FI57610C - FLYTANDE SYNTHETIC TVAETTMEDELKOMPOSITIONER UTAN STOEDSUBSTANSER - Google Patents

Abstract

Concentrated heavy duty liquid detergent compositions containing a mixture of a nonionic surfactant, an anionic surfactant and ethanolamine and being especially adapted to stain and soil removal from fabrics, either applied directly to such fabrics before washing or employed as detergent compositions for conventional fabric laundering.

Description

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Patent · och rtilitentynlNn 'Antfiktn utltgd och utl.skrtftcn publicend 30.05.80 (32) (33) (31) Privilege claimed — Begird prlorltst 31.01.72 USA (US) 222363 (71) The Procter & Gamble Company, 301 East Sixth Street , Cincinnati,

Ohio ^ 5202, USA (US) (72) Jerome Howard Collins, Cincinnati, Ohio, USA (US) (7 * 0 Oy Kolster Ab (5 * 0 Synthetic Detergent Compositions without Liquid Ingredients - Flytande synthetica tvättmedelkompositioner utan stöd-substantanser

The invention relates to concentrated, liquid high-performance detergent combinations. As used herein, the term "liquid" is understood to mean a semi-solution or gel combination as well as more conventional free-flowing formulations. Such combinations include a nonionic surfactant component as well as a mixture of union surfactants and an ethanol component.

Liquid high performance detergent combinations are already well known. Typically, such combinations (see, e.g., TT.S. Patents $ 2,908,651 $ 2,920,045 $ 3,272,753 »$ 3,393,154 and Belgian Patents 613,165 and 665,532) contain a synthetic organic washbasin component, which is generally Union in nature, not -ionic or mixed anionic-non-ionic inorganic structural salt and solvent, usually water and / or alcohol. These combinations often contain a hydrotropic or solubilizing agent that allows the addition of sufficient amounts of surfactant and structural salt to provide a reasonable space use / performance ratio. While some such liquid detergent combinations have been found to be effective for some types of spot washes, the presence of inorganic structural salts in such combinations may be undesirable from an ecological point of view if such combinations are used on a larger scale.

Several attempts have been made to form structural material-free and hydrotrope-free liquid detergent combinations. For example, U.S. Patent 3,528,925 discloses substantially anhydrous liquid detergent combinations comprising an alkylarylsulfonic acid, a nonionic surfactant and an alkanolamine component. U.S. Patent 2,875,153 discloses liquid detergent combinations comprising a nonionic surfactant component and a sodium soap component. U.S. Patent 2,5U3,7UU discloses a low-foam dishwashing combination comprising a nonionic, water-soluble, synthetic detergent and water-soluble soap in the form of an alkali metal, ammonium or amine salt. All of these detergent combinations are effective in certain types of laundry deliveries, but none of the commercially available combinations of this type are very effective as pretreatment and high performance detergents for cleaning both natural and synthetic fabrics.

Thus, it is an object of the invention to provide concentrated, liquid high performance detergent combinations which are highly effective for all types of fabrics both as soil pre-treatment agents and as laundry detergents.

It is a further object of the invention to provide liquid detergent combinations which do not contain inorganic building materials or conventional hydrotropes.

It is a further object of the invention to provide liquid high power detergent compositions which are chemically and physically stable as well as relatively non-toxic and non-irritating.

It has been found that the use of specific nonionic and anionic surfactants in combination with certain ethanolamine compounds in very specific ratios of these components can achieve the objectives described above and can form liquid detergent combinations which are surprisingly much better than liquid detergents previously known in the art. combinations of substances.

The liquid composition of the invention is characterized in that it contains (a) 30 to 60% by weight of a nonionic surfactant having an HLB value of 8 to 15 and prepared by condensing an alkylene oxide and an organic hydrophobic compound, namely an alkylphenol, straight or branched alkyl group having 6 to 16 carbon atoms, aliphatic alcohol having a straight or branched alkyl chain containing 8 to 22 carbon atoms, condensation product of propylene oxide and propylene glycol having a molecular weight of 1500 to 1800, 3,57610 or propylene oxide and ethylenediamine (b) a mixture of anionic surfactants in an amount such that the weight ratio of nonionic to anionic surfactant in the free acid form is 2.5: 1 to 3.5: 1, anionic surfactants a mixture consisting of (i) ethanolamine alkyl benzene sulfonate having 9 to 15 carbon atoms in the alkyl chain, and (ii) ethanolamine in a soap having a fatty acid portion containing 8 to 2 U of carbon atoms, wherein the ethanolamine portion of the sulfonate and soap consists of monoethanolamine, diethanolamine or triethanolamine, and the mixture of anionic surfactants contains sulfonate and soap in amounts such that the acid portion of the sulfonate and soap is from 20: 1 to 1: 1, and (c) ethanolamine, consisting of monoethanolamine, diethanolamine, triethanolamine, or a mixture thereof, in an amount such that it provides a free ethanolamine content of at least 1% w / w by weight of the total composition. counting.

