WO1999028423A1

WO1999028423A1 - Method for cleaning hydrocarbon-containing soils from surfaces

Info

Publication number: WO1999028423A1
Application number: PCT/US1998/025860
Authority: WO
Inventors: Terry Crutcher
Original assignee: Tomah Products, Inc.
Priority date: 1997-12-04
Filing date: 1998-12-04
Publication date: 1999-06-10
Also published as: CA2278788A1

Abstract

This invention is directed to an improved method for removing hydrocarbon-containing soils. The invention consists of preparing a detergent composition and applying the composition to the surface to be cleaned. Broadly, the detergent composition consists of from 1 to 99 % by weight of a polyalkoxylated amine and from 99-1 % by weight of a water-soluble surfactant. Other constituents may be added to enhance performance. The invention has desirable foamability characteristics.

Description

Title: METHOD FOR CLEANING HYDROCARBON-CONTAINING SOILS FROM SURFACES

Field of the Invention

This invention is related generally to cleaning and, more specifically, to a method of cleaning hydrocarbon- containing soils using an improved detergent composition.

Background of the Invention

It is well known that removing oily, greasy and other hydrocarbon-containing soils from surfaces can be a difficult task. These hydrocarbon-containing soils include a wide range of substances such as motor oils, lards, lithium greases and other oily, greasy materials. Such soils are present in almost any household or commercial environment and can adhere to almost any surface including, without limitation, surfaces such as metal, wood, glass, synthetic and fabric.

Typical cleaning compounds used for removing these types of soils include solvents to solubilize the hydrocarbon-containing soils. While solvents present an effective method of removing these types of soils, they also include volatile organic compounds ("V.O.C.") which may be hazardous . In recent years many of the solvent containing cleaners have been completely banned or highly regulated because of the V.O.C. discharge. This regulation has created a need for alternative cleaning agents which do not include chlorofluorocarbons, V.O.C. s or other potentially hazardous constituents.

In addition, it is desirable to select a cleaning composition wherein the foamability of the composition can be easily controlled. Such control should include the ability to increase as well as decrease the level of foaming.

An improved method of cleaning oily, greasy and other hydrocarbon-containing soils from surfaces which is efficacious and yet avoids the need for potentially hazardous solvents and which has easily controllable foam characteristics would represent an important advance in the art .

Objects of the Invention

It is an object of this invention to provide an improved method of cleaning hydrocarbon-containing soils that overcomes some of the problems and shortcomings of the prior art.

Another object of this invention is to provide an improved method of cleaning hydrocarbon-containing soils that includes a detergent composition with improved synergistic, cost-effective surface cleaning capabili- ties.

It is a further object of this invention to provide an improved method of cleaning hydrocarbon-containing soils that offers versatile high o low foamability suitable for a variety of applications. Yet another object of this invention is to provide an improved method of cleaning hydrocarbon-containing soils that includes a detergent composition which can be prepared and used in a dilute form or as a 100% actives concentrate . An additional object of the invention is to provide an improved method of cleaning hydrocarbon-containing soils which is effective yet does not require the use of organic solvents or builders .

These and other important objects will be apparent from the descriptions of this invention which follow. Summary of the Invention

The present invention is directed toward an improved method of cleaning oily, greasy and other hydrocarbon- containing soils from a wide range of surfaces including, without limitation, surfaces such as metal, wood, glass, synthetic materials and fabric. The invention is highly efficacious in removing these types of soils. Indeed, and as set forth in the Examples below, the constituents of the composition appear to have a synergistic effect in removing hydrocarbon-containing soils. The method accomplishes this desirable result without the need for solvents typical of the prior art cleaning compositions and methods .

The invention comprises the steps of preparing a detergent composition and applying the detergent composition to the object or surface to be cleaned. In one embodiment, the detergent composition comprises from 1 to 99% by weight of a polyalkoxylated amine and from 99-1% by weight of a water-soluble surfactant. The polyal- koxylated amine has a general structural formula selected from the group consisting of:

R³

/ R¹ - RHOCH₂CH₂CH₂-)-_nN

R⁴

wherein R¹ is selected from an alkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms, R² is from 0 to 7 moles of alkoxylated units, n is 0 or 1, R³ and R⁴ are each selected from a hydrogen atom ("H") and from 1 to 5 moles of alkoxylated units such that R³ and R⁴ are not both H and R³ and R⁴ combined include about 5 or fewer moles of alkoxylated units, and

R⁷ R⁸

I / R⁵ -R⁶ 0CH₂CH₂CH_{2 n} NCH₂CH₂CH₂N

R⁹ wherein R⁵ is selected from an alkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms, R⁶ is from 0 to 7 moles of alkoxylated units, n is 0 or 1, R⁷, R⁸ and R⁹ are each selected from H and frc.n 1 to 5 moles of alkoxylated units such that R⁷, R⁸ and R⁹ are not each H. Mixtures of the amines may be used.

