FI73731C - Fabric cleaner suitable for clay based stains. - Google Patents

Abstract

Stain removal composition comprise mixtures of grease-cutting solvents and polyamines. The compositions are particularly useful for removing stains comprising a mixture of grease and particulate matter from fabrics. Liquid detergents containing said solvents and polyamines in the form of stable oil-in-water microemulsions are disclosed.

Description

1 ^ 3731

This invention relates to compositions and methods for removing clay-based dirt and stains from fabrics. The compositions are particularly suitable for removing cosmetic stains consisting of a mixture of a clay-based substance and an oily or greasy binder. The compositions disclosed contain a solvent component for dispersing the binder and polyamine for dispersing the clay. These compositions can be used in the form of a simple fabric pre-stain remover or in full formulations. in laundry detergents consisting of a mixture of several different ingredients designed to remove a wide variety of stains and soils from fabrics, which provides a particularly significant benefit in the removal of stains caused by cosmetic cinnamon.

It is the job of detergent manufacturers to design products that are well suited for removing a wide variety of dirt and stains from fabrics. Chemically and physically-chemically, the large number of dirt and stains extends mainly through oily, protein and carbohydrate content, inorganic and tracer compositions have become increasingly complex as manufacturers strive to provide products that remove all types of dirt and stains simultaneously. For example, protease enzymes are commonly used in detergents to remove blood and sauce stains; ions tower surfactants are used to remove hydrocarbon oils; and anionic surfactants and bu LIdore L ta are used to remove particulate dirt. Bleaching is used to chemically decompose stains that cannot be removed by lighter treatment.

One of the most difficult stains to remove from fabrics is a stain caused by a cosmetic agent, and since time immemorial 35, a stubborn revealer of a lint red stain on a shirt or handkerchief has meant the destruction of many "villains" 2,73731. Moreover, the significant ability of the current cosmetics industry to produce products that last longer and longer on the wearer's skin means that current cosmetics are increasingly adhering to the fabrics to which they are accidentally exposed.

Chemically, many cosmetics contain a clay base which acts in part as a filler, thickener, colorant carrier, etc., mixed with an oily substance which acts in part as a binder, gloss and emollient. Cosmetics are usually prepared with great care so that the clay and colorants are mixed and covered with very fine particles and very thoroughly and completely in an oily substance, which may be a hydrocarbon oil, silicone, lipid or a complex mixture thereof. Although ideal for a cosmetic manufacturer, a modern cosmetic product poses major problems for detergent manufacturers, as cosmetics form a combination of widely differing liquids (oily, particulate, clay), all of which are thoroughly mixed and often brightly colored. No single detergent component can reasonably be expected to survive such a complex mixture.

The present invention utilizes oil-releasing solvents and clay-releasing polyamines. Solvents dissolve the oil base of cosmetics, exposing their clay component to polyamines, which disperse the clay component and remove it from the fabrics.

The use of solvents of the type used in the present invention as grease and oil removing ingredients in various types of cleaning agents is commercially known and familiar from the patent literature. See. for example, U.S. Patent 2,073,464, EP Patent Applications 0 072 488 and 40 882 35 and GB Patent 1,603,407.

This invention relates to compositions and methods for removing cosmetic and other similar stains from fabrics using a solvent (particularly solvents such as isoparaffin hydrocarbons, kerosene, petroleum fractions, D-limonene or mixtures of terpenes, fatty alcohols or benzyl alcohols, benzyl alcohols thereof). with an alkoxylated polyamine (described in more detail below) in a weight ratio of solvent to polyamine of from 100: 1 to 1:20, preferably at least 2: 1. The invention 10 also relates to fully formulated detergent compositions comprising conventional detergent ingredients, such as surfactant builders, enzymes, detersive surfactants and the like, and characterized in that these compositions contain at least about 5 % by weight of the above-mentioned mixture of solvent and polyamine. Preferably, such fully formulated detergent compositions contain at least 5% solvent and at least 0.2% polyamine.

The essential solvent and polyamine ingredients, as well as the preferred surfactant components and other possible ingredients used in the practice of this invention, are described in detail below. All percentages and ratios used in this specification are by weight percentages and ratios unless otherwise indicated.

Solvent The solvents used in the present invention may be any of the known "degreasing" solvents generally known to be used, for example, in the commercial laundry and dry cleaning industries, the hard surface cleaning industry, and the metal industry. Such solvents usually contain hydrocarbon or halogenated hydrocarbon groups of the alkyl or cycloalkyl type and usually have a boiling point well above room temperature.