The components of these detergent combinations are explained in more detail as follows:

Non-ionic surfactant

About 30 to about 60 weight percent of the liquid detergent combination of this invention is a nonionic surfactant derived by condensing an alkylene oxide (hydrophilic in nature) with an organic hydrophobic compound that is generally aliphatic or alkyl aromatic in nature. The chain length of the hydrophilic or polyoxyalkylene moiety condensed with the hydrophobic compound can be easily selected to provide a water-soluble compound having the desired degree of equilibrium between the hydrophilic and hydrophobic bases. Examples of suitable nonionic surfactants include: (1) Polyethylene oxide condensates of alkylphenols. These compounds contain condensation products of alkylphenols having an alkyl group containing 6 to 12 carbon atoms in either straight or branched chain form with ethylene oxide, this ethylene oxide being present in amounts of 5 to 25 moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds may be derived from, for example, polymerized propylene, diisobutylene, octene or nonene. Examples of this type of compound are nonylphenol condensed with about 9 * 5 moles of ethylene oxide per mole of nonylphenol, dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonylphenol fused with 5761 moles of ethylene. per mole of phenol, di-isooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 marketed by GAF Corporation and Triton X-U5, X-11U, X-100 and X-102, all marketed by Rohm and Haas Company.

(2) Condensation products of aliphatic alcohols and ethylene oxide.

The alkyl chain of the aliphatic alcohol may be straight or branched and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols are the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, alcoholic co is a mixture of 10 to 1 carbon atoms, and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and about 9 moles of ethylene oxide condensation product with the coconut alcohol described above. Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9, marketed by Union Carbide Corporation, Neodol 23-6.5, marketed by Shell Chemical Company, and Kyrö EIB, marketed by Procter & Gamble Company.

(3) Condensation products of ethylene oxide with a hydrophobic base, which is the condensation product of propylene oxide and propylene glycol. The hydrophobic portion of these compounds has a molecular weight of about 1500-1800 and is, of course, insoluble in water. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the overall water solubility of the molecule, and the liquid nature of the product remains up to a point where the polyoxyethylene content is about 50% of the total weight of the condensation product. Examples of this type of compound are certain commercially available Pluronic surfactants marketed by Wyandotte Chemicals Corporation.

(U) Condensation products of ethylene oxide with the product obtained from the reaction between propylene oxide and ethylenediamine. The hydrophobic base of these products is the reaction product of ethylenediamine and excess propylene oxide, having a molecular weight of about 2,500 to about 3,000. This base is condensed with ethylene oxide to an amount where the condensation product contains about 10 to about 80 weight percent polyoxyethylene, and is from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain commercially available Tetronic compounds marketed by Wyandotte Chemicals Coiporation.

The detergent compositions of this invention preferably use a surfactant having a hydrophilic-lipophilic balance (HLB) of about 8 to about 15. A highly preferred nonionic surfactant in this range is 6 moles of ethylene oxide condensation product with coconut fatty alcohol. . (HLB = 12).

The presence of a nonionic surfactant in these liquid detergent combinations at a substantially defined concentration allows the removal of oily dirt when used in both pretreatment and wash water. Such a nonionic surfactant also promotes the physical stability of liquid detergent combinations.

Mixture of Anionic Surfactants The anionic component of these detergent combinations comprises a mixture of an ethanolamine salt of an alkylbenzenesulfonic acid (ethanolamine alkylbenzenesulfonate) and an ethanolamine salt of a fatty acid (hereinafter referred to as ethanolamine soap). Both of these salts are prepared by neutralizing the corresponding anionic acids with monoethanolamine, diethanolamine or triethanolamine. The mixture of salts of anionic surfactants is used herein in an amount sufficient to give a weight ratio of nonionic surfactant to the mixture of anionic surfactants of about 2.5: 1. 3.5: 1 »calculated on the free acid form of anionic surfactants.

