 1 to 5, preferably 1 to 2. Suitable alkoxylated aromatic alcohols are benzoxyethanol and / or benzoxypropanol.

Aromatic alcohols suitable for use in the present invention are R-OH, wherein R is an alkyl substituted or non-alkyl substituted aryl consisting of 1 to 20 carbon atoms, preferably 1 to 15 and even more preferably 1 to 10. For example, a suitable alcohol for use in of the present invention is benzyl alcohol.

Aliphatic branched alcohols suitable for use in the present invention are R-OH, wherein R is a branched saturated or unsaturated alkyl having 1 to 20 carbon atoms, preferably from 2 to 15 and even more preferably from 5 to 12. Particularly suitable aliphatic branched alcohols which can be used by

of the present invention are 2-ethylbutanol and / or 2-methylbutanol.

Alkoxylated aliphatic branched alcohols suitable for use in the present invention are R (A) _n -OH, wherein R is a branched saturated or unsaturated alkyl having 1 to 20 carbon atoms, preferably 2 to 15, and even more preferably 5 to 12, wherein A is alkoxy, preferably butoxy, propoxy and / or ethoxy, and n is an integer of 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol.

Suitable alkoxylated linear C ₁ -C ₅ alcohols which can be used according to the present invention are R (A) _n -OH, wherein R is a linear saturated or unsaturated alkyl having 1 to 5 carbon atoms, preferably 2 to 4, wherein: A is alkoxy, preferably butoxyl, propoxyl and / or ethoxy, and n is an integer of 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic linear C ₁ to C ₅ alcohols are butoxypropoxypropanol (n-BPP), butoxyethanol, butoxypropanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxypropoxypropanol is commercially available under the trade name n-BPP ° from Dow Chemical.

Linear C ₁ -C ₅ alcohols suitable for use in the present invention are R-OH, wherein R is a linear saturated or unsaturated alkyl having 1 to 5 carbon atoms, preferably 2 to 4. Suitable linear C ₁ to C ₅ alcohols are methanol , ethanol, propanol and mixtures thereof.

Other suitable solvents include butyldiglycol ether (BDGE), butyltriglycol ether, teramyl alcohol and the like. Partially preferred solvents suitable for use in the present invention are butoxypropoxypropanol, butyldiglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol, and mixtures thereof.

Other suitable solvents include light petrols, more preferably light petroleum commonly known as white spirit.

Typically, the compositions of the present invention that are aqueous comprise up to 30% by weight of the total solvent composition or mixtures thereof, preferably up to 10% by weight and even more preferably up to 8% by weight.

However, if the composition is non-aqueous as described below, optionally it preferably comprises 60% to 99.5% by weight, more preferably 70% to 99% by weight, even more preferably 90% to 99% by weight, and most preferably 95% by weight. up to 99% by weight of the total solvent composition or mixtures thereof.

pH buffers

In an embodiment of the present invention, the compositions are prepared at a neutral pH, typically 5.5 to 8.5, more preferably 7 to 8. The compositions of the present invention further comprise a pH buffer or a mixture thereof, i. a system consisting of a compound or combination of compounds whose pH changes only slightly when the strong acid or base is added.

pH buffers suitable for use in the present invention under neutral to basic conditions include borate pH buffer, phosphonate, silicate, and mixtures thereof. Borate pH buffers suitable for use in the present invention include the alkali metal salts of borates and alkyl borates and mixtures thereof. Borate pH buffers suitable for use in the present invention include the alkali metal salts of borates, metaborate, tetraborate, octoborate, pentaborate, dodecaborate, boron trifluoride and / or alkyl borates consisting of 1 to 12 carbon atoms and preferably 1 to 4 carbon atoms. Suitable alkyl borates include methyl borate, ethyl borate and propyl borate. Particularly preferred according to the present invention are alkali metal salts of metaborate (eg sodium metaborate), tetraborate (eg sodium tetraborate decahydrate) or mixtures thereof.