4,73731 The formulation of compositions of the type of this invention is guided in the choice of solvent by the need to provide good degreasing properties and by aesthetic aspects. For example, kerosene hydrocarbons perform quite well in the compositions of this invention, but may be malodorous. Kerosene can be used in commercial laundries. For household use where unpleasant odors are not tolerated, the formulator would be more likely to select solvents that have a relatively pleasant odor 10 or an odor that can be tolerably altered by perfume.

Examples of such solvents are citrus terpenes and terpenoid solvents, in particular orange terpenes and D-limonene. Benzyl alcohol is another relatively pleasant-smelling solvent suitable for this purpose.

Excellent solvents for use in the compositions of this invention include paraffins and mono- and bicyclic monoterpenes, i. compounds belonging to the group of hydrocarbons such as terpinenes, li-20 monenes and pinenes and mixtures thereof. Highly preferred substances of this type are mixtures of D-limonene and terpene hydrocarbons obtained from orange extract (e.g. cold-pressed apeezine terpenes and your orange terpene oil derivative from fruit juice). Terpenes such as dipentene, Qf-pinene, β-pinene and mixtures of terpene hydrocarbons pressed from lemons and grapefruits are also useful.

The examples below provide a variety of other solvents that can be used in the compositions of this invention.

polyamines

It is to be understood that the term "polyamines" as used herein generally refers to alkoxylated polyamines, which may be in both amine and quaternized forms. Such substances can well be described as molecules with an empirical structure of repeating units.

5,73731 (f N - R -) - Amine form I 1 alkoxyl and R 't Φ Θ 5 - (N - R -) - X Quaternized form I x alkoxyl wherein R is a hydrocarbon group usually containing 2 to 6 carbon atoms; R 'may be a _2Q hydrocarbon group; alkoxy-10 groups are polyethoxy or polypropoxy groups or the like having a degree of polymerization of the polyethoxy chain of 2 to 30, most preferably 10 to 20; x is an integer of at least 2,

Q

preferably 2-20, most preferably 3-5; and X is an anion resulting from the quaternization reaction, such as a halide or methyl sulfate.

The most preferred polyamines for use in this invention are the so-called ethoxylated polyethyleneimines, i.e. a polymerized reaction product between ethylene oxide and ethyleneimine having the general formula 20 + N - CH 2 - CH 2 + -x (EtO) y wherein EtO is ethyleneoxy, x is an integer of 3-5 and y is an integer of 10-20.

25 Surfactants

It is possible and highly preferred that the compositions of this invention contain, in addition to a solvent and a polyamine, organic surfactants in order to achieve the conventional cleaning benefit associated with the use of these agents.

Water-soluble cleaning surfactants suitable for use in the compositions of this invention include anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are alkylbenzene sulfonates, alkyl and alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, 6,73731 cilCoxyloxy and the like. (orally ethoxylated) alcohols and alkyl-'-ifenols, nin oxides, α-sulfonates of fatty acids and ra 3 να ha ppoe s t e r i t and the like known in the detergent art. Detergent surfactants generally contain a C 1-6 alkyl group; anionic detersive surfactants are most commonly used in the form of sodium, potassium or triethanolammonium salts; nonionic surfactants generally contain about 5-17 ethylene oxide groups. U.S. Patent Nos. 4,111,855 and 3,995,669 contain detailed lists of typical such detersive surfactants. C 1-6 alkylone sulfonates, C 1-6 araraffin sulfonates and alkyl-Z 1 O 6 sulfates, as well as ethoxylated alcohols and alkylphenols are particularly preferred in the type 15 compositions of this invention.

The surfactant may be present in only 18 of the compositions of the invention, but preferably the compositions contain 1-40%, even more preferably 5-30%, of a surfactant. Ethoxylated nonionic surfactants and anionic surfactants such as alkylene. Mixtures of Onua 11, allyl sulphates and paraffin sulphonates, have the advantage of cleaning fabrics from a wide range of solutions and stains in the actual washing.

2 5 R fatty acid / soap ingredient

Fatty acids (generally 10 to 18 carbon atoms in chain length) already have their water-soluble salts (i.e., common "soaps", especially early metal soaps) in the compositions of this invention, not only because of their surfactant properties but also to enhance surfactant the action of the substance, as they are able to react with the cations that cause water hardness. As will be explained in more detail below, fatty acids and soaps are particularly useful in the preparation of fully formulated 35 homogeneous liquid oil-in-water detergents which

II

7,73731 contain solvent and polyamine in a carrier. Typical concentrations used are 0.5 to 50 3.

Other Optional Ingredients The compositions of this invention may contain 5 other ingredients that enhance their cleaning performance. For example, it is highly preferred that the detergent compositions used in the actual wash contain a detergent builder and / or a metal ion scavenger. Compounds that can be classified as builders and are known as such in the art include nitrile triacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphosphate and sodium ortho- and pyrophosphate, silicates, and mixtures thereof. Metal ion binding agents include all of the above, as well as substances such as ethylenediaminetetraacetate, aminopolyphosphonates and phosphates (DEQUEST), and a large number of other polyfunctional organic acids and salts that are too numerous to be described in detail herein. U.S. Patent No. 3,579,454 provides typical examples of the use of such agents in various cleaning compositions. The composition generally contains about 0.5 to 15% builder and / or metal ion binding agent. One of the most expensive builders is citrate, as it readily dissolves in the aqueous phase of liquid high power detergent compositions.

The compositions of the present invention preferably also contain enzymes in order to improve their cleaning performance in the actual washing against a wide variety of soils and stains. Amylase and protease enzymes suitable for use in detergents are known in the art and are used in commercial liquid and granular detergents. Commercial cleaning enzymes (usually a mixture of amylase and protease) are usually used in the compositions of this invention in concentrations ranging from 0.001 to 2% or higher. Ingredients such as propanediol and / or formate as well as calcium may be added to the compositions as desired by the formulator to stabilize the enzymes in a known manner.

73731

O

In addition to the ingredients already mentioned, the compositions of the present invention may contain a wide variety of other ingredients typically used in commercial products to improve the aesthetics or effectiveness of the product. Typical ingredients include pH adjusters, perfumes, colorants, optical brighteners, dirt suspending agents, hydrotropes and gel regulators, freeze-thaw stabilizers, bactericides, preservatives, foam regulators and the like.

Mixtures of water and alcohol (e.g., ethanol, isopropanol, etc.) can be used as a carrier in liquid compositions, and alkylated polysaccharides can be used to improve the stability and performance of the compositions.

The pH of the compositions of this invention is preferably adjusted to neutral or basic, generally in the range of 5.5 to 9.0, preferably to approximately 6.8 to 7.5. Substances such as sodium hydroxide, potassium hydroxide, alkanolamines such as triethanolamines and magnesium hydroxide can be used to adjust the pH to the desired value. Preferred pH adjusting agents are described below.

Preferred compositions of this invention are liquid compositions which can be prepared simply by mixing the main ingredients and excipients with a liquid (preferably aqueous) carrier. As mentioned above, a fatty acid or soap may be used in such liquid compositions to provide a clear and homogeneous microemulsion of the solvent in an aqueous vehicle. Solid or granular compositions can be prepared by impregnating a solvent and a polyamine on the surface of a suitable granular carrier, for example, sodium sulfate, sodium perborate (bleach), or a granular spray-dried detergent carrier.

Considering the process side, the liquid or pasty compositions of this invention can be used to pretreat soiled fabrics by rubbing a few milliliters of the composition directly onto the soiled area, followed by washing in a conventional manner. In the actual washing, the compositions are usually used in concentrations of at least 500 ppm, preferably 0.1 to 1.5%, in washing water having a pH of 6.5 to 10, for washing fabrics. Washing can be performed between 5 ° C and boiling temperature so that the results are excellent.

The following examples illustrate many different formulations that can be prepared in accordance with this invention using a mixture of a solvent component and a polyamine component. They are given by way of example only and are not intended to limit the scope of the invention. In the formulas shown, the terms "x" and "y", which indicate the degree of polymerization and alkoxylation of the polyamine, are mentioned in parentheses. Some of the "polyamines" mention the term R ', which means quaternized polyamine. In the case of such quaternized substances, the anion X formed is not relevant for purification efficiency and is omitted. In all examples, R is -CH 2 -CH 2 - and the alkoxyl group 20 is ethoxyl unless otherwise specifically stated.

Example I

Prepared according to the instructions of U.S. Pat. No. 3,664,962 by removing the stain in the form of a stick and mixing the following ingredients together, pressing the resulting mass through a 1.25 cm die and wrapping the resulting stick in an aluminum foil wrapper.

Ingredient Percentage

Sodium stearate 22.0 D-limonene 15.0 30 Benzyl alcohol 8.0 2-propanol 22.0

Polyamine (x = 2; y = 6 avg) 10.0

Sodium dodecylbenzenesulphonate 3.5

Water to 100 35 In use, the foil wrapper is peeled off a portion of the wand, which is then rubbed vigorously on the area of the garment where there are stains caused by a cosmetic or the like. The garment is then brushed or possibly washed to remove stains and debris from the wand.

5 Example II

Your liquid fabric pre-treatment and the washing agent that improves the washing performance of the actual wash are prepared by mixing the following ingredients together:

Ingredient Weight 10 Paraffin oil (deodorized) 20

Polyamine (x = 3; y = 5 avg) 7

Water 50

Ethoxylated sorbitan oleate 3

In the preferred method of use, a few milliliters (1-10 ml) of the composition of Example II are applied directly to the fabric stained with clay / grease and rubbed within the heavily soiled area. The fabric is then washed with a commercial laundry detergent (eg VIZIR) according to the instructions on the package.

In an alternative method, the composition of Example II is added directly to the wash water, generally from 500 to 5,000 ppm according to the user's preference and dirt load, together with a commercial laundry detergent to improve the washing performance.

The composition of Example II can be diluted (1: 1) with water or water-ethanol and packaged in an aerosol or hand pump bottle for use as a stain remover.

Example III

A granular detergent composition containing the solvent-polyamine composition of this invention can be prepared by mixing the solvent and polyamine with a spray-dried commercial laundry detergent. However, in a preferred method, the solvent and polyamine are mixed with an unneutralized anionic surfactant, which is then mixed with the alkaline builder and any other detergent components, whereby the surfactant is neutralized in situ in the product. This method for formulating solvent-containing granular detergents is described by A. Davidsohn in his original lecture in the 3rd International Congress of Surface Activity, Cologne (1960), 5 165-172 (p. 171).

Following the procedures proposed by Davidsohn, a granular detergent is prepared with the following formula: Ingredient Percentage 2 (average) - alkylbenzenesulfonate 9.6 10 (in acid form) 2'-alkyl alkyl ethoxylate (EO average 9) 1.4

Sodium perborate tetrahydrate 22.0

Sodium tripolyphosphate 19.0

Orange terpene 10.0 Polyamine (x - 3; y = 16) 1.0

Sodium sulphate 20.0

Cured ^ g soap (foam control) 1.5

Enzymes (protease-amylase mixture) 1.5

Carboxymethylcellulose 2.0 20 Water, optical brightener, secondary substances to 100

The composition of Example III is used in a conventional manner to wash fabrics. In a preferred method, about 2 q of the composition is mixed with about 5 ml of water to form a paste, which paste is then rubbed into the run-25 soiled areas of the fabrics before washing the fabric with said composition.

Examples IV-IX

The following examples relate to solvent-containing compositions of this invention that are particularly suitable for use in industrial large-scale laundry and purification plants and the like. The formulation should be understood that some of the solvents used in such compositions may not be suitable for general household use due to bad odor, potential for skin irritation, low flash point, and the like. However, such compositions are perfectly suitable for use by 12,73731 rammers who take these factors into account under properly controlled conditions. In Examples IV-IX, all ingredients are listed by weight.

Ingredient IV V VI VII VIII IX

5 Stoddard solvent 100 - - - 250

Trichlorethylene - 10 - - - -

Naphtha - - 30 - - -

Petroleum ether (b.p.

80-85 ° C) - - - 60 100 - 10 White spirit - - 20 - -

Benzyl alcohol - - - - 100 -

Butyl carbitol (trade name) - - - - - 50

Polyamine (A-F *) 5 (A) 10 (B) 15 (C) 100 (D) 20 (E) 150 (F) 15 Water 100 100 200 - 250 350

Coconut soap - - 25 - - 2 ~ α-alkyl: Lt, Gntseen: i- ·· sulfonate 50 5 - - 10 20 C 1-4 alcohol ethoxylate (EO avg. 9) 50 - - - 20

Ethoxylated C8-alkylphenol (EO average 6) - 2 10 100 10

Mg (OH) 2 to pH 7.0 7.1 7.5 to 7.7 8.1 * The polyamines A-F used in Examples IV-IX have the above general formulas and the polyamines are as follows: A: x = 2; y = 2; R - ethylene; alkoxyl = ethoxyl B: x - 20; y = 30; R = propylene; alkoxyl = propoxyl C: x = 3; y - 15; R = ethylene; alkoxyl = ethoxyl; R '= butyl D: x = 5; y = 9; R = butylene; alkoxyl = butoxyl E: x - 20; y = 10; R = hexylene; alkoxyl = ethoxyl; R '= dodecyl F: x = 3; y = 20; R = ethylene; alkoxyl = ethoxyl; R '= eikosvilli u 73731

Non - native aero - glazing agents

After describing the various compositions of this invention, special attention will now be paid to those highly preferred formulations which are particularly useful as high performance detergents suitable for washing all types of fabrics by a typical household laundry method. The high performance liquid detergents shown below are formulated from a variety of detergent ingredients to provide excellent dirt and stain removal, and of these ingredients, solvent and polyamine contribute significantly to the removal of clay / grease stains and used engine seat stains from fabrics.

It is to be understood that while such formulations may be formulated as water-in-oil memories, they are preferably prepared in the form of oil-in-water emulsions (in which the solvent is considered an "oil" phase) and most preferably are substantially clear, homogeneous oil-in-water -mikroemul-outlets. The formulator of liquid high performance detergents should note that the use of water in such compositions as a carrier phase provides significant cost savings and that the aqueous carrier glass also significantly holothesizes the formulation, as water-soluble detergents are easier to incorporate into oil-in-water emulsions than water-in-oil emulsions. . When using the pretreatment procedure, the degreasing ability of the oil-in-water emulsions of this invention is surprisingly comparable to the degreasing ability of water-in-oil emulsions with much higher solvent concentrations.

The compositions of this invention with high surfactant content and high fatty acid / soap content can be packaged in HD polyethylene bottles without loss of solvent.

14,737 31

Example X

Liquid high-performance detergents in the form of a clear, homogeneous oil-in-water emulsion with an excellent ability to remove a wide variety of clay-type stains are prepared as follows:

Ingredient Weight part

Polyamine (x = 5; y = 15) 1.5

Ethanol 3.0

Potassium hydroxide (50% aqueous solution) 8.0 10 g-alkylbenzenesulfonic acid 11.0

C 1-4 alkyl ethoxylate (EO t) 15.0

Potassium citrate monohydrate (63.5% aqueous solution) 2.4 Dequest * 2060 S (trade name) 1.2

Sodium formate (40% aqueous solution) 2.5 Ca + + as CaCl 2 · 10 ppm

Orange terpenes 10.0

Mixture of lauric acid and myristic acid (60:40) 12.5 Oleic acid 2.5

Maxatase ** - enzyme (trade name) 0.71 20 Termamyl *** - enzyme (trade name) 0.10

Optical brightener (anionic) 0.23

Perfume 0.5 Toner 20 ppm

Water to 100 25 Product pH 7.3 * Diethylenetriamine pentamethylenephosphonic acid (Monsanto) ** KNGS, supplier *** NOVO, supplier

The above composition is prepared by mixing said ingredients together to give a clear stable microemulsion. In washing tests, especially in the pretreatment stage, the ability of the composition to remove a wide variety of stains, including stains caused by cosmetics and used engine oil, is excellent.

Preferred compositions of the microemulsion type described above generally contain 10-20% of the fatty acid mixture and are formulated to a pH of 6.6 to 7.3.

7 7 T 7 Ί 15 /..-/ΟΙ

Example XI

The composition of Example X is slightly modified by using 0.6 parts by weight of magnesium hydroxide instead of 50% potassium hydroxide (1.2 parts) to adjust the pH to 7. The resulting product is a homogeneous microemulsion.

Example XII

The composition of Examples X and XI is modified by replacing the orange terpenes with a mixture of deodorized para-10 finin oil (iso-C 2 g 2 ^ 2_Paraffins; 7.5% of the total composition) and orange terpenes (2.5% of the total composition). This change in the solvent component does not in any way impair the performance of the compositions, but gives the fragrance greater freedom to use shades other than citrus scents. If desired, an anionic optical brightener (0.01 to 0.5%) can be added.

Solvent selection

As mentioned above, the final choice of solvent system for the compositions of this invention depends on the type and load of li-20, aesthetic factors (odor), etc. However, a few characteristics can be used to aid in this choice. For example, the solvent should not be significantly miscible with water and should, of course, be able to dissolve a wide variety of problematic fat soils. The thermodynamic solubility parameters (Hansen parameters) of this latter relationship are useful in selecting a solvent.

Each solvent can be described by the Hansen parameters <f ^, ^ h: <^ d ° n DisPersao '<omPonentti' <5D is the polarity component and £ is the hydrogen bonding component. Similarly, the main problematic fat classes can be described by "pseudo" -Hansen parameters. To do this, the solubility of each grease stain in several stallion solvents with different Hansen parameters must first be determined. This can be done by immersing the grease stain on several different types of fabrics (cotton, wood-wool polyester, acrylic) alternately, 6 73731 in each solvent for a specified time (say, five minutes) while stirring evenly. When the fabric is removed from the solvent, the excess solvent is drained off and the stained fabric is washed for five minutes in cold water containing 1% of a standard liquid laundry detergent. Finally, after cold water rinsing and drying, the loss of stain can be assessed visually or by any other suitable method. By doing so, the solvents with which each problematic grease stain is best removed can be determined, and thus the range of variation required for the best possible removal of that particular stain can be determined for each tiansen parameter. In this way, the Hansen parameters for each stain can be mapped and the solvent / solvent combination selected on this basis to achieve the desired result.

Without intending to limit the present invention in any way, the above procedure reveals that a mixed solvent / solvent combination with Hansen parameters in the ranges (7-9), $ (0-4) and (0-7) makes it possible to formulate microemulsions with has excellent grease stain removal ability. The solvent combination can be selected with certain grease stains, such as engine oil, in which case the most preferred ranges for the Hansen parameters are (7-9), 6h (0-4) and $ p (0-3), or the stamp ink in which the Hansen parameters the most preferred ranges are (7-9), (2-11) and (2-7), removal or, more broadly, removal of miscellaneous stains, with an intermediate point being selected from the range of Hansen parameters.

Some of the preferred solvents and solvent mixtures mentioned herein, especially orange terpenes (D-limonene), paraffins (especially iso-C 2 -C 2 paraffins), cyclohexane, kerosene, orange terpene-benzyl alcohol mixture (60:40) and For a mixture of 2-i-n-paraffins and hexanol (50:50), the Hansen parameters are within said limits.

These solvents and solvent mixtures are usually used in the compositions of this invention in concentrations of 5-20%, preferably 5-10%. Mildly polar solvents such as benzyl alcohol or n-hexanol can be used with water-immiscible solvents such as terpenes and paraffin oil in concentrations of 0-10%. Various other solvent mixtures are shown in Example XIX below. As can be seen from the above, many different formulations in the form of stable solvent-containing emulsions are within the scope of this invention. An excellent liquid high performance detergent composition can also be prepared using a solvent system comprising diethyl phthalate (preferred) or dibutyl phthalate in combination with terpenes (preferably orange terpene) or dipentene or paraffin oils or (most preferably) a mixture thereof. A typical example of such a composition is as follows:

Example XIII

Ingredient Weight 20 Polyamine (x = 5; y = 15) 1.5

Potassium hydroxide (50% aqueous solution) 8.0

Ethanol 3.0 C 1-10 alkylbenzenesulfonic acid 11.0 1 I / I C) 4/1-Alkyl ethoxylate (EO 7) 15.0 25 Potassium citrate (63.5% aqueous solution) 2.4

Deodorised paraffin oil (C) 2_if-isoparaffins) 7.5

Orange terpene 2.5

Dibutyl phthalate 3.0 30 Mixture of lauric and myristic acid (60:40) 12.5

Enzymes (according to Example X) 1.0

Water and secondary substances and cyclohexylamine to adjust the pH to 6.9 to 100

In Example XIII, dibutyl phthalate can be replaced with 35 equivalents of diethyl phthalate.

is 73731

It should be noted that many of the terpene hydrocarbon compositions described above necessarily have a rather strong citrus odor, which is not fully accepted by all manufacturers of such compositions. It has now been found that C8-8 alkyl-substituted aromatic solvents, in particular C1-6-alkylbenzenes, preferably octylbenzene, have excellent degreasing properties and a weak, pleasant odor. Olefin solvents having a boiling point of at least about 100 ° C, especially α-olefins, are also excellent degreasing solvents.

Further examples of preferred mixtures of non-polar and polar solvents which can be advantageously used in the practice of this invention include the above-mentioned alkyl-substituted aromatic solvents or olefin solvents and solvents such as benzyl alcohol, n-hexanol, Butyl Carbitol / commercial; 2- (2-Butoxyethoxy) ethanol and phthalic acid esters, combinations.

The following additional examples further illustrate oil-in-water microemulsions. In Example XVII, the use of a quaternary ammonium compound to adjust the pH of the formula just below neutral contributes significantly to the effectiveness of the product while maintaining the microemulsion's long-term stability.

19 7 3 7 3 1

Example XIV

Ingredient Weight%

C 1-6 alkylbenzenesulfonic acid 10.0

C 1-4 alkyl ethoxylate (EO 7) 10.9 5 Coconut fatty acid (broad fraction) 18.2 oleic acid 2.3

Monomethylethanolamine 5.8 1-decene 9.1

Ethanol (95%) 2.7 10 Dequest® (50% 1.09

Formic acid 0.18 K 2 citrate monohydrate (63.5% aqueous solution) 4.4

CaCl 2 a 0.0 5

Maxatase enzyme (protease) 0.73 15 Termamvl enzyme (amylase 0.10 2

Ethoxylated polyamine 1.73

Perfume / optical brightener / toner 0.5

Water to 100

Product pH 6.6 20 1. Diethylenetriamine pentamethylene phosphone hood 2. Tetraethylene pentamine (105 EO units, / molecule 1 i)

The composition of Example XIV is a stable oil-in-water microemulsion suitable for use as a laundry detergent.

25 Example XV

The composition of Example XIV is modified by replacing 1-decene with the same amount (9.1% of the total formula) of n-octylbenzene. PH of the product "as is": 6.6.

Example XVI

The composition of Example XIV is modified by replacing 1-decene with one of the following solvent mixtures (percentage of total formula is given in parentheses): a mixture of 1-de-Keen (6.1%) and diethyl phthalate (3.0%), 1-dode-Keen (5, 9%) and a mixture of benzyl alcohol (3.2%), a mixture of n-octyl-35 benzene (6.2%) and diethyl phthalate (2.9%), a mixture of n-octylbenzene (5.0 L) and butylcarbitol (4.1%). %) 20 7 37 31 and a mixture of diethyl phthalate (6%), liquid N-isoparaffin (2%) and orange terpene (2%). PH of products as such: 6.6.

Example XVII

The compositions of Examples XIV, XV and XVI are modified by the addition of a sufficient amount of cyclohexylamine or dioctyldimethylammonium chloride to adjust the pH of the compositions ("as is") to 6.6-6.94. The resulting compositions have exceptionally good fabric-10 cleaning and whitening retention.

Example XVIII

The composition of the special high wash additive is as follows: Ingredient Weight% 1-decene 20 15 n-octylbenzene 10

Diethyl phthalate 10

Polyamine (x = 5; y = 15) 10

Sodium tripolyphosphate to 100

Another preferred olefin solvent in this case, due to its relatively low odor, is the so-called A "P-4" polymer available as a feedstock for branched alkylbenzenes for the detergent industry from a few petrochemical suppliers. P-4 is a mixture of isomers formed as a condensation product of four moles of propylene, i.e. a mixture of branched 2 ° leucines. P-4 is non-polar and is preferably used in combination with a polar solvent such as benzyl alcohol, diethyl phthalate, butyl carbitol or the like.

Other polar solvents useful herein include "cellosolves", for example, alkoxyalkanols such as 2-butoxyethanol, C 1-6 alkanols (including 0-12 benzyl alcohol) such as dodecanol, phenethyl alcohol, di-glycol ether acetates, hexylcellosolve, hexylcellosolve, hexyl .

2i 73731

Example XIX

The following are further examples of degreasing solvent compositions that can be used with alkoxylated polyamines in accordance with the present invention.

5 Composition Component Percentage A Octylbenzene 70

Diethyl phthalate 30 B 1-decene 70

Diethyl phthalate 30 10 C Octylbenzene 80

Benzyl alcohol 20 D n-octylbenzene 90

Butyl carbitol 10 E 1-decene 65 15 Dibutyl phthalate 35 F n-octylbenzene 30 1-decene 40

Benzyl alcohol 10

Butylcarbitol 20 20 G 1-decene 80 n-hexanol 20 H 1-decene 60

Diethyl phthalate 40

I 1-dodecene SO

25 Hexylcellosolve 20 J Mixture of nonyl and hexylbenzene (1: 1) 35 2-dodecene 35

Dimethyl Phthalate In a preferred method of use, the compositions of this invention are used in wash water (the composition is measured in 1% water) at a pH of 6.5 to 8.0 to wash fabrics. Excellent cleaning results are achieved by mixing the fabrics in such solutions at this operating pH.

22 7 3 7 31

Nitrogen functional groups include stabilizers / pH adjusters

As mentioned in Examples XIII and XVII above, various alkyl and cycloalkylamines, quaternary ammonium compounds, and amine oxides form a highly preferred group of pH adjusters and stabilizers for oil-in-water microemulsion detergent compositions of the type of this invention. Apparently, such agents are in some way capable of binding to a fatty acid or anionic surfactants and forming a complex that stabilizes the microemulsified oil (solvent). Although the compounds containing functional groups do not change the pH particularly much in the basic direction (only a few tenths of a unit, measured from the product "as such"), the resulting increase in washing power, especially enzymatic cleaning power, is considerable.

In addition, it should be noted that any known basic substance can be used to adjust the pH of the compositions to approximately 6.5 to 6.6, for example, triethanolamine, alkali metal hydroxide, and the like. Potassium hydroxide is more preferred than sodium hydroxide because the potassium cation greatly facilitates the formulation of stable systems.

Dioctyldimethylammonium chloride is a highly preferred quaternary compound used as a pH adjusting agent in the compositions of this invention, but the following quaternary compounds may also be mentioned (in ascending order of preference): coconutalkyltrimethylammonium chloride (6.66), dichloroammonium dichloro ), coconut alkylbenzyldimethylammonium chloride (6.84) and dihexyldimethylammonium chloride (6.89). The figures in parentheses indicate the pH obtained by adding the quaternary compounds in question to a liquid oil-in-water microemulsion containing a fatty acid and having a pH "as such" of 6.5. In the case of the preferred dioctyldimethylammonium chloride, the pH is 6.94.

t! 23 7 3 7 3 1

Suitable alkyl and cycloalkylamines (and related pHs) useful herein include coconut alkyldiethanolamine (6.65), coconut alkyldiethylamine (6.75), trioctylamine (7.0) and cyclohex-5-cylamine (7, 5).

Suitable amine oxides include coconut alkyldimethylamine oxide (6,7) and dioctylmethylamine oxide (approximately 7).

It should be noted that the aforementioned nitrogen compounds 10 may be added to the compositions until the desired ohm is achieved. To achieve the stated pH, 0.5 to 5% of these compounds are usually used in the compositions. Most preferred in this context, cycloxyl amyl is for use. i (1-5 h).

In general, the most preferred oil-in-water microemulsion form of the compositions of this invention contains a) 10-70 L of water (carrier), b) 5-20% degreasing solvent or solvent mixture, c) 5-35% fatty acid or fatty acid soap mixture, d) 1-40% of a cleaning surfactant, e) 0.001 to 2% of a cleaning enzyme, f) at least 0.2% of an alkoxylated polyamine, and u) to adjust said composition to oK 6.6 to 7.5 nitrogen-containing substances (as described), in particular cyclohexylamine.

The stability of such microemulsions can be assessed visually by observing phase separation or monitored quantitatively by conventional turbidity measurement methods. The pH of the product ("as such") was measured at ambient temperature (23 ° C) with a standard commercial pH meter. The electrode is immersed in the product and allowed to stabilize before taking the reading.

Example XX

Highly preferred liquid laundry detergent due to the slight odor of its degreasing solvent system, its stability in 35 (microemu] form and its oncymatic cleaning effect (due to low pH) or scura: 24 73731

Ingredient Weight C-. -Alkylbenzenesulfonic acid 11.0

I / O

C 4 -C 4 alkyl ethoxylate (EO 7) 12.0

Coconut fatty acid fraction from which light ingredients 5 have been distilled off (1) 20.5 C.n .1-isoparaffins 4.0

Diethyl phthalate 6.0

Cyclohexylamine 2.0

Monomethylethanolamine (2) 4.3 10 Potassium citrate monohydrate (63.5% aqueous solution) 2.4

Dequest 2060 S 1.7

Ethoxylated polyamine (x = 5; y = 15) 1.5

Potassium hydroxide (50% aqueous solution) (2)

Formic acid 0.2

CaCl2 · 2H2O 0.05

Optical brightener (anionic) 0.18

Maxatase enzyme (3) 0.71 20 Termamyl 300L enzyme (4) 0.10 Dye 20 ppm

Perfume 0.5

Water into 110

Product pH 6.9 25 (1) Chain length of the components of the mixture: (5%), Cl 2 (55%), (22%), Cl 2 (2%), oleic acid (10%) (2) for pH adjustment to 6.6 (3) KNGS (4) from NOVO 30 The composition of Example XX is used in wash water per 100 ml per 10 liters to give an operating pH of about 7.2 (varies according to the hardness of the water).

Claims (11)

1. A stain removal composition, characterized in that it contains a) a) a fat-removing solvent and b) an alkoxylated polyamide having the formula R '-fN-Rf- or 4N®-Rf-Χθ x. x is alkoxy alkoxy wherein R is a hydrocarbon group of 2-6 carbon atoms, R 'is a hydrocarbon group of 1-20 carbon atoms, alkoxy is polyethoxy, polypropoxy or polybutoxy group or a mixture thereof, the degree of polymerization in this chain is 2-30, x is an 0 integer which is at least 2 and X is an anion. 2. A composition according to claim 1, characterized in that said alkoxylated polyamine is a polymerized reaction product of ethylene oxide and ethyleneimine. 3. Composition according to claim 2, characterized in that the alkoxylated polyamine has the formula - + N-CH 2 -CH 2 t -x (EtO) y wherein EtO is ethyleneoxy, X is an integer of 3-5 and y is a integers 10-20. 4. A composition according to any one of claims 1-3, characterized in that the weight ratio of solvent to alkoxylated polyamines is in the range 100: 1-1: 20. Composition according to claim 4, characterized in that it contains at least 5% of the mixture of solvent and alkoxylated polyamine. 6. Detergent composition for washing fabric and containing customary washing ingredients, characterized in