The non-soap component of the mixture of anionic surfactants is the mono-, di- or tri-ethanolamine salt of a straight or branched chain alkylbenzenesulfonic acid in which the alkyl group contains from about 9 to about 15 carbon atoms. Preferred surfactants of this type are those in which the alkyl chain is straight and has an average length of 12 carbon atoms. Examples of ethanolamine alkylbenzenesulfonates useful in this invention include monoethanolamine decylbenzenesulfonate, diethanolamine undecylbenzenesulfonate, triethanolamine dodecylbenzene benzene ethanesulfenethylate decathiene triethylate triethylbenzene, trioethanolamine tridecylbenzene. Examples of commercially available alkylbenzenesulfonic acids useful in preparing the ethanolamine sulfonates of this invention include Conoco SA 515, SA 597 and SA 697, all marketed by Continental Oil Company, and Calsoft L AS 99, marketed by Pilot Chemical Company.

The soap component of the mixture of anionic surfactants comprises fatty acids containing from about 8 to about 2k carbon atoms and preferably from about 10 -n. 20 carbon atoms, mono-, di- and triethanolamine soaps. Suitable fatty acids can be obtained from natural sources, for example vegetable or animal fatty acid esters (e.g. palm oil, coconut oil, babassu oil, soybean oil, safflower oil, pine oil, castor oil, tran and fish oils, fat, lard and mixtures thereof).

6 57610

Fatty acids can also be prepared synthetically (e.g. by oxidizing petroleum or with hydrogen carbon monoxide by the Fischer-Tropsch method). Examples of suitable soaps for use in this invention include monoethanolamine caproate, diethanolamine laurate, triethanolamine myristate, triethanolamine palmitate, monoethanolamine stearate and diethanolamine palmitoleate. Preferred soaps are mono-, di- and triethanolamine soaps derived from mixtures of fatty acids derived from coconut oil and tallow. A highly preferred soap for use in this invention is triethanolamine oleate. Examples of commercially available fatty acids for use in the preparation of ethanolamine soaps in this invention include C-105, C-108, C-110, T-10, T-11 and 01-910, all marketed by The Procter & Gamble Company, and Hyfac, a hydrogenated fish oil fatty acid , marketed by Emery Industries Inc.

In the mixture of anionic surfactants, its two components are present in amounts sufficient to give a weight ratio of the acid part of the sulfonate (alkylbenzenesulfonic acid) and the acid part of the soap (fatty acid) of n, 20: 1 to about 1: 1, preferably n. U: 1 - about 8: 1. It has been found that the weight ratios of the components of the mixture of anionic surfactants in this range give an unexpectedly high degree of stain and soil removal and at the same time a low rate in both washing and rinsing.

As will be appreciated, the entire mixture of anionic surfactants must be present in these liquid detergent combinations in an amount such that the weight ratio of nonionic surfactant to union surfactant (calculated as free acid) is approximately 3: 1, i.

2.5: 1 - approx. 3.5: 1 · The reasons for this substantial weight ratio limitation are discussed more fully below.

Ethanol Amine The third essential component of the liquid detergent combination of this invention is an ethanol aluminum compound. An otolamine amine useful herein is a monoethanolamine, diethanolamine, triethanolamine or a mixture thereof. Mixtures of these three ethanolamine compounds are prepared by reacting ethylene oxide with ammonia. The pure compounds can be separated from this mixture by standard distillation methods.

The ethanol amine component of this invention has two purposes. As will be more fully explained below, the preferred advantage of ethanolamine in the process for preparing these combinations neutralizes the free acid form of the mixture of anionic surfactants to give ethanolamine salts (which are essential components in these detergent combinations.) In addition to 7,57610 excess ethanolamine salts, i.e. necessary, promotes washing performance, and acts as a buffer to maintain the pH of the wash water of these combinations in the range of about 7 to about 9. It is essential that the combinations of this invention contain at least 1% by weight of free ethanolamine from the total combination.

The combinations described above containing nonionic, anionic and ethanolamine components can be formed by preparing each component separately and thoroughly mixing them together in any order. In a preferred method of preparing these combinations, the anionic and ethanolamine components are formed simultaneously by over-neutralizing the ethanolamine with suitable mixtures of sulfonic and fatty acids. This process produces the necessary ethanolamine alkyl benzene sulfonate and ethanolamine soap in situ and also provides the free ethanolamine component of this combination.