The water-soluble surfactant is selected from the group consisting of nonionics, alkyl ether sulfates, amine oxides, amphoterics and water soluble quaternary ammonium compounds. Mixtures of surfactants may be used. These compounds will be described in greater detail below.

In another embodiment, the detergent composition of the inventive method comprises three main components. The first component is from 0.5-99% by weight of a polyalkoxylated amine as set forth above while the second component is from 99-0.5% by weight of a water-soluble surfactant selected from the group consisting of non- ionics, alkyl ether sulfate and am hoteric compounds as set forth above.

The third component consists of from 99-0.5% by weight of a third constituent selected from the group consisting of the amine oxides and quaternary ammonium compounds set forth above and an alkyl acid alkanolamide compound component described more fully below.

As used throughout the specification and claims, terms such as "between 6 and 22 carbon atoms," C3 to CIO and C_x_₅ are used to designate carbon atom chains of varying lengths and to indicate that various conformations are acceptable including branched, cyclic and linear conformations. The terms are further intended to designate that various degrees of saturation are acceptable. The inventive polyalkoxylated amines, water soluble surfactants and the third component set forth above may be isolated or present within a mixture and remain within the scope of the invention. Detailed Descriptions of the Preferred Embodiments

The detergent composition of the invention may be prepared as a solid or liquid using any conventional method. There is no particular order in which the constituents are combined. Liquid and solid forms of the invention require good dispersal of the constituents for maximum effectiveness. Solid forms of the composition may be prepared through known methods such as dry blending or spray drying in which the composition is applied to a dry substrate such as a zeolite.

The detergent composition may be applied in any suitable manner such as with an atomizer or other form of spray, by immersing the surface to be cleaned in the composition, pouring the detergent composition on the soil to be removed or by mixing a solid form of the composition with a solvent and the article to be cleaned. As will be discussed in the Examples below, the detergent composition is effective in degrading and removing the soil upon application. As summarized above, one embodiment of the detergent composition comprises from 1 to 99% by weight of a polyalkoxylated amine and from 99-1% by weight of a water- soluble surfactant. The polyalkoxylated amine has a general structural formula selected from the group consisting of:

R³

/ R¹ - R²- OCH₂ CH₂ CH₂ -_nN \

R⁴

wherein R¹ is selected from an alkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms, R² is from 0 to 7 moles of alkoxylated units; n is 0 or 1, R³ and R⁴ are each selected from a hydrogen atom ("H") and from 1 to 5 moles of alkoxylated units such that R³ and R⁴ are not both H and R³ and R⁴ combined include about 5 or fewer moles of alkoxylated units, and R⁷ R⁸

I /

R⁵ - R⁶ 0CH₂CH₂CH_{2 n} NCH₂CH₂CH₂N R⁹

wherein R⁵ is selected from an alkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms; R⁶ is from 0 to 7 moles of alkoxylated units; n is 0 or 1; R⁷, R⁸ and R⁹ are each selected from H and from 1 to 5 moles of alkoxylated units such that R⁷, R⁸ and R⁹ are not each H. The alkoxylated units are preferably selected from the group consisting of ethyleneoxy, propyleneoxy, butyleneoxy and mixtures thereof. Preferably, R³ and R⁴ combined include from about 1 to 2 moles of alkoxylated units. R⁷, R⁸ and R⁹ combined preferably include from about 3 to 5 moles of alkoxylated units.

Tomah Products, Inc. of Milton, Wisconsin manufactures and sells polyalkoxylated amines useful in practicing the invention. Examples of suitable Tomah polyalkoxylated amines include E-14-2 and E-DT-3.