·

Boron salts such as sodium metaborate and sodium tetraborate are commercially available from Borax and Societa Chimica ® ®

Larderello under the trade names sodium metaborate and Borax.

pH buffers suitable for use in the present invention under acidic conditions include organic acids and mixtures thereof. Organic acids suitable for use in the present invention include monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids or mixtures thereof. Organic acids preferred for use in the present invention include acetic acid, citric acid, malonic acid, maleic acid, lactic acid, glutaric acid, glutamic acid, aspartic acid, methylsuccinic acid, succinic acid, or mixtures thereof. Citric acid and succinic acid and mixtures thereof are particularly preferred in the present invention.

Citric acid is commercially available as an aqueous solution from Jungbunzlauer under the trade name Citric acid (R).

Typically, the composition of the present invention comprises up to 15% by weight of the total pH buffer composition or mixtures thereof, preferably 0.01% to 10% by weight, more preferably 0.01% to 5% by weight, and most preferably 0.1% to 3% by weight weight.

problems.

resin

Thickener

The composition of the present invention preferably comprises a thickener. A thickener is a component that is specifically added to the composition of the present invention to increase the viscosity of the composition.

Suitable thickeners are those known in the art. Examples of thickeners include polymers of the type (eg, xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof, and polycarboxylate polymers.

• · ·············································

In a particularly preferred embodiment of the present invention, the thickener comprises a resin type polymer or a polycarboxylate polymer. Particularly preferred examples of such thickeners are xanthan resin and crosslinked polycarboxylate polymer.

The resin type polymer may be selected from the group consisting of polysaccharide hydrocolloids, xanthan gum, guar gum, succinoglucan gum, cellulose, derivatives thereof and mixtures thereof.

In a preferred aspect of the present invention, the resin type polymer is xanthan resin or a derivative thereof.

The polycarboxylate polymer is a homo or copolymer of monomer units selected from acrylic acid, methacrylic acid, maleic acid, malic acid and maleic anhydride. Preferred polycarboxylate polymers are carbopol from BF Goodrich. Suitable polymers have a molecular weight of 10,000 to 100,000,000, and most preferably 1,000,000 to 10,000,000.

Radical scavengers

The compositions of the present invention optionally comprise radical scavengers or mixtures thereof.

Radical scavengers suitable for use in the present invention include the well-known substituted mono and dihydroxybenzenes and analogs thereof, alkyl and aryl carboxylates, and mixtures thereof. Preferred radical scavengers for use in the present invention include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butylhydroxyanisole, banzoic acid, toluic acid, catechol, tert-butylcatechol, benzylamine,

1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, propyl gallate or mixtures thereof, and di-tert-butylhydroxytoluene is highly preferred. radical scavengers such as N46

propyl gallate is commercially available from Nipa Laboratories under the trade name Nipanox SI.

When used, radical scavengers are typically present in an amount of up to 10% by weight of the total composition and preferably 0.001% to 0.5% by weight.

Fragrances

Fragrances suitable for use in the present invention include materials that provide olfactory aesthetic benefits and / or cover any " chemical odor that the product may have. The main function of the small proportion of highly volatile, low-boiling (low boiling) aromatic components in these fragrances is to improve the odor of the product itself rather than to affect the subsequent odor of the purified product. However, some less volatile, higher-boiling fragrance ingredients provide fresh and clean impact to the surfaces to be cleaned, and it is desirable that these ingredients be placed and present on a dry surface. The fragrance components can be readily solubilized in the compositions, for example, with an amphoteric surfactant. Fragrance ingredients and compositions suitable for use in the present invention are well known in the art. The choice of any fragrance ingredient or amount of fragrance is based solely on aesthetic requirements.

Suitable fragrances and compositions can be readily found in the art, including, for example, U.S. Pat. Nos. 4,145,184, Brain and Cummins, issued March 20, 1979, 4,209,417, Whyte, issued June 24, 1980, 4,515,705, Moeddel, issued May 7, 1985, and 4,152,272, Young, Issued 1. all of these patents are incorporated herein by reference. Generally, the degree of shelf life of the fragrance is roughly in proportion to the percentage of fragrance material used. The relatively long-lasting fragrances contain at least 1% by weight, preferably 10% by weight, of the fragrance materials. Durable fragrance materials are those that leave fragrance compounds on the surface during • · · ·

4Ί cleaning and are detectable by people with normal sense of smell. Such materials typically have vapor pressures lower than the average fragrance material. They also typically have a molecular weight of 200 or more and are detectable in amounts lower than the average fragrance material. The fragrance ingredients useful in the present invention, together with their fragrance characteristics and their physical and chemical properties such as boiling point and molecular weight, are listed in "Perfume and Flavor Chemicals" by Steffen Arctander, published by the author, 1969, which is are incorporated herein by reference.