When this preferred combination formation method is used, the total amount of ethanolamine used will vary depending on the nature and ratio of the particular alkylbenzenesulfonic and fatty acids and the particular ethanolamine used. A particularly preferred ethanolamine concentration to form the anionic-ethanolamine moiety of the combination is a weight percentage of ethanolamine that is approximately equal to the weight percentage of the mixture of anionic surfactants (based on free acid) present in the detergent combination. By adding this preferred amount, ethanol amine is always present in an amount greater than the stoichiometric amount required to completely neutralize the acid mixture, regardless of which ethanolamine is used and which anionic acid mixture is used.

Optional components

Although the liquid detergent compositions of this invention need not contain any of the three components described above (i.e., anhydrous combinations), highly preferred combinations of this invention contain, in addition to the three active ingredients, a solvent, which may be water or a water-alcohol mixture. In general, such solvents can be added up to an amount of 1-1 * 5% by weight of the total detergent combination. In preferred combinations, the proportion of solvent is from about 25 to about 1 * 5% by weight. The addition of such solvents has several advantages. First, the physical stability of detergent combinations can be improved with such solvents in that the brightness points can thus be lowered to give combinations that do not cloud at lower temperatures that may occur during transport and storage of commercially available detergent combinations.

Second, the addition of solvents, especially water / alcohol mixtures, helps to control the tendency to gel with these types of liquid detergent combinations when diluted with water.

Finally, detergent combinations of this type containing such solvents are desirable for many safety reasons. Dilute solutions are usually less toxic and less irritating to the eye than more concentrated or anhydrous detergent combinations containing the three active ingredients.

When an alcohol / water mixture is used as a solvent, the weight ratio of water to alcohol is preferably considered to be greater than about 3: 1, more preferably between about 1 *: 1 to about 7: 1. Higher concentrations of alcohol (especially ethanol) are preferably avoided in the present invention. in water / alcohol mixtures due to the risk of ignition due to higher alcohol contents.

Any alcohol containing 1 to about 5 carbon atoms can be used in the water / alcohol mixture if such a mixture is used in these detergent combinations. Examples of useful alcohols are methanol »ethanol, 957610 propanol, isopropanol, butanol, ieobutanol and pentanol. Ethanol is particularly preferred in terms of toxicity.

Another optional component that can be added to the detergent compositions of this invention is the electrolyte salt. The addition of the electrolyte salt reduces gel formation, which tends to occur when diluting these detergent combinations. When used in combination with a water / alcohol solvent, 0.5-5% by weight of electrolyte salt can completely eliminate gel formation without using alcohol concentrations that exceed the safe flammability levels mentioned above.

Suitable electrolyte salts include alkali metal chlorides, sulfates and carbonates, as well as salts formed by the reaction of ethanolamines with other, acetic, propionic, butyric, citric or sulfuric acids. Specific examples of such salts include sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanolamine nitrate, triethanolamine acetate, triethanolamine formate, and diethanolamine, monoethanolamine. Potassium chloride is preferred and is preferably added to these combinations in an amount of about 1-3% by weight.

As can be seen, the use of a solvent and an electrolyte salt helps to control and regulate - gel formation in these liquid detergent combinations. However, if gel formation is desired, it is possible to select specific water-solvent concentrations that give gelled combinations in the absence of alcohol and electrolyte salt. (As will be appreciated, a gel combination is a "solution" for the purposes of this invention). Thus, combinations containing the three active components in the concentrations defined above, as well as about 13 to 35% by weight of water as solvent, are gel combinations, provided that no alcohol or electrolyte is present.

Other optional el-essential, non-interfering components can be added to these combinations to improve performance and provide aesthetic appeal. Preferred combinations of the invention are those to which a color stabilizing agent, for example citric acid, has been added. These combinations have surprising resistance to the tendency of such combinations to discolor during storage. In addition, the presence of citric acid in the combinations of the invention has a significant effect in preventing the development of stains observed on the outer surfaces of plastic bottles due to spillage, leakage or manual handling of bottles which have previously been in contact with the combinations of the invention. Like Union surfactants, citric acid forms ethanolamine citrate when added to these combinations containing excess ethanolamine. However, for convenience, this concentration of ethanolamine citrate in the combinations is expressed as a percentage by weight of the free acid form of the citrate, i.e. citric acid added to the combinations. The amount of citric acid that rises to n * 1 by weight of the combination is generally added to achieve these color benefits. A very preferred amount of added citric acid is from about 0.05 to about 0.10% by weight of the combination.