A wide range of nonionic water-soluble surfactants are suitable for use in the invention. Such surfactants include alkoxylated alkyl phenols, alkoxylated alcohols, polypropylene glycol alkoxylates, alkoxylated diamines, alkoxylated glycosides and amine oxides.

Preferred alkoxylated alkyl phenols include the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the poly- ethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles of ethylene oxide per mole of alkyl phenol . Preferred alkoxylated alkyl phenols are nonylphenol 9 mole ethoxylate and octylphenol 9 mole ethoxylate. Commercially available nonionic surfactants of this type include Igepal™ CO-630, marketed by the Rhone-Poulenc; and Triton™ X-45, X114, X100 and X102, all marketed by the Union Carbide Corporation. Useful alkoxylated alcohols include the alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either by straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols having an alkyl group containing from 10 to 14 carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of alcohol.

Preferred alkoxylated alcohols include dodecyl alcohol 7 mole ethoxylate, tridecyl alcohol 7 mole ethoxylate, tetradecyl alcohol 7 mole ethoxylate, pentadecyl alcohol 7 mole ethoxylate and hexadecyl alcohol 7 mole ethoxylate .

Examples of commercially available nonionic surfactants of this type include Tergitol™ 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide) , Tergitol™ 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution) , both marketed by Union Carbide Corporation; Neodol™ 45-9 (the condensation product of

C14 - C15 linear alcohol with 9 moles of ethylene oxide) , Neodol™ 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol™ 45-7 (the condensation product of C14 - C15 linear alcohol with 7 moles of ethylene oxide) , Neodol™ 45-4 (the condensation product of C14 - C15 linear alcohol with 4 moles of ethylene oxide) , marketed by Shell Chemical Company, and Kyro™ EOB (the condensation product of C13 - C15 alcohol with 9 moles ethylene oxide) , marketed by The Procter & Gamble Company.

Suitable polypropylene glycol alkoxylates include the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol . The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydro- phobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.

Preferred polypropylene glycol alkoxylates include block polymers of propylene oxide and block polymers of ethylene oxide. Examples of compounds of this type include certain of the commercially-available Pluronic™ surfactants, marketed by BASF.

Preferred alkoxylated diamines include the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine . The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydro- phobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about

40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Preferred alkoxylated diamines are selected from the group consisting of block polymers of propylene oxide and block polymers of ethylene oxide. Commercial examples of this type of nonionic surfactant include certain of the commercially-available Tetronic™ compounds, marketed by BASF.

Suitable alkoxylated glycosides include alkylpolysaccharides disclosed in U. S. Patent 4,565,647 (Llenado) having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside . ) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units .

The preferred alkylpolyglycosides have the formula:

R²0 (C_nH_2nO)_t (glycosyl)_x

wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxylalkyl , hydroxyalkylphenyl , and mixtures thereof in which the alkyl groups contain from

10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.

The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position) . The additional glycosyl units can then be attached between their 1- position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2- position. Dodecylpolyglycoside is an illustrative preferred alkoxylated glycosides.

A representative commercially-available example of a C12 to C16 alkyl polyglycoside is GLUCOPON™ 600 which is an alkyl polyglycoside surfactant solution (50% active) which has an average degree of polymerization of 1.4 glucose units, a hydrophilic-lipophilic balance of 11.6 (calculated value) and in which the alkyl group contains 12 to 16 carbon atoms (average C12.8). A representative example of a C3 to CIO alkyl polyglycoside is GLU0C0P0N™ 225 which is an alkyl polyglycoside surfactant solution (65% active) which has an average degree of polymerization of 1.6 glucose units, a hydrophilic-lipophilic balance of 13.6 (calculated value) and in which the alkyl group contains 8 to 10 carbon atoms (average C9.1) . Such surfactants are commercially available from Henkel Corporation, Ambler, PA 19002 and are described in U. S. Pat. No. 5,266,690.

The amphoteric water-soluble surfactants may include cocoamidopropyl betaine and isodecyloxypropylimino- propionate, sodium salts. Commercially-available forms of these amphoterics include Tomah Products, Inc . ' s

Amphoteric L and Alkalai Surfactant NM and Monoteric COAB from Mona Industries, Inc., Paterson, New Jersey.