Examples of highly volatile, low-boiling, fragrance ingredients are anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, isobornylacetate, camphene, ciscitral (neral), citronellal, citronellol, citronelllyl acetate, p-cymene, decanal, dihydrolinalool, dihydromyrbinol, geresialenyl , geraniol, geranyl acetate, geranylnitrile, cis-3-hexenylacetate, hydroxycitronellal, d-limonene, linalooloxide, linalylacetate, linalylpropionate, methylanthranilate, α-methylionone, methylnonylacetaldehyde, methylphenylcarbinylacetate, 1-methyl acetate, menthen, myenol, isenonethronone , nerylacetate, nonylacetate, phenylethyl alcohol, α-pinene, β-pinene, γ-terpine, α-terpineol, β-terpineol, terpinyl acetate and vertenex (p-tert-butylcyclohexyl acetate). Some natural oils also contain a large percentage of highly volatile fragrance ingredients. For example, lavandine contains as main ingredients: linalool, linalyl acetate, geraniol and citronellol. Lemon oil and orange terpenes both contain 95% by weight of d-limonene.

Examples of moderately volatile fragrance ingredients are amyl cinnamic aldehyde, isoamyl salicylate, β-caryophyllene, cedren, cinnamon alcohol, coumarin, dimethylbenzylcarbinylacetate, ethylvanillin, eugenol, isoeugenol, fluoroacetate, heliotropin, 3-cis-hexenylsalicylate, t-hexylsalicylate, [alpha] -methyl-cinnamic aldehyde), [gamma] -methylionone, • nerolidol, patchouli alcohol, phenylhexanol, [beta] -seline, trichloromethylphenylcarbinyl acetate, triethyl citrate, vanillin and veratraldehyde. The cedar wood terpenes consist mainly of α-cedrene, β-cedrene and other C ₁ H ₂ 4 sesquiterpenes.

Examples of low-volatility, high-boiling fragrances are benzophenone, benzyl salicylate, ethylenebrassylate, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2 -). benzopyran), hexyl cinnamic aldehyde, lyral (4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-10-carboxaldehyde), methylcedrylon, methyldihydrojasmonate, methyl-β-naphthyl ketone, musk indanone, musk ketone, musk tibetene and phenylethylphenene.

The choice of a particular fragrance component is primarily determined by aesthetic requirements.

The compositions of the present invention optionally comprise the fragrance component or mixtures thereof in amounts of up to 5.0% by weight of the total composition, preferably in amounts of 0.1% to 1.5% by weight.

Minority components

Dyes, including well known dyes and pigments, can be added to the composition in small amounts.

Other preferred, albeit minor, components are preservatives. Preservatives refer to any compound that, when added to a composition, kills or at least inactivates microbes, such as bacteria and fungi. Any preservatives currently available on the market can be used in the present invention. See, for example, those disclosed in HAPPI, May 1999, pp. 78-94. Particularly preferred preservatives are phenoxyethanol available, for example, from BASF under the trade name Protectol PP or gluteraldehyde available, for example, from BASF under the trade name Protectol GDA.

Form of the device

The compositions of the present invention are in any form, for example, in the form of a liquid, gel, foam, particle or tablet.

When the composition of the present invention is a liquid, it is aqueous or non-aqueous, diluted or concentrated. When the composition is aqueous, it preferably comprises from 1% to 99% by weight of water, more preferably from 50% to 99% by weight, and most preferably from 80% to 95% by weight of water. As noted above, the composition is alternatively non-aqueous. Non-aqueous means that the composition is substantially free of water. More specifically, the compositions do not contain any intentionally added water and thus only crystalline water is present in the composition, for example after mixing the raw materials.

Packaging form of preparations

The compositions of the present invention may be packaged in various suitable containers known to those skilled in the art depending on the form of the composition. The liquid compositions are preferably packaged in conventional bottles that do not chemically react with the stored composition. The bottles are preferably made of plastics.