Other optional components include brighteners, fluorescent agents, enzymes, bleaches, antimicrobials, corrosion inhibitors, and dyes. Preferably, the proportion of such substances does not exceed 5% by weight of the total combination.

The use of ratios of nonionic surfactants to anionic surfactants (calculated as free acid) ranging from about 2.5 * 1 to about 3.5: 1 in combination with the use of excess free ethanolamine is critical to form detergent combinations having this unexpected performance and performance characteristics of the invention. The formation of mixed cells as a result of the use of the specific nonionic / anionic surfactant of the invention gives an unexpected washing achievement which is not affected by the hardness of the water.

The use of molten ethanolamine melts and excess ethanolamine also enhances the effectiveness of these detergent combinations. For example, these combinations containing the ethanolamine counterion together with an excess of free ethanolamine are much better for purifying polyester / cotton than the corresponding combinations containing the more conventional sodium or potassium salts of anionic surfactant acids but no free ethanolamine.

The combinations of this invention are used in two different ways to clean a fabric. They can be used as pretreatments which are applied in concentrated form directly to the stains of the fabric before washing the fabric. These combinations are also useful as detergents for conventional fabric washing operations. The removal of both stains and dirt is achieved when these combinations are dissolved in the washing solution up to about 0.10% by weight. (Approximately 1/4 cup to 64-72 liters of wash water).

In terms of treatment efficiency, the combinations of the present invention, which contain the specified components and component ratios, are capable of removing oily stains from polyester or polyether / cotton fabrics much better than the corresponding pretreatment using conventional anionic detergent combinations. The effectiveness of the combinations according to the invention in removing oily stains is, in fact, comparable to that obtained with the non-ionic surfactants which 11

5761 C

is specifically intended for such pre-treatment stain removal. On the other hand, the specific combinations of this invention have a much better soil removal ability than conventional nonionic surfactant-based products (especially cotton) in wash water at normal home wash rates. The washing performance is in fact comparable to that achieved with conventional granular anlonic detergent combinations in composition.

The following examples further illustrate the liquid detergent compositions of this invention:

Example 1

100 g of a liquid high-performance detergent combination having the following composition are formed:

Component Weight # 6 moles of ethylene oxide condensation 33 »0 product with coconut fatty alcohol

The triethanolamine salt of a straight alkylbenzenesulfonic acid having an average alkyl chain length of 12 carbon atoms

Triethanolamine oleate 2.3

Free triethanolamine 3 * 3

Ethanol 5 * 5

Potassium chloride 2.3

Brighteners, perfume, dye 1,2

Water Rest

In the above combination, the weight ratio of nonionic surfactant to anionic surfactant (calculated as free acid) is 2.64: 1 and the weight ratio of sulfonate acid form to soap acid form is 7 * 33 * 1. The anionic surfactant-ethanolamine portion of this combination is prepared by mixing 11 g of C 1-4 alkylbenzenesulfonic acid, 1.3 g of oleic acid and 11 g of triethanolamine.

Such a combination is a permanent, clear liquid detergent that does not gel when diluted with water and is relatively non-toxic (U> - 8 ml / kg 50 ED <1 ml / kg), persistent on freezing-thawing, relatively non-flammable 50 (Tagliabue flash point in open cup - 69 C t and which gives a uniform medium foam in the washing water, the temperature and hardness of which vary, as well as an excellent pre-treatment and washing water washing result.The addition of 0.05 6 tn of citric acid to the above-described combination significantly increases its color fastness.

is 5761 0

Several liquid high performance detergent combinations are formed having the compositions shown in Table 1. Combinations of Anionic and Ethanolamine Components in such combinations are all prepared by neutralizing the acid form of ethanolamine 11a anionic surfactants as described in Example 1.

table 1

Component weight II III IV V VI VII VIII IX X XI

}, - »i - —— '' 1 1 1 '» - 1 1 1 1 -', 6 moles of ethyleneoxy- 52.8 52.8 - U1.1 - - - 33.8 - U1.1 dia condensation product with coconut fatty alcohol i __________ _____ _____ _____ ______ _______ _______ _____ 'Kyrö EOB (HLB = 13.3) 1 ----- ___ 52.8 -! 9.5 moles of ethylene - - 52.8 - 33, 0 - - - - - 'oxide condensed product with nonyl-ifenol I-5 -----------' Pluronic L — U3 - - - - - U1,1 - (HLB = 12)