Preferred amine oxide water-soluble surfactants have the general structural formula:

R¹³

R¹⁰ -Rθ0CH₂CH₂CH₂-)-_nN→0 R¹⁴ wherein R¹⁰ is selected from an alkyl, alkylamidopropyl , hydroxyalkyl , aryl or alkylaryl group having between 6 and 22 carbon atoms, R¹¹ is from 0 to 7 moles of alkoxylated units, n is 0 or 1, R¹³ and R¹⁴ are each selected from 1 to 8 moles of alkoxylated units, a C^ alkyl group, hydroxyalkyl and an organic group having between 6-26 atoms.

Preferably R¹³ and R¹⁴ combined include from about 2 to 7. Lauryl dimethyl amine oxide and isodecyloxypropyl bis-hydroxyethyl amine oxide are examples of preferred amine oxide compositions. Tomah Products AO-14-2, Albemarle Corp., Baton Rouge, Louisiana Admox, 1214 and Akzo Nobel Chemical, Chicago, Illinois Aromex C/12-N are commercially-available amine oxides useful in practicing the invention.

Preferred water soluble quaternary ammonium compound surfactants have the general structural formula:

X-

wherein R¹⁵ is selected from an alkyl, alkylamidopropyl , hydroxyalkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms, R¹⁶ is from 0 to 7 moles of alkoxylated units, n is 0 or 1, R¹⁷ and R¹⁸ are each selected from 1 to 8 moles of alkoxylated units, a C^ alkyl group, hydroxyalkyl and an organic group having between 6-26 atoms, R¹⁹ is a methyl group or ethyl group and X- is a halide or sulfate group.

The preferred alkoxylated units are selected from the group consisting of ethyleneoxy, propyleneoxy, butyleneoxy and mixtures thereof. R¹⁷ and R¹⁸ combined preferably include from about 2 to 10 moles of alkoxylated units. Suitable alkylammonium compounds include dodecyl trimethyl ammonium chloride and isodecyloxypropyl dihydroxyethylmethylammonium chloride. Commercially-available alkylammonium compounds include Q- 17-2 from Tomah Products, Inc . and Foamquat 112 from Alzo, Inc. Matawan, New Jersey.

It is preferred that the polyalkoxylated amine comprises from about 15-70% by weight of the composition and that the water-soluble surfactant comprises from about 85-30% by weight of the composition. A diluent may be added to the detergent composition at any time prior to the application step. The diluent may be used to achieve a final percent actives of between about 99.99 and 0.01%. Water is the most preferred diluent but organic solvents such as ethanol , xylene, toluene, isopropanol, propylene glycol, hexylene glycol and petroleum distillates may also be used. Mixtures of such diluents are also acceptable. The alternative detergent composition of the inventive method summarized above comprises three main components. The first component is from 0.5-99% by weight of a polyalkoxylated amine as set forth above while the second component is from 99-0.5% by weight of a water-soluble surfactant selected from the group consisting of nonionics, alkyl ether sulfate and amphoteric compounds as set forth above .

The third component consists of from 99-0.5% by weight of a third constituent selected from the group consisting of the amine oxides and quaternary ammonium compounds set forth above and an alkyl acid alkanolamide compound component having the general structural formula:

0 R²¹

20 II /

-c- -N

\

R²²

wherein R₂₀ is an alkyl or alkyloxyethyl group having between 10 and 18 carbon atoms, R²¹ and R²² are each a -CH₂CH₂OH group or H such that R²¹ and R²² are not both H. Examples of alkanolamides useful in the invention include Mackamide C from Mclntyre Group, Ltd. , University Park, Illinois and Scherca id SLM from Scher Chemicals, Inc. of Clifton, New Jersey.

In this embodiment, the polyalkoxylated amine preferably consists of from about 10-40% by weight of the composition, the water-soluble suriactant consists of from about 20-80% by weight of the composition and the third constituent consists of from about 10-40% by weight of the composition. At any time prior to the application step, there may be a further step of adding water to the composition to achieve a final percent actives of between about 99.99 and 0.01%. Water is the most preferred diluent but organic solvents such as ethanol , xylene, toluene, isopropanol, propylene glycol, hexylene glycol and petroleum distillates may also be used. Mixtures of such diluents are also acceptable.