In one preferred embodiment, the composition may be packaged in spray dispensers. Such containers are usually made of synthetic organic polymeric plastic materials. The sprayer on the container is manual or electric. The hand sprayer includes a trigger actuated sprayer or a pump actuated sprayer. Suitable sprayers useful in the present invention include foam type trigger sprayers sold, for example, by Specialty Packagign products, Inc. or Continental Sprayers, Inc. These types of scavengers are described, for example, in U.S. Pat. No. 4,601,311 to Dunnining et al. and US-4,646,973 and US-4,538,745, both • ·

Focarracci. Especially preferred for use herein are nebulizers such as T 8500 ° commercially available from Continental Spray International or T 8100 ° commercially available from Canyon, Northern Ireland. In such a nebulizer, the liquid composition is divided into fine liquid droplets in a spray directed towards the surface to be treated. In this sprayer, the means contained in the sprayer body is pushed out by the sprayer head by the energy delivered to the pump mechanism by the user as the user activates the pump mechanism. More specifically, in this sprayer head, the device is pushed against an obstacle, such as a grid or cone, and the like, to achieve shocks that help atomize the liquid composition, i. assist in the formation of fluid droplets.

Alternatively, the composition may be packaged in an electric sprayer in which the electric power is used for spraying.

In another preferred embodiment of the present invention, the liquid composition of the present invention is applied to the surface by a dispensing device

This nebulizer is a container through which the composition is dispensed: a spray.

Such nebulizers include a pump means ("nebulizer using any source of compressed gas, such as an aerosol can or a volume compensator. Pump nebulisers can be driven manually or electrically. These nebulisers are particularly preferred when large areas are treated and / or large quantities of product are applied. These sprayers ensure that a large amount of product is applied to the heavily soiled surface, as well as providing even coverage.

with benefit atomizers. at least one opening, so that they arise droplets means for transport pump) or pracuj e

to optimize spraying time, the product will best dry on the surface to be cleaned within a reasonable time.

Preferred atomizers according to the present invention are hand or electrically driven pump atomizers. Typical, powered actuated sprayers include a button operated or trigger actuated pump. A preferred sprayer of the present invention is a container in which the means for conveying the composition comprises an electrically driven pump and a spray arm. The spray arm is either elongated or extendable and has at least one opening such that during operation the means is pumped by an electrically driven pump from the container through the spray arm into the opening from which it is dispensed. Preferably, the spray arm is connected to the container by a flexible connector. The spray arm has at least one opening located along its length. The spray arm facilitates control when the device is sprayed and therefore the application accuracy is higher. The electrically driven pump is, for example, a gear pump, centrifugal pump, piston pump, screw pump, peristaltic pump, diaphragm pump or any other miniature pump. In a highly preferred embodiment of the electrically driven pump for use in the present invention, the pump is a gear pump with a typical speed of 6000 rpm to 12,000 rpm. The electrically driven pump is driven by means such as an electric motor having a typical torque of 1 mN.m to 20 mN.m. An electric motor having an energy source. The power source is either electricity (possibly via a transformer) or disposable batteries or rechargeable batteries. Spray extended. However, such an arm is optionally a fixed spray arm is difficult to store and preferably the spray arm is extendable either in a telescopic or collapsible manner.

Method of cleaning

The present invention also encompasses a method of cleaning a surface, for example an exterior surface of a vehicle, eg a car, wherein the surface to be cleaned is contacted with the composition of the present invention.

Surfaces in the present invention refer to any kind of surfaces typically found in houses, such as kitchens, bathrooms or exterior surfaces of a vehicle such as floors, walls, bags, windows, sinks, showers, shower curtains, washbasins, toilets, dishes, solid fixtures and the like made of a variety of materials such as ceramics, vinyl, non-waxed vinyl, linoleum, melamine, glass, any plastic, plasticized wood, metal or any painted or varnished or sealed surface and the like. Surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, dryers, stoves, microwaves, dishwashers and so on. The present composition is particularly effective for cleaning painted surfaces of, for example, the outer painted surfaces of vehicles such as cars.

Alternatively, the surface to be cleaned can be pre-rinsed with water. The composition is then applied to the surface. The composition can be applied using a cloth or sponge to which the composition has been applied. The composition can be applied by pouring onto the surface. Alternatively, the composition may be applied by spraying onto the surface with a sprayer as described above.

Once applied to the surface, the surface can then be rinsed, usually with water, and allowed to dry naturally. Alternatively, the user may wait between applying the composition and rinsing with water to give the composition maximum exposure time. It is particularly advantageous due to the present invention that when the surface is cleaned as described above and allowed to dry naturally, no stains or streaks of water are produced.

···· · · «• · · · · * ·

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be further illustrated by the following examples. All amounts are in percent by weight of the composition.

AND II III IV IN C12 alkyl sulfate ₅ 2 C12 LAS 0.7 2 1,2 2 Dioctylsulfosuccinate 0.2 Ethoxysulfosuccinate 1 Cio (E11) 2 C12 to _C14 (E05) 0.1 6 0.5 C ₉ to Cn (E05) 1.3 0.5 C12 to Cn (EO2,2) 6 Cn (E05) 0.1 6 1.3 C12 to C14 dimethylamine oxide 1.4 Sodium cumenesulfonate 2.5 5 Ethoxylated tetraethylene- pentamine 0.05 0.08 Ethoxylated hexamethylenediamine quart. 0.05 0.08 Poly (ethyleneimine) ethoxylate 0.05 0.02 SSP 0.05 - Xanthan resin 0.05 HEDP 2 3 4 Nitriloacetic acid 4 1 Citric acid 2 Sodium silicate 0.3 Butyldiglycol ether 4 N-butoxypropoxypropanol 1 2-butoxyethanol 4 6 -

• 00000 0 «0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Gluteraldehyde 0,035 0,025 0,025 0,025 0,035 Phenoxyethanol 0.2 0.2 NaOH to pH 7.5 to pH 7.5 to pH 7.5 to pH 7.5 Acetic acid to pH 7.5 Water like the rest

SSP is a polyethylene amine of 3000 molecular weight propoxylated to step 3 and ethoxylated to step 27.

Industrial applicability

The compositions of the present invention are industrially useful for the production of cleaning compositions suitable for cleaning the exterior surface of vehicles, particularly automobiles.

PP Am »AA AA

Claims (10)

PATENT CLAIMS CLAIMS 1. A detergent composition suitable for cleaning the exterior surface of vehicles, comprising a chelating agent, an anionic surfactant in a ratio of 4: 1 to 1: 4 and a polymeric compound selected from the group consisting of a soil-repellent polymer, a soil-suspending polymer, and a mixtures thereof. A detergent composition according to the preceding claim, wherein the chelating agent is a chelating agent comprising phosphorous acid or salts thereof. 3. A detergent composition according to claim 2 wherein the chelating agent is selected from alkali metal ethane-1-hydroxy diphosphonate, alkylene poly (alkylene phosphonate), aminoaminotrimethylene phosphonic acid, nitrilotrimethylene phosphonate, ethylenediaminetetramethylene phosphonate, diethylenetriaminpentamethylene phosphonate. A detergent composition according to any preceding claim wherein the anionic surfactant is selected from alkyl sulfate, alkyl or alkylarylsulfonate, sulfosuccinate surfactants, and mixtures thereof. A detergent composition according to any one of the preceding claims, further comprising a nonionic surfactant, preferably an alkoxylated alcoholic nonionic surfactant. cø vo 7 ~ W / -S ~ 03 ** ···· · · · »f f f f f f f l l. “• · ·« Γ! * 56 ´ .. · · .. ’... .... A detergent composition according to any one of the preceding claims, wherein the polymer is a soil repellent polymer selected from vinylpyrrolidone homo or copolymers, polysaccharide polymers, polyalkoxylene glycols, and mixtures thereof. A cleaning composition according to any one of the preceding claims, wherein the polymer is a soil-suspending polymer selected from the group consisting of polyalkoxylated polyamines, preferably ethoxylated polyethylene amines. A cleaning composition according to any one of the preceding claims, further comprising a surface-retaining polymer described in the present invention. A method of cleaning the exterior surface of a vehicle comprising: (i) wetting the means of transport, if any; (ii) contacting the vehicle with the vehicle of any preceding claim; and (iii) rinsing the vehicle with water. Use of a cleaning composition according to any one of claims 1 to 9 for cleaning the exterior surface of a vehicle.