Tetronic 70 ^ - - - - - - 52.8 - l (HLB = 15) j -----------

Direct alkylbenz-25.6 12.8 25.6 20.0-16.2-16.5 25.6-ene Siphonic acid ethanolamine salt of an acid having an average alkyl chain length of 12 carbon atoms

Petrapropylene benz- - - - - 16.0 - 20.8 - - 11.1 Ethanol amine salt of mushenesulfonic acid i_______. ----- —...... ...

ethanol salt of oleic acid - - - 2,3 2,3 - - - - 11,6; amine salt j ------------

Tallow fatty acid ethano - 13.6 1.5 - "1.8 1» 2 - 1.5-lamine salt i .... I -. ............... ----- '-' '' "1 '

A 3: 1 mixture by weight of the ethanolic salt of the fatty acid ethanol-1.5 - ~ "" - "1,1-lamininex and the ethanolamine salt of the saturated fatty acid. Commercially known as j ^ Hyfac ”___ [____ j returns 13 5761 0

Component weight- # II III IV V VI VII VIII IX X XI

Free tri ethanol amine 8.9 8.7 8.9 6.5 5.2 - “5.9 8.9 6.2

Free monoethanolamine - - - - - 10.7 1 ^, 0 -

Ethanol - 2.3 - 5.1 - 5.1 - 17.0

Butanol - - - - 5.5

Kali umk.lori di - - - 1,0- - -

Triethanolamine acetate - - - - 2,5 tate

Potassium carbonate _____ 1.0 - -

Additives (brightener - 0.9 0.9 0.9 1, 2 1, U 1.2 0.9 0.9 0.9 1.2 met, color stabilizers, perfume, dyes)

Water the rest

Weight ratio of nonionic surfactant 2.8U 3.00 2.8Π 2.70 2.6U 2.70 2.8U 2.81 2.8U 2.70 active substance to anionic surfactant (calculated as anionic free acid)

Weight ratio of sulfonate component 11.7 1.0 17.6 9.1 7 * 3 9.1 11 »7 16.1 17.6 1.0 nent acid form to the acid form of the soap component X · · ·

Triethanolamine salt for combinations L-V and VIII-IX; monoethanolamine salt for combinations VI and VII

1 Ethoxylated fatty alcohol 2 Condensation product of ethylene oxide with a hydrophobic base formed by condensing propylene oxide with propylene glycol 3 Condensation product of ethylene oxide with a compound obtained from the reaction between propylene oxide and ethylenediamine.

Ill 5761 0

Examples II-XI represent various detergent combinations within the scope of the invention. Examples II, III, IV, VIII and X represent highly concentrated liquid detergent combinations. The active detergent content of Examples V, VI, VII and XI is lower. Example XI represents a detergent gel. All combinations give an excellent pretreatment result, are applied directly to fabric stains and give an excellent washing result when used in an amount of about 1/1 cup per 6I + -72 liters of wash water.

Wash-use test

The washing performance of several combinations of the present invention was compared to the washing performance of commercially available granular laundry structure detergents in a washing and use test. The test used was performed as follows: White shirts, cotton T-shirts and other fabrics were distributed to different users. Each shirt and T-shirt was held for one normal working day under equal conditions, and other products were used for their intended general purpose. The soiled clothes and fabrics were then washed in an automatic turbulence washing machine for 10 minutes at a detergent solution of l »0.5 ° C. The detergents used were combinations of Examples II, III, IX and X with a concentration of 1/1 + cup / 61+ liters of water, and Tide, a commercially available granular structural detergent marketed by The Procter & Gamble, used in concentrations of 1 l / 4 to 1 cup / 64 liters of water.

The pH of the wash water was about 7.2 for the liquid detergent solution and about 9.5 for the Tide solutions. The hardness of the wash water was about 6.7 ° dE. After washing, the clothes were rinsed (6 shower rinses and one deep rinse) and then dried.

A panel composed of expert reviewers made direct visual comparisons between pairs of shirts and fabrics worn and soiled by the same person. Shirts, T-shirts, and other perceived fabrics were evaluated for degree of whiteness and degree of purity obtained, with the latter feature paying particular attention to shirt collars and sleeve twists.

For purposes of this invention, the term "cleaning" or "cleanliness" measures the ability of a detergent combination to remove actual streaks or stains, such as the fold line of collars and cuffs, where the dirt has had a deep feel. Whiteness, on the other hand, is a more general term for measuring the ability of a blend compound to whiten surfaces that are slightly or moderately soiled. The relative cleaning performance of each detergent combination on each surface was evaluated visually on a nine-point rating scale in artificial light, with the highest degree being determined to mean the relatively best washing result obtained.

Based on such comparisons, it was found that all of the liquid detergent combinations of this invention gave a purity comparable to 1 1/4 cups of Tide. In addition, all combinations of this invention gave a combined whiteness result comparable to 1 '1/4 cups of Tide except Example IV, which gave a combined whiteness result comparable to 1 cup of Tide The representative combination of this invention was compared to other commercially available laundry products in terms of its ability to remove various types of oily stains from polyester / cotton (65 96/55 &) fabrics. 28 x 28 cm olive-colored polyester / cotton patches were stained with one drop of Crisco cooking oil, bacon oil, mineral oil, dirty machine oil and French cassette and suntan oil and aged for 16-20 hours. In the first Tue 1 ml of product was applied directly to each stain in the second, 2 ml per stain, in the third 3 ml per stain and in the fourth 4 ml per stain. After application of the product, ‘each stain was rubbed 10 seconds horizontally and 5 seconds vertically to mimic home pretreatment * 16 5761 0

The products tested were (l) a citric acid-containing liquid detergent combination from the previous Example 1 | (2) a commercially available liquid * high performance structure detergent; (3) a commercially available liquid * non-texture * high performance detergent; and (4) a 50% water paste * made from a granular texture laundry detergent, Tide * marketed by The Prooter & Gamble Company.

Four patches * of each product pre-treated as above were washed in an automatic washing machine with 70 liters of water with a hardness of 6.7 ° dH / 52 ° C and a normal family laundry load. Each filling contained approximately enough product to be tested (including the product already rubbed into four patches) to give the "recommended" working concentration for the wash water solution, te., The combination of Example 1 - 1/4 cup; structure solution-1/2 cups; non-structural solution - 1/4 cup; and Tide'a - 1 cup.

For each patch of each stain, two reviewers rated it on a scale of 10 to 10, where 0 corresponded to a condition where the stain had not been removed at all, and 10 to complete stain removal, respectively. The degrees of the six stains were summed and divided by 60. This quotient was multiplied by 100 to give a combined stain removal index for each patch. The results of the tests are summarized in Tables 2 and 3 17

Table 2 5761 0

Combination of Example I RakSS Compound 1 olsn / 2 ml / 3 ml / ml / ml mlm / Jcl: a / <1 wl: n / stain stain stain stain stain stain stain

Crisoo oil '9.5 8.'0 9.0 9.5 7.5 7.0 6.5 6.5

Bacon fat 8.5 8.5 8.5 8.0 6.0 6.5 5.5 7.0

Mineral oil 9-5 9.5 9.5. 9.5 7.0 7.5 6.5 7.5 i

Dirty machine- 9.5 8.0 8.0 8.5 7.5 6.0 6.5 6.0 oil sauce 10.0 9.5 ·· 9 · ° 9.5 -7 · 5 7 · ° 6.5 '7 · °

Suntan oil 10.0 10.0 9.5 9.5 7.0 7.0 7.5 .7.0

Total 57.0 53.5 53.5 54.5 42.5 41.0 39.0 41.0

Stain removal index .95.0 89.1 89.1 90.8 70.8 68.3 65.0 68.3 1 -------- I ------ I I I - _ I I -,

Table 3 i

Commercial Non-Texture Liquid Tide Paste 1 ml / 2 ml / j ml 4 ml / l ml / 2ml / 5 nl / 4 mlsn 'stain stain stain, stain stain stain tahra tahra '1 ...........

. · ... .. · I

Crisoo oil 6.5 6.0 6.5 7.5 4.0 2.5 3.0 2.5

Bacon platform 5.0 7.C 5.5 6.5 3.0 2.5 3.0 1.5

Mineral oil 6.5 7.0 6.5 7.5 3.0 2.0 3.5 3.5

Dirty machine oil 3.5 6.5 4.5 5.5 1.5 1.5 1.5 1.5

Baneca sauce 7.0 5.5 6.5 9.0 2.5 2.5 2.5 3.5

Sultan oil 6.0 7.5 6.0 8.5 2.5 2.0 1.5 2.0

Total 34.5 39.5 35.5 44.5 16.5 Jjy0_ J 5.Q 12.5_.

Stain Removal Indox 57.5 65.8 59.1 74.1 27.5 21.6 25.0 20.8 IE 5761 0 From these results, it can be seen that the combination of the present invention was much better than others formed to remove oily stains from a polyester-containing fabric.

Foaming Test The unusual foam tightness of these liquid high performance detergent combinations is demonstrated by the following foam height assessment. The citric acid-containing combination of Example 1 was used under various water temperature and water hardness conditions. Electric top-loading automatic washing machine at a concentration of 1/1 + cup / 6U liters with normal laundry filling. After 10 minutes of wedging, the height of the foam in cm was measured and averaged for a 2k filling from each combination of conditions. The results of such foaming tests are summarized in the following table:

Conditions Foam height

Mean (cm) 21 ° C; 0.05 g 6.6 38 ° C; 0.13 g 8.6 38 ° C 0.1 + 5 g 8.6 38 ° C; 0.90 g 6.1 + 52 ° C; 0.1 + 5 g 6.6 at 60 ° C; 0.13 g 7.1 60 ° C 0.1 + 5 g 7.9

It can be seen that under different temperature and hardness conditions, the composition according to the invention gave average foam heights ranging up to 2 cm.

Claims (9)

Liquid detergent composition, characterized in that it contains (a) 30-60% by weight of a nonionic surfactant, which has an HLB value of 8-15 and is prepared by condensation of an alkylene oxide and an organic hydrophobic compound, namely alkylphenol, wherein the alkyl group is straight or branched and contains 6-16 carbon atoms, an aliphatic alcohol, with a straight or branched alkyl chain containing 8-22 carbon atoms, the condensation product of propylene oxide and propylene glycol having a or the reaction product of propylene oxide and ethylenediamine having a molecular weight of 2500-3000; (b) a mixture of anionic surfactants in such an amount that the weight ratio between the nonionic and the free acid forms the anionic surfactant is 2.5: 1 - 3.5: 1, wherein the mixture of the anionic surfactants consists of (i) an ethanolamine alkylbenzenesulfonate having 9 to 15 carbon atoms in the alkyl chain, and (ii) an ethanol mint with 8-2U carbon atoms in the fatty acid moiety, wherein the ethanolamine portion of the sulfonate and the doubt consist of monoethanolamine, diethanolamine or triethanolamine and the mixture of the anionic surfactants contains sulfonate and stale in side amounts, so that the weight ratio between the acid portion of the sulfonate and the acid portion the doubt is 20: 1 - 1: 1, and (c) an ethanolamine consisting of monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, and present in sufficient quantity to constitute at least 1 weight-free ethanolamine of the total weight of the composition . A composition according to claim 1, characterized in that it further contains 1-1 + 5 # of a solvent, which consists of water and an alcohol of 1-5 carbon atoms, the weight ratio of water / alcohol being greater than 3: 1. Composition according to claim 2, characterized in that the alcohol is ethanol. A composition according to claim 3, characterized in that it further contains from 0.5 to 5% by weight of an electrolyte salt. · Composition according to claim 1 +, characterized in that electrolyte salts are potassium chloride. 6. A composition according to claim 5, characterized in that the mixture of the anionic surfactants contains sulfonate and quail in such amounts that the weight ratio of the acid portion of the sulfonate to the acid portion of the quail is 1+: 1 - 8: 1. , that the solvent consists of a mixture of water and ethanol, wherein the weight ratio of water / ethanol is 1+: 1 - 7 + 1, and that the solvent is 25-1 + 5% by weight of the composition and that the potassium chloride electrolyte salt is 1-3 weight of the composition. A composition according to any one or more of claims 1-1 +, characterized in that it contains: (a) 35-00% by weight of a nonionic surfactant having an HLB value of 8- And is prepared by condensation of alkylene oxide and an organic hydrophobic compound, namely alkylphenol, wherein the alkyl group is straight or branched and contains 6-12 carbon atoms, an aliphatic alcohol, with a straight or branched alkyl group containing 8-22 carbon atoms, the product of propylene oxide and propylene glycol, having a molecular weight of 15ΟΟ-