The interaction between certain anionic surfactants and alkoxylated amines in aqueous detergent micelles can lead to formulations with undesirable physical and commercial properties. To avoid this problem, a number of incompatible anionic surfactants have been excluded from the anionic compositions claimed in this application. The anionic surfactants not included in this application have been anticipated to lead to insoluble solid heterogeneous mixtures, unstable two phase formulations, or gelatinous compositions. Gelatinous detergents are typically difficult to pour, pump, prepare, and handle commercially and are therefore undesirable.

Table 1 immediately below shows the physical state, stability, and formulatability of a group of common anionic surfactants combined with an alkoxylated amine of the present invention. The data table indicates that alkyl ether sulfates are the preferred anionic surfactants for the purpose of making generally stable formulations . TABLE 1 Anionic Surfactant & Alkoxylated Amine Binary Detergents

N/A means not applicable; the compositions were unstable (two phases, layered)

In each example set forth in Table 1, aqueous compositions consisting of the listed anionic surfactant and bis- (hydroxyethyl) dodecyloxypropyl amine were prepared at 50:50 wt. % active blends. As shown, the alkyl ether sulfate was compatible with the invention whereas the other anionic surfactants were not .

It is anticipated that other optional constituents can be added to the detergent compositions of the invention. By way of example only, such optional components include dyes, perfumes, thickeners, chelating agents, suds control compounds, buffering agents, bactericides, soil suspension polymers, hydrotropes. These additives are not required to practice the invention, and such adjuvants are known to one of ordinary skill in the art that affect, for instance, the aesthetics, shelf-life, etc., of the compositions.

EXAMPLES AND DATA

The cleaning tests were based on a standard procedure. The test protocol for Examples 1-5 consisted of placing 140mL of a detergent solution into a beaker with stirring at a lOOOrpms, 23°C, and at the specified concentration. Then a soiled substrate was immersed in the detergent for 15 minutes. After which time, the percent soil removed from the substrate was calculated based on an average of three runs. The cleaning efficacy of the various surfactant compositions included in this application was determined by this method.

Example 1

Detergent Composition With Different Component Ratios

A detergent composition consisting of two main components was prepared. Component A was a polyalkoxylated amine consisting of bis- (2 -hydroxyethyl) isodecyloxypropylamine and component B was an alkyl ether sulfate consisting of lauryl ethoxy 4 -mole sulfate. The detergent composition was diluted with water prior to the application step and had 1% actives. The hydrocarbon- containing soil to be removed from a glass test plate included a mixture of motor oil and lithium grease.

The test was performed at 23 °C. The soil -containing glass substrate was immersed in the dilute detergent composition for 15 minutes.

CLEANING PERFORMANCE

Example 1 illustrates the importance of identifying the optimum component ratios of the detergent compositions which provide maximum detergency and cleaning. The data set also shows the synergistic improvement achieved by blending (combining) the components. Example 2

Ternary Detergent Compositions Detergent compositions consisting of three main components were prepared to evaluate the efficacy of the inventive detergent composition versus a prior art composition. Component A was an alkoxylated alcohol (nonionic surfactant) nonylphenol 9-mole ethoxylate, component B is a polyalkoxylated amine bis- (2 -hydroxyethyl) isodecyloxypropylamine, component C is a polyalkoxylated amine oxide bis- (2 -hydroxyethyl) isodecyloxypropylamine oxide and component D- is a quaternary ammonium compound bis- (2- hydroxyethyl) isodecyloxypropyl methyl ammonium chloride.

The detergent compositions were diluted with water prior to the application step and had 1% actives. The hydrocarbon-containing soil to be removed from a glass test plate included a mixture of soybean oil and Crisco shortening oil .

CLEANING PERFORMANCE

Example 2 shows that the ternary compositions of the present invention outperform prior art detergent compositions which lack any polyalkoxylated amine component. These ternary compositions of the invention, which are based on the central component of alkoxylated amines, broaden the utility of the invention. Example 3

Binary Detergent Compositions

Detergent compositions consisting of two main components were prepared to evaluate the efficacy of the inventive detergent composition. The components are set forth in the table below, weight percent ratios of the active ingredients were 1:1.

The detergent compositions were diluted with water prior to the application step and had 0.1% actives. The hydrocarbon-containing soil to be lemoved from a glass test plate included a mixture of motor oil and lithium grease .

The test was performed at 23 °C. The soil-containing glass substrate was immersed in the dilute detergent composition for 3 minutes.

CLEANING PERFORMANCE

Example 3 illustrates that various water soluble surfactants and alkoxylated amine binary compositions enhance the degreasing of hydrophobic hydrocarbon soils. Example 4

Binary Detergent Compositions Detergent compositions consisting of two main components were prepared to evaluate the efficacy of other forms of the inventive detergent composition. The components are set forth in the table below. Weight percent ratios of the active ingredients were 1:1.

The detergent compositions were diluted with water prior to the application step and had 1% actives. The hydrocarbon-containing soil to be removed from a glass test plate again consisted of a mixture of motor oil and lithium grease.

CLEANING PERFORMANCE

Example 4 demonstrates the utility of water soluble quats, amphoterics, and amine oxides in combination with alkoxylated amines to boost their degreasing performance. Example 5

Detergent Composition With Different Component Ratios

A detergent composition consisting of two main components was prepared. Component A was a polyalkoxylated amine consisting of bis- (2-h} droxyethyl) isodecyloxypropylamine and component B was an amine oxide consisting of poly (5) oxypropylene isodecyloxy- propylamine oxide. The detergent composition was diluted with water prior to the application step and had 1% actives. The hydrocarbon-containing soil to be removed from a glass test plate included a mixture of motor oil and lithium grease.

The test was performed at 23 °C. The soil-containing glass substrate was immersed in the dilute detergent composition for 15 minutes.

CLEANING PERFORMANCE

Example 5 illustrates that the optimum performance for different detergent composition of the present invention may not have the same optimal detergency ratio. In Example 5, a 2:1 ratio is the relative optimum whereas in Example 1 a 3:1 ratio is the optimum. The synergistic, favorable results achieved at the foregoing ratios of active ingredients of the alkoxylated amine detergent compositions are advantageous and were not expected. Example 6

Detergent Composition Foamability As discussed above, it is advantageous to be able to control the level of foaming of the detergent composition based on the needs of the end user. Examples 6 and 7 are directed to the foamability of the detergent composition of the invention.

In this example, a detergent composition consisting of two main components was prepared. Component A was a polyalkoxylated amine consisting of bis- (2 -hydroxyethyl ) isodecyloxypropylamine and component B was an amine oxide consisting of poly (5) oxypropylene isodecyloxypropylamine oxide. The detergent composition was diluted with deionized water prior to the application step and had 0.10% actives. The weight percent ratio of the components was varied to determine the effect of the ratios on foam production and stability as indicated in the following table. The test protocol followed was ASTM designation: D- 1173 -53 titled the "Standard Test Method for Foaming Properties of Surface-Active Agents." Pursuant to the test protocol, 200mL of each detergent composition was added to a reservoir containing 50mL of the detergent composition. The detergent composition was added in a continuous flow at a vertical height of 90cm above the level of detergent in the reservoir. Measurements of the level of foam generated by addition of the detergent to the reservoir were made at 0 minutes and again at 5 minutes. The test was performed at 23 °C. The data appear in the following table. CLEANING PERFORMANCE

Example 6 illustrates how the components included in the detergent compositions herein disclosed affects the foamability of the compositions. In the case of example 6 it is a low foaming composition v.hich has unique application barring high foaming detergents.

Example 7

Detergent Composition Foamability

In Example 7, a detergent composition consisting of two main components was prepared. Component A was a polyalkoxylated amine consisting of bis- (2 -hydroxyethyl) isodecyloxypropylamine and component B was an alkyl ether sulfate consisting of lauryl ethoxy ether sulfate. The detergent composition was diluted with water prior to the application step and had 0.10% actives. The weight percent ratio of the components was varied as indicated in the following table.

Example 7 used the foamability protocol of Example 6. The test was again conducted at 23 °C. The foam stability data are presented in the following table. CLEANING PERFORMANCE

Example 7 demonstrates the foamability of a medium to high foaming composition of the present invention which illustrates the versatility of foam profile the invention provides for many different application opportunities. This is a unique and valued feature of the present invention.

While the principles of this invention have been described in connection with specific embodiments, it should be understood clearly that hese descriptions are made only by way of example and are not intended to limit the scope of the invention.

Claims

WHAT IS CLAIMED:

1. A method for cleaning hydrocarbon-containing soils from a surface comprising the steps of: -preparing a detergent composition consisting essentially of:

-from 1-99% by weight of a polyalkoxylated amine having a general structural formula selected from the group consisting of:

R³ /

R¹ - R²40CH₂CH₂CH₂ - _nN

R⁴ wherein

-R¹ is selected from an alkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms; -R² is from 0 to 7 moles of alkoxylated units; -n is 0 or 1;

-R³ and R⁴ are each selected from H and from about 1 to 5 moles of alkoxylated units such that R³ and R⁴ are not both H and R³ and R⁴ combined include about 5 or fewer moles of alkoxylated units; and

R⁷ R⁸

I / R⁵-R⁶40CH₂CH₂CH_{2 n} NCH₂CH₂CH_rN

R⁹ wherein

-R⁵ is selected from an alkyl, aryl or alkylaryl group having between 6 and

22 carbon atoms;

-R⁶ is from 0 to 7 moles of alkoxylated units;

-n is 0 or 1 ; -R⁷, R⁸ and R⁹ are each selected from

H and from 1 to 5 moles of alkoxylated units such that R⁷, R⁸ and R⁹ are not each H; and -from 99-1% by weight of a water-soluble surfactant selected from the group consisting of nonionics, alkyl ether sulfates, amine oxides, amphoterics and water soluble quaternary ammonium compounds; and

-applying the detergent composition to the object to be cleaned. 2. The method of claim 1 wherein R³ and R⁴ combined include from about 1 to 2 moles of alkoxylated units.

3. The method of claim 1 wherein R⁷, R⁸ and R⁹ combined include from about 3 to 5 moles of alkoxylated units .

4. The method of claim 1 wherein the polyalkoxylated amine consists of from about 15-70% by weight of the composition and the water-soluble surfactant consists of from about 85-30% by weight of the composition.

5. The method of claim 1 including, at any time prior to the application step, the further step of adding a diluent to the composition to achieve a final percent actives of between about 99.99 and 0.01%.

6. The method of claim 1 wherein the nonionic water-soluble surfactant is selected from the group consisting of alkoxylated alkyl phenols, alkoxylated alcohols, polypropylene glycol alkoxylates, alkoxylated diamines, alkoxylated glycosides and amine oxides.

7. The method of claim 1 wherein the alkyl ether sulfate water-soluble surfactant is dodecyl 4 mole ethoxy sulfate, sodium salt.

8. The method of claim 1 wherein the amphoteric water-soluble surfactants are selected from the group consisting of cocoamidopropyl betaine and isodecyloxypropyliminopropionate, sodium salts.

9. The method of claim 1 wherein the amine oxide water-soluble surfactants have the general structural formula : R¹

_R╬╣o__R╬╣ⁱ oCH₂CH₂CH₂-)-_nNΓåÆ0

R¹ wherein

-R¹⁰ is selected from an alkyl, alkylamidopropyl, hydroxyalkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms ;

-R¹¹ is from 0 to 7 moles of alkoxylated units;

-n is 0 or 1,

-R¹³ and R¹⁴ are each selected from 1 to 8 moles of alkoxylated units, a C_x_₅ alkyl group, hydroxyalkyl and an organic group having between 6-26 atoms.

10. The method of claim 9 wherein R¹³ and R¹⁴ combined include from about 2 to 7 moles of alkoxylated units .

11. The method of claim 1 wherein the water soluble quaternary ammonium compound surfactants have the general structural formula:

R¹ ' R¹⁵ -R¹⁶40CH₂CH₂CH₂-)-_nN-R¹⁹ X-

_R18

wherein

-R¹⁵ is selected from an alkyl, alkylamidopropyl , hydroxyalkyl , aryl or alkylaryl group having between 6 and 22 carbon atoms ;

-R¹⁶ is from 0 to 7 moles of alkoxylated units;

-n is 0 or 1, -R¹⁷ and R¹⁸ are each selected from 1 to 8 moles of alkoxylated units, a C₁_ s alkyl group, hydroxyalkyl and an organic group having between 6-26 atoms;

-R¹⁹ is a methyl group or ethyl group; and -X- is a halide or sulfate group.

12. The method of claim 22 wherein R¹⁷ and R¹⁸ combined include from about 2 to 7 moles of alkoxylated units.

13. A method for cleaning hydrocarbon-containing soils from a surface comprising the steps of:

-preparing a detergent composition comprising:

-from 0.5-99% by weight of a polyalkoxylated amine having the general structural formula:

R³

/ R¹-R²40CH₂CH₂CH₂-)-_nN \

R⁴

wherein

-R¹ is selected from an alkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms;

-R² is from 0 to 7 moles of alkoxylated units; -n is 0 or 1 ;

-R³ and R⁴ are each selected from H and from 1 to 5 moles of alkoxylated units such that R³ and R⁴ are not both H and R³ and R⁴ combined include about ^'5 or fewer moles of alkoxylated units; or

R⁷ R⁸ I /

R⁵-R⁶40CH₂CH₂CH₂-_n NCH₂CH₂CH₂N

R⁹

wherein -R⁵ is selected from an alkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms;

-R⁶ is from 0 to 7 moles of alkoxylated units;

-n is 0 or 1,

-R⁷, R⁸ and R⁹ are each selected from H and from 1 to 5 moles of alkoxylated units such that R⁷, R⁸ and R⁹ axe not each H; and -from 99-0.5% by weight of a water-soluble surfactant selected from the group consisting of nonionics, alkyl ether sulfates and amphoteric compounds ;

-from 99-0.5% by weight of a third constituent selected from the group consisting of an amine oxide component having the general structural formula :

R¹³

R¹ ┬░ - R¹ HOCH₂ CH₂ CH₂-)-_nNΓåÆ0

R¹⁴ wherein

-R¹⁰ is selected from an alkyl, alkylamidopropyl, hydroxyalkyl, aryl or alkylaryl group having between 6 and 22 carbon atoms ; -R¹¹ is from 0 to 7 moles of alkoxylated units;

-n is 0 or 1,

-R¹³ and R¹⁴ are selected from 1 to 8 moles of alkoxylated units, a C^ alkyl group, hydroxyalkyl and an organic group having between 6-26 atoms ; -a quaternary ammonium compound component having the general structural formula:

X-

10 wherein

-R¹⁵ is selected from an alkyl, alkylamidopropyl, hydroxyalkyl, aryl or alkylaryl group having between 6 and 22 carbon

15 atoms ;

-R¹ is from 0 to 7 moles of alkoxylated units ;

-n is 0 or 1,

-R¹⁷ and R¹⁸ are each selected from 1

20 to 8 moles of alkoxylated units, a

Ci-_s alkyl group, hydroxyalkyl and an organic group having between 6-26 atoms ;

-R¹⁹ is a methyl group or ethyl group; and

25 -X- is a halide or sulfate group; and

-an alkyl acid alkanolamide compound component having the general structural formula:

30 0

/

R⁰-C-N

\

R²

35 wherein

-R₂₀ is an alkyl or alkyloxyethyl group having between 10 and 18 carbon atoms ;

40 -R²¹ and R²² are each a -CH₂CH₂OH group or H such that both R²¹ and R²² are not

H ; and -applying the detergent composition to the object to be cleaned.

14. The method of claim 13 wherein R³ and R⁴ combined include from about 1 to 2 moles of alkoxylated units.

15. The method of claim 13 wherein R¹³ and R¹⁴ combined include from about 2 to 7 moles of alkoxylated units .

16. The method of claim 13 wherein R¹⁷ and R¹⁸ combined include from about 2 to 10 moles of alkoxylated units .

17. The method of claim 13 wherein R⁷, R⁸ and R⁹ combined include from about 3 to 5 moles of alkoxylated units .

18. The method of claim 13 wherein the polyalkoxylated amine consists of from about 10-40% by weight of the composition and the water-soluble surfactant consists of from about 20-80% by weight of the composition and the third constituent consists of from about 10-40% by weight of the composition.

19. The method of claim 13 including, at any time prior to the application step, the further step of adding a diluent to the composition to achieve a final percent actives of between about 99.99 and 0.01%.

20. The method of claim 13 wherein the nonionic water-soluble surfactant is selected from the group consisting of: alkoxylated alkyl phenols, alkoxylated alcohols, polypropylene glycol alkoxylates, alkoxylated diamines, alkoxylated glycosides.

21. The method of claim 13 wherein the alkyl ether sulfate water-soluble surfactant is dodecyl 4 mole ethoxy sulfate, sodium salt.

22. The method of claim 13 wherein the amphoteric water-soluble surfactants are selected from the group consisting of cocoamidopropyl betaine and isodecyloxypropyliminopropionate, sodium salts.