FI78730C - LOESNINGSMEDEL INNEHAOLLANDE FLYTANDE TVAETTMEDELSKOMPOSITIONER AVSEDDA FOER TVAETTNING AV TYGER. - Google Patents

Description

1 78730

This invention relates to compositions and methods for washing fabrics using solvent 5 in high concentrations to promote the removal of grease and stains. The liquid compositions of the invention are prepared in the form of clear, or substantially clear, homogeneous stable emulsions which not only have excellent cleaning ability when used as pretreatments, but also improved washing performance and whiteness retention of the fabric when used in wash water. In addition to better removing grease stains, the compositions according to the invention also excellently remove particles in the form of dirt from fabrics. The compositions are formulated and stabilized to a pH that can range from near neutral to basic.

A wide variety of organic solvents, including terpenes and terpenoid compounds, are known to be used in hard surface cleaners due to their degreasing ability. Such detergents often contain 10%, or more, of a solvent such as D-limonene, as well as a surfactant, especially nonionic surfactants, which are also known for their degreasing properties. Such compositions have also been proposed for cleaning carpets. GB Patent 1,603,047, 1981. EP-A-40882 deals with hard surface cleaners consisting of a mixture of benzyl alcohol, terpenes, surfactants and other cleaning ingredients.

Citrus juices containing relatively small amounts of terpenes have been proposed for use in hand soaps and dishwashing liquids. U.S. Patent 3,650,968, 1972; MÖmoire descriptif 873 051 (accompanied by GB publication 2010892).

35 Terpineols, such as those obtained from tall oil, have been proposed for use in the wet rubbing of textiles.

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In particular, U.S. Patent 2,073,464, 1937, discloses clear compositions that can be prepared from pine oil terpineol, such as cX-terpineol, and fatty acid soap or free acid neutralized in situ to a basic pH of 5.

A more recent article, Soap Perfumery Cosmetics, April 1983, pp. 174-175, states that only small amounts (3%) of terpenes can be included in high performance liquid detergents.

EP 0 072 488 (August 3, 1982) discloses that terpenes such as D-limonene can be included in fabric pretreatment compositions as inhomogeneous emulsions. Such emulsions are apparently intended to be packaged in relatively small volume containers that can be shaken immediately prior to use to restore a substantially homogeneous shape, and then applied directly to the fabrics by spraying.

Clear emulsions containing water, surfactant, and various other solvents have been discussed by Davidsohn, 3rd International Congress of Surface Activity, Cologne (1960).

The use of relatively high solvent concentrations in liquid high power detergents offers many advantages.

25 The liquid form of such products makes it possible to use them as pre-treatment agents. When used in actual washing, solvents such as terpenes have now been found to offer additional advantages over cleaning compared to detergent surfactants. Unfortunately, the inhomogeneity of compositions such as those disclosed in EP-A-0 072 488 makes them unsuitable for general purpose detergents, as most high performance liquid detergents are packaged in relatively large containers which are difficult for the user to shake properly.

35 In addition, only a small amount (about 3%) of terpenes in detergent compositions used in the actual washing process offers only a small additional advantage in cleaning, as dilution with washing solution nullifies their effect.

This invention relates to fully formulated liquid high power detergents containing as much as 20% by weight or more of a solvent which is not substantially soluble in water and which are homogeneous fatty acid enhancing liquids which are well suited for use in both fabric pretreatment and actual washing.

It is possible to formulate the compositions of the invention into stable microemulsions having a pH of about 6.5 or higher.

The compositions of this invention may be briefly described as high performance liquid detergents comprising conventional detergent ingredients such as surfactant enhancers ("builders"), enzymes, detergent surfactants, enzyme stabilizers, and the like. formulated as oil-in-water emulsions (with the solvent being the "oil" phase) in an aqueous medium.

The detergent composition of the invention comprises an aqueous carrier, 10-40% by weight of a non-soap surfactant detergent and 5-20% by weight of a degreasing solvent comprising a non-polar solvent component which may be terpene, paraffin oil, halogenated hydrocarbon, C 8 -C 6 alkyl-substituted aromatic compound, liquid olefin or a mixture thereof. The composition is characterized in that it comprises from 5 to 30% by weight of C 2 -C 2 -g-ras-30 waxic acid or C 2 -C 2 -g-fatty acid soap and a microemulsion stabilizer, the stabilizer being a water-soluble, high ionic strength substance, which is a formate, sulfate or nitrate, a non-polar solvent-soluble substance having an HLB of 2-5, a nitrogen-functional compound or a mixture thereof, wherein the composition has a pH of 6.5-8.0 and is stable in oil-in-water- in the form of a microemulsion.

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The following describes in more detail the essential emulsification system of solvent, fatty acid (or soap) and water, detergent surfactants, means for stabilizing formulations to pH values above 6.5, and a variety of other possible ingredients used in the practice of this invention. applications. All percentages and ratios mentioned in this specification are weight percentages and ratios unless otherwise indicated.

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

The formulation of compositions of the type of this invention is guided in the choice of solvent partly by the need to provide good degreasing properties and partly by aesthetic considerations. 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 or odor that can be changed from tolerable to perfume. Examples of such solvents are citrus-terpene solvents, in particular orange-terpenes and D-limonene. Another relatively pleasant-smelling solvent suitable for this purpose is benzyl alcohol. Mixtures of orange terpene and benzyl alcohol are particularly suitable for removing certain types of stains, such as stamp ink, shoe polish and used engine oil.

Excellent solvents for use in the 5,78730 compositions of this invention include paraffins and mono- and bicyclic monoterpenes, i. hydrocarbon compounds such as terpinenes, limonenes and pinenes and mixtures thereof. Highly preferred substances of this latter type are mixtures of D-limonene and terpene hydrocarbons obtained from orange extract (e.g. cold-pressed orange terpenes and orange terpene oil phase from fruit juice). Also, for example, terpenes such as dipentene, learned, β-pinene, and mixtures of terpene hydrocarbons compressed from lemons and grapefruits are useful.

A variety of other solvents, and particularly preferred mixtures of non-polar and polar solvents, that can be used in the compositions of this invention are set forth below.

Fatty acids and soaps

Fatty acids such as lauric, myristic, palmitic, stearic, and oleic acids, as well as polyunsaturated fatty acids, as well as their water-soluble salts (i.e., "soaps"), are used in the compositions of this invention to provide clear, homogeneous, solvent- and water-containing formulations. Mixtures of fatty acids (or soaps), e.g. palm oleic acids, coconut oil acids and the like having carbon chain lengths of 25 to 18 ° C can be used. In general, the content of fatty acid (or soap) is 5-50%, preferably 5-35% and most preferably 5-30%, and the weight ratio of fatty acid (or soap): solvent is 4: 1 to 1: 4, preferably 3: 1 to 1: 2. When using a fatty acid soap, potassium and sodium salts are preferred, but any suitable water-soluble salt may be used.

Not only do these fatty acids and soaps act as microemulsion stabilizers, they also significantly enhance the action of the surfactant in the compositions of this invention. However, it has now been found that when formulating oil-in-water microemulsion compositions having a pH higher than about 6.5, the presence of a fatty acid / soap can in fact destabilize the system. Means to prevent this destabilizing effect while maintaining the pH of microemulsions containing a surfactant-enhancing amount of fatty acid / soap at 6.5 or above are described in more detail below.

Water The compositions of this invention can be aptly described as "aqueous", as opposed to organic solvent-based cleaners known in the art.

Surprisingly, water can adversely affect the ability of solvents, such as terpenes, to remove grease stains from fabrics. For example, a fabric stained with engine oil that has been moistened with water prior to treatment with terpene alone will not release fat very well with terpene, if at all. In contrast, the compositions of this invention containing a non-polar solvent, such as terpenes, microemulsified in water are excellent degreasers when applied directly to a dry or damp fabric.

Not only is water clearly environmentally friendly, safe, and inexpensive compared to organic solvents, water-based liquid high performance detergents have the advantage of ease of formulation with respect to ingredients such as most builders, disinfectants, chelating agents, dirt suspending agents, and pH adjusting agents. , which are usually water soluble.

Thus, the compositions of this invention have the advantages of water-based formulation flexibility as well as better degreasing properties than solvent-based compositions.

As discussed in more detail below, the compositions of this invention generally contain 10-70%, preferably 20-50%, water. The weight ratio of water to solvent is generally 7,78730 10: 1 to 1: 1, preferably 5: 1 to 2: 1.

pH / Stabilizer

As is known in the detergent industry, the pH of detergent compositions is preferably close to neutral or basic, i.

5 6.5 or higher. There are many reasons for this. For example, many dirt pepticize or emulsify in part under the influence of alkalinity itself. In addition, many commercially available cleaning enzymes (e.g., "basic proteases") work best in alkaline wash solutions.

It has now been found that stable detergent compositions in the form of an oil-in-water microemulsion containing fatty acid / soap in concentrations such that it acts as a builder destabilize when their pH is adjusted to approximately 6.5 or higher. (The pH at which instability is observed may vary slightly depending on the actual degreasing solvent used in the microemulsion and its concentration, as well as the length and degree of unsaturation of the fatty acid carbon chain). This problem is particularly significant when using relatively non-polar, degreasing hydrocarbon solvents, such as orange terpenes and paraffin oils.

The stability problem appears to be caused by a fatty acid with an HLB of about 2 and which is almost completely converted to a soap with an HLB of about 20, in a very narrow pH range, 25 in the range of about 6.5-6.9. Thus, due to the presence of significant amounts of fatty acid (about 5% or more), this large change in HLB oscillates the HLB of the emulsification system and leads to destabilization.

It should be noted that, in theory, a stable formula could be obtained by selecting suitable surfactants (discussed below) with a low HLB. For example, nonionic surfactants such as C 1-4 alcohols with a low degree of ethoxylation (1-3) would be useful. However, such low HLB surfactants do not function well as cleaning surfactants, and it is an object of the present invention to provide not only stable microemulsions but also good cleaning performance in pretreatment and actual washing.

It has now been found that the microemulsion can be stabilized either by increasing the ionic strength of the aqueous phase or by adding solvent-soluble ingredients with low HLB and increasing the polarity of the solvent to the solvent phase, or by using both methods together.

In particular, the addition of water-soluble ingredients having high ionic strength, such as formates, sulfates, citrates and the like, increases stability. In contrast, the addition of water-soluble substances with low ionic strength, such as ethanol, does not have a stabilizing effect.

Also, the addition of slightly polar components with low HLB and soluble in a non-polar solvent such as n-hexanol, benzyl alcohol, fatty alcohol mixtures and the like improves the stability.

The simultaneous addition of ionic strength enhancing ingredients and solvent soluble ingredients further improves stability. The formulator can, of course, select ingredients with the goal of not only increasing the stability of the microemulsion but also achieving the best possible cleaning benefit. For example, citrate, which also has surfactant-enhancing properties, or a format that also stabilizes detergent enzymes, and n-hexanol or benzyl alcohol, which also removes fat, can be selected as the ionic strength enhancer.

The amount of ionic strength enhancing ingredient and / or solvent-soluble low HLB (e.g. 2-5) ingredient used in the compositions depends to some extent on the desired pH, fatty acid content, degreasing solvent content, detergent surfactant composition. composition and 9 78730 other similar matters. The stability of the microemulsion can be monitored in a fairly simple way, as the actual microemulsions are clear but become cloudy and inhomogeneous, possibly causing phase separation when a point of instability is reached.

With respect to adjusting the pH of the compositions, any known basic substances may be used to adjust the pH to approximately 6.5-6.6; Examples include Triethanolamine, alkali metal hydroxides and the like. Potassium hydroxide is more preferred than sodium hydroxide because the potassium cation greatly facilitates the formulation of stable systems.

One useful neutralization base is magnesium-15 hydroxide. In use, the magnesium cation is believed to be associated with the anionic surfactants contained in the composition, thereby improving their degreasing ability.

The preferred use of various amines, amine oxides, and quaternary ammonium compounds (i.e., "nitrogen-containing" compounds) to adjust the pH above 6.5-6.6 and to promote stabilization of the microemulsions is described in more detail below.

Detergent Surfactants The compositions of this invention typically contain organic surfactants to provide the conventional cleaning benefit associated with the use of these agents.

Detergent surfactants useful in the compositions of this invention include known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are alkylbenzenesulfonates, alkyl and alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl-35 phenols, amine oxides, known. Such detersive surfactants generally contain a C 1 -C 6 alkyl group; anionic surfactants may be used in the form of sodium, potassium or triethanolammonium salts, but it should be noted that the presence of magnesium cations in the composition usually means that at least a portion of the anionic surfactant is in the form of a magnesium salt; nonionic surfactants generally contain about 5-17 ethylene oxide groups. U.S. Patent Nos. 4,111,855 and 10,399,669 contain detailed lists of such typical detergent surfactants.

C11-8 alkyl benzene sulfonates, 2- g-paraffin sulfonates and alkyl sulfates as well as ethoxylated alcohols and alkylphenols are particularly preferred for use in compositions of the type of this invention.

The surfactant component may comprise only 1% of the compositions of this invention, but preferably the compositions contain 1-40%, more preferably 10-40%, of a surfactant. Mixtures of ethoxylated nonionic surfactants and anionic surfactants such as alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for cleaning fabrics from various soils and stains by actual washing. The HLBs of such surfactants and mixtures are typically at least 20.

polyamines

Potential ingredients in the compositions of this invention include polyamines, as they are capable of interacting with a solvent to remove solids present in many grease stains (e.g., soot in engine oil stains or clay and color particles in cosmetic stains).

It should be noted that as used herein, the word "polyamines" generally refers to alkoxylated polyamines, both in their amine-35 form and in their quaternized form. These substances can be conveniently presented as molecules with an empirical structure of repeating 11,78730 units: -f N R Amine Form I * 5 alkoxyl and.

R

-f ϊΡ - R -h} E) Quaternized form I x 10 alkoxyl wherein R is a hydrocarbon group usually containing 2 to 6 carbon atoms; R 'may be a _2Q hydrocarbon group; alkoxyl groups are polyethoxy or polypropoxy groups or the like having a degree of polymerization of the polyethoxy group of 2 to 30, most preferably 10 to 20; x is an integer of at least 2, preferably 2-20 and most preferably 3-5; and X® is an anion resulting from the quaternization reaction, such as halide or methyl sulfate. Anion X® has no particular effect on the function of the polyamine in the compositions of this invention and is mentioned only to complete the above formula.

The most preferred polyamines for use in the compositions of this invention are the so-called ethoxylated polyethyleneimines, i. a polymerized reaction product of ethylene oxide and ethyleneimine having the general formula 30 -f-N-CH2-CH2 + (E + O) y wherein x is an integer of 3-5 and y is an integer of 10-20.

The proportion of polyamines in the preferred compositions of this invention is typically at least about 0.2%, 12,78730 generally 0 / 5-5%.

Other Optional Ingredients The compositions of this invention may contain other ingredients that enhance their cleansing ability.

For example, it is highly preferred that the detergent compositions used in the actual wash contain a surfactant and / or a metal ion scavenger. Compounds classified as detergent builders and known 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 scavengers include all of the above, as well as substances such as ethylenediaminetetraacetate, aminopolyphosphonates and phosphates (DEQUEST), and several other polyfunctional organic acids and salts that are too numerous to list in detail herein. U.S. Patent 3,579,454 provides typical examples of the use of such agents in various detergent compositions. Builder and metal ion scavenger generally make up about 0.5-15% of the composition. One of the most preferred builders is citrate, as it readily dissolves in the aqueous phase of liquid high power detergent compositions. These ingredients are also useful in hard surface cleaners.

For the reasons set out above, a source of magnesium ion can be used in the compositions. In addition to magnesium hydroxide, water-soluble salts such as magnesium chloride, acetate and sulfate and the like are useful.

The laundry detergent compositions of this invention preferably also contain enzymes that enhance their ability to clean in the actual wash from a variety of soils and stains. Amylase and protease enzymes suitable for use in detergents and their use in commercial liquid and granular detergents are known in the art. Commercial cleaning enzymes (preferably a mixture of 13,7730 amylase and protease) are typically used in concentrations of 0.001-2% or greater in the compositions of this invention. If the formulator so desires, ingredients such as propanediol and / or formate as well as calcium may be added to the compositions to promote stabilization of the enzymes in a known manner.

In addition, the compositions of this invention may contain, in addition to the ingredients already mentioned, a wide variety of other ingredients commonly used in commercial products to improve the aesthetics or performance of the products. Typical ingredients include perfumes, colorants, optical brighteners, dirt suspending agents, hydrotropes and gel regulators, freeze-thaw stabilizers, bactericides, preservatives, defoamers and the like, which may be present in a concentration of 0.1-15 %.

Water or mixtures of water and alcohol (e.g. ethanol, isopropanol, etc.) are used as the carrier, and alkylated polysaccharides can be used to improve the stability and performance of the compositions.

The compositions of this invention are liquids and can be prepared simply by mixing the main ingredients and any other ingredients with an aqueous vehicle. The stability of the microemulsion can be assessed visually by observing the phase separation or monitored more quantitatively by conventional turbidity measurement methods.

The compositions can be used to pre-treat soiled fabrics by rubbing a few milliliters of the composition directly into and within the soiled area, followed by washing in the conventional manner. In the actual wash, the compositions are typically used to wash fabrics of at least 500 ppm, preferably 0.1-1.5%, in wash water having a pH of 6.5 or higher. The washing can be performed at a temperature between 5 ° C and the boiling temperature of 35, with excellent results.

For use on hard surfaces, as carpet cleaners and 14,78730 all-purpose cleaners, the compositions are diluted with water, or used undiluted, both in the conventional manner.

Industrial Application The following examples illustrate various formulations that can be prepared in accordance with the present invention. The examples are provided to illustrate the invention and are not intended to limit the scope of the invention. In the polyamine-containing formulations shown, the terms "x" and "y" in parentheses indicate the degree of polymerization and the degree of alkoxylation of the polyamine. For some "polyamines", the term R 'is also mentioned, indicating the quaternized polyamine in question. In the case of such quaternized substances, the resulting anion is not relevant for purification efficiency and has not been reported.

High performance liquid detergents

Particular attention is paid to those particularly advantageous formulations which can be used in particular as liquid high-performance detergents which are suitable for washing all kinds of fabrics by a typical household washing method. A variety of detergent ingredients are used in the formulation of the High Power Liquid Detergents shown below to provide an excellent cleaning result for a variety of dirt and stains and particularly significant advantages for stains caused by cosmetics and used engine oil.

It should be noted that the following formulations are in the form of oil-in-water emulsions (in which the solvent is considered to be an "oil" phase) and are approximately clear, homogeneous and stable microemulsions. Surprisingly, when used as pretreatments, the degreasing ability of the oil-in-water microemulsions of this invention is comparable to the degreasing ability of water-in-oil emulsions with much higher solvent contents. The compositions also excellently retain the whiteness of cotton fabrics, apparently because the solvent reduces the accumulation of fatty acid soap on the surface of the fabrics. These performance benefits are particularly significant after multi-stage washes.

5 Example I

Ingredient Weight part

Ethanol 3.0

Potassium hydroxide (50% aqueous solution) 10.0 C 1-4 alkylbenzenesulfonic acid 11.0 1 1 φ ö 10 g alkyl ethoxylate (EO 7) 15.0

Potassium citrate monohydrate (63.5% aqueous solution) 4.8

Dequest * 2060 S (trade name) 1.2

Sodium formate (40% aqueous solution) 2.5 15 Ca ++ as CaCl 2 * 6H 2 O 60 ppm

Orange terpenes 10.0

A mixture of lauric and myristic acid (60:40) 12.5 oleic acid 2.5

Maxatase ** enzyme (trade name) 0.71 20 Termamyl *** enzyme (trade name) 0.10 FWA 0.23: Fragrance 0.5 Dye 20 ppm

Water to 100 25 Product pH 7.5 * Diethylenetriamine pentamethylenephosphonic acid (Monsanto) ** KNGS, supplied by *** NOVO, supplied 30 The above composition is prepared by mixing said ingredients together to give a clear stable microemulsion. In the washing tests, especially in the pretreatment step, the ability of the compositions to remove a wide variety of stains, especially those caused by cosmetics and used 35 motorized rice, is excellent.

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Example II

The composition of Example I is slightly modified by replacing 2 parts of 50% KOH with 0.6 parts by weight of magnesium hydroxide and adjusting the pH to 7.5. The resulting product 5 is a clear homogeneous and stable microemulsion.

Example III

The composition of both Example I and Example II is modified by the addition of 1.5 parts by weight of tetraethylene pentamine ethoxylated with an average of 15 moles of ethylene oxide per nitrogen atom. The resulting composition is a clear homogeneous and stable microemulsion above pH 6.9.

As another example, any of the above compositions can be modified by replacing the orange-15 terpene probe with a mixture of deodorized paraffin oil (C10-120 ° Paraffins; 7.5% of the total composition) and orange terpenes (2.5% of the total composition). This modification of the solvent component does not in any way impair the performance of the compositions but gives the odorant 20 greater freedom to use shades other than citrus scents. If desired, an anionic optical brightener (0.01-0.5%) can be added.

Solvent selection

As discussed above, the final choice of solvent system to be used in the compositions of this invention will depend on the type and load of dirt, aesthetics (odor), etc. However, a few characteristics may be used to assist in this selection. For example, the solvent should not be significantly miscible with water, and should, of course, be able to dissolve a wide variety of problematic grease stains. With respect to this latter property, thermodynamic solubility parameters (Hansen parameters) are useful in solvent selection.

Each solvent can be described by the Hansen parameters of 35 g and: is the dispersion component, is the polarity component and is the hydrogen bonding component.

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Similarly, the main problematic grease stains can be described by the “pseudo” -Hansen parameters by first determining the solubility of each grease stain in several different solvents with different Hansen-para-5 meters.This can be done by immersion in different types of fabrics (cotton, cotton-polyester, acrylic) grease stain alternately in each solvent for a specified period of time (say 5 minutes) while stirring evenly.When removing the fabric from the solvent, excess solvent is drained off and the stained fabric is washed for 5 minutes in cold water containing 1% of a typical liquid laundry detergent. -after rinsing and drying, the loss of the stain is assessed visually or by any other suitable method, in order to identify the solvents which best remove each of the problematic grease stains and thus to determine the pa the range required for the best possible removal for each Hansen parameter. This allows the Hansen-20 parameters to be mapped for each stain, and the solvent / solvent combinations can be selected on this basis to achieve the desired efficiency.

By no means limiting the present invention, the above procedure shows that solvents / solvent combinations with Hansen parameters in the ranges (C, (7-9), <£ (0-7) and S (0-4) are critical dnp The solvent combination can be selected for certain grease stains, such as 30 engine oils, in which case the most preferred ranges for the Hansen parameters are (7-9), (0-4) and (0-3), or for the labeling ink, in the formulation of microemulsions with excellent grease removal. , wherein the most preferred ranges are 6 ^ (7-9), (2-11) and (2-7), removal or, more broadly, removal of miscellaneous stains, in the latter case an intermediate point is selected from a range of 35 Hansen parameters.

The solvents and solvent mixtures preferably used in the compositions of this invention are, in particular, orange terpenes (D-limonene), paraffins (especially C 10-12 paraffins), cyclohexane, kerosene, orange terpene-benzyl alcohol (60:40), -5 mixture of paraffins and hexanol (50:50), Hansen parameters are in the indicated range.

Any of the above examples can be modified by replacing the solvents shown with the above-mentioned mixtures, in particular of terpenes or paraffin oil and benzyl alcohol-10-alcohol, n-hexanol or 1-butanol. The preferred pH for high performance detergents is 6.5-8.0, more preferably 6.6-7.3. The pH of the product ("as is") is measured at ambient temperature (23 ° C) using a commercial pH meter. The electrode is immersed in the product and the meter is allowed to stabilize before taking the reading.

The following examples relate to solvent-containing compositions within the scope of this invention which are particularly suitable for large industrial laundries and cleaning plants and the like. The formulator should note 20 that some of the solvents used in such compositions may not be suitable for general household use due to their odor, potential for skin irritation, low flash points, and the like. However, such compositions are perfectly suitable for use by professionals 25 who take such factors into account under properly controlled conditions. In Examples IV-IX, the pH of all compositions is adjusted with magnesium hydroxide, as mentioned. The proportions of all other ingredients are given in parts by weight.

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A_ineosa -χν v VT VII vm K

Stoddard solvent 100 _ _ _ _ 250

Trichlorethylene - 10 - - -

Naphtha _ _ 30 - _ 5 Petroleum ether (b.p. 80-85 ° C) _ go 100

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) 10 Water 100 100 200 100 250 350

Coconut fatty acids 20 20 25 60 100 15 C. 2 ”alkylbenzenesulfonic acid50 5 - - 10 20 C10 .., - alcohol ethoxylate 1Z” 13 50 20 (EO av. 9) 15 C 1-4 alkylphenol (ethoxylated; EO av. 6) 2 10 100 10 MG (OH) 2 to pH 7.0 7.1 7.5 _ 7.7 8.1 * The polyamines 20 AF used in Examples IV-IX have the general formulas given above and 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 25 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 * = eicosyl As can be seen from the foregoing, the present invention encompasses a wide variety of formulations in the form of stable solvent-containing emulsions. An excellent liquid high performance detergent composition can also be prepared using a combination of diethyl phthalate (preferred) or dibutyl phthalate and terpenes (preferably orange terpene) or dipentene or paraffin oils or (preferably) a mixture thereof as a solvent. The following is a typical example of such a composition.

Example X

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

Potassium hydroxide (50% aqueous solution) 8.0

Ethanol 3.0

C 1-4 alkylbenzenesulfonic acid 11.0 C14 / 1 alkyl ethoxylate (EO 7) 15.0 10 Potassium citrate (63.5% aqueous solution) 2.4

Ha j unpo i stokä s sted pa pa f i in iö1j y (C10-isoparaffin) 7.5

Orange terpene 2.5

Dibutyl phthalate 3.0 15 A mixture of lauric and myristic acid (60:40) 12.5

Enzymes (according to Example I) 1.0

Water and secondary ingredients as well as MgiOH to adjust the pH to 7.3 to 100. In Example X, dibutyl phthalate can be replaced with an equivalent amount of diethyl phthalate.

It should be noted that many of the terpene hydrocarbon-containing compositions described above necessarily have a fairly strong citrus odor, which may not be fully accepted by all formulators of such compositions. It has now been found that C8-C8-substituted aromatic solvents, in particular C8-C8-alkylbenzenes, of which octylbenzene is preferred, have excellent degreasing properties and a mild, pleasant odor. Olefin-30 solvents having a boiling point of at least about 100 ° C, especially α-olefins, preferably 1-decene and 1-dodecene, are also excellent degreasing solvents. Isoparaffins (especially those with a carbon chain of 10-12 C atoms) are also noteworthy due to their mild odor and good degreasing properties.

Additional examples of preferred mixtures of non-polar and polar 21,78730 solvents that can be used in the practice of this invention include the above-mentioned alkyl-substituted aromatic solvents or paraffin or olefin solvents and polar solvents such as benzyl alcohol, n-hexarbol, But-hexanol, Butyl; - (2-butoxyethoxy) ethanol) or phthalic acid esters, combinations.

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

Example XI

15 Ingredient Weight% C ,. O-alkylbenzenesulfonic acid 10.0 J 1 f

C 14-1g alkyl ethoxylate (EO 7) 10.9

Coconut fatty acid (broad fraction) 18.2 oleic acid 2.3 20 Monomethylethanolamine 5.8 1-decene 9.1

Ethanol (95%) 2.7

Dequest (50%) 1.09

Formic acid 0.18 25 Kj citrate monohydrate (63.5% aqueous solution) 4.4

CaCl2-2H2O 0.05

Maxatase enzyme (protease) 0.73

Termamyl enzyme (amylase) 0.10 2

Ethoxylated polyamine 1.73 30 Perfume / optical brightener / colorant 0.5

Water to 100

Product pH 6.6 1. Diethylenetriamine pentamethylenephosphonic acid 35 2. Tetraethylenepentamine (105 EO units / molecule) 22 7 8 7 30

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

Example XII

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

Example XIII

The composition of Example XI is modified to replace -10 miles of 1-decene with any of the following solvent mixtures (percentages in parentheses indicate the proportion of the total formula): a mixture of 1-decene (6.1%) and diethyl phthalate (3.0%); A mixture of 1-dodecene (7.3%) and benzyl alcohol (1.8%); a mixture of n-octylbenzene (6.2%) and diethyl phthalate (2.9%); and a mixture of n-octylbenzene (6.0%) and butylcarbitol (3.1%). The pH of the products as such is 6.6.

Example XIV

The compositions of Examples XI, XII and XIII are modified by the addition of a sufficient amount of dioctyl di-20 methylammonium chloride to adjust the pH of the compositions ("as is") from 6.6 to 6.94. The resulting compositions have exceptionally good fabric cleaning and whitening retention.

It should be noted that the preferred compositions of Examples XI-XIV are true oil-in-water microemulsions. When diluted with water, the compositions appear cloudy. Water-in-oil emulsions, on the other hand, tend to gel upon dilution, while oil-in-water blend compositions remain clear upon dilution.

Example XIV illustrates the use of a nitrogen functional component (quaternary compound) to adjust the pH of a product. Other such pH adjusters include (product pH in parentheses): coconut alkyldiethanolamine (6.65), coconut alkyldimethyl-35 amine (6.75), trioctylamine (7.0), cyclohexylamine (7.5), coconut alkyltrimethylammonium chloride (6 , 66), 23,78730 coconut alkyldimethylamine oxide (6.70), dicocoalkyldimethylammonium chloride (6.84), coconutalkylbenzyldimethylammonium chloride (6.84), dihexyldimethylammonium chloride (6.89) and dioctyldiimethylamine Such nitrogen-functional substances are used in the compositions to adjust the pH at concentrations of 0.5-5% and contribute significantly to maintaining the purity and whiteness of the washed fabrics. For this application, cyclohexylamine (1-5%) is preferred. Another preferred olefin solvent for use in the compositions of this invention is the so-called "P-4" polymer due to its relatively mild odor, which the detergent industry can obtain as a feedstock for branched alkylbenzene from a few petrochemical suppliers.

P-4 is a mixture of isomers obtained as a product when 4 moles of propylene condense, i. a mixture of branched C ^ 2 ~ ° ^ -e ^ etins. 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.

In addition to "carbitols" (2- (2-alkoxyethoxy) ethanol), other solvents useful in the compositions of this invention include "cellosolvents", for example, 2-alkoxyalkanols such as 2-butoxyethanol, 2 "alkyl" alcohols such as dodecanol, phenethyl alcohol and diglycol-25. ether acetates and the like.

Example XV

A composition which is preferred for its mild odor and suitability for packaging in polyethylene containers is prepared by replacing the 1-decene in Example XI with a solvent-30 mixture (as a percentage of the total composition) of 6% diethyl phthalate, 2% liquid isoparaffins ^ C10-12 ^ and 2% orange terpene. .

Significantly, not all of the microemulsion compositions of this invention damage HD polyethylene, and thus can be packaged in HD polyethylene bottles. In contrast, many solvent-based cleaners, 24 7 8 7 3 0 that are not true microemulsions, must be packaged in more expensive metal cans or PVC bottles.

Example XVI

Further examples of degreasing solvent mixtures consisting of a polar and a non-polar solvent suitable for use in the compositions of this invention include the following:

Composition Ingredient Percentage A Octylbenzene 70 10 Diethyl phthalate 30 B 1-decene 70

Diethyl phthalate 30 C Octylbenzene 80

Benzyl alcohol 20 15 D n-octylbenzene 90

Butyl carbitol 10 E 1-decene 65

Dibutyl phthalate 35 F n-octylbenzene 30 20 1-decene 40

Benzyl alcohol 10

Butylcarbitol 20 G 1-decene 80 n-hexanol 20 25 H 1-decene 60

Diethyl phthalate 40 L 1-dodecene 80

Hexylcellosolve 20 J Mixture of nonyl and hexylbenzene 30 (1: 1) 35 2-dodecene 35

Dimethyl phthalate 30

With respect to the use of the compositions, in a preferred method, the compositions are used in wash water (pH 6.5-8.0 with water containing 1% of the composition) for washing fabrics.

25 78730

Excellent cleaning results are achieved by mixing the fabrics in such solutions at this operating pH.

Example XVII

A highly preferred liquid laundry detergent due to the mild odor properties of this degreasing solvent mixture, its stability in microemulsion form and its enzymatic cleaning performance (due to low pH) is as follows:

Ingredient Weight 10 g of alkylbenzenesulfonic acid 11.0 C 1-4 alkyl ethoxylate (EO 7) 12.0

Coconut fatty acid fraction from which light ingredients have been distilled off (1) 20.5 Q_ii-isoparaffins 4.0 15 Diethyl phthalate 6.0

Cyclohexylamine 2.0

Monomethylethanolamine (2) 4.3

Potassium citrate monohydrate (63.5% aqueous solution) 2.4

Dequest 2060 S 1.7 20 Ethoxylated polyamine (x = 5, y = 15) 1.5

Ethanol 3.0

Potassium hydroxide (50% aqueous solution) (2) 3,0

Formic acid 0.2

CaCl 2 * 2H 2 O 0.05 25 Optical brightener (anionic) 0.18

Maxatase enzyme (3) 0.71

Termamyl 300L enzyme (4) 0.10 Dye 20 ppm

Perfume 0.5 30 Water 110 into

Product pH 6.9 (1) Mixture of carbon chain lengths of the components: C. q (5%), Cl 2 (55%), Cu (22%), Cl 2 (2%) and oil. acid (10%) (2) for pH adjustment to 6.6 26 78730 (3) KNGS (4) from NOVO

The composition of Example XVII 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).

The most preferred cleaning solvent mixtures containing paraffins, especially c 1-6 isoparaffinic hydrocarbons (most preferably C 1-4 isoparaffin), and diethyl phthalate (or dibutyl phthalate, which is less preferred), clean the fabrics exceptionally well in both pretreatment and actual nesting. These particular solvents, which are used in a ratio of 5: 1 to 1: 5, are particularly preferred due to their exceptionally mild odor. The use of mixtures of these solvents and cyclohexylamine (ratio of solvent mixture to cyclohexylamine 10: 1 to 1:10, preferably 5: 1 to 2: 1) provides homogeneous oil-in-water microemulsion type liquid compositions which are preferred for any kind of degreasing.

In addition to their excellent cleansing ability, an important feature of the microemulsion compositions of this invention is their gentle application to the skin. This advantage, which is surprising with solvent-containing compositions, makes it possible to use the compositions for hand washing delicate fabrics, porcelain, glass-25 articles and the like.

Claims (8)

1. Liquid detergent composition intended for washing fabrics comprising an aqueous carrier, 10-5 to 40% by weight of a non-detergent surfactant and 5 to 20% by weight of a fat-removing solvent, comprising an unpolar solution & agent component which is a terpene, paraffin oil, a halogenated hydrocarbon, a Cg-C ^ alkyl-substituted aromatic compound, a liquid olefin or a mixture thereof, characterized in that the composition comprises 5-30% by weight of a C C ^ g fe fatty acid or C ^-C ^ g fatty acid well and a stabilizer for the microemulsion, wherein the stabilizer is a high ionic water soluble form formed, sulfate or citrate, a substance which is soluble in a non-polar solvent and having an HLB of 2-5, a nitrogen-functional compound or a mixture thereof, the composition having a pH of 6.5-8.0 and being in the form of a stable oil-in-water microemulsion. . 2. A composition according to claim 1, characterized in that C 1 mixtures thereof. Composition according to claim 1 or 2, characterized in that as solvents are used terpenes, paraffin oil, C compounds or olefins together with benzyl alcohol, C 1-6 -alkylsol / phthalic acid esters, 2- (2-alkoxyethoxy) ethanols or 2-alkoxy alkanols. 4. A composition according to claim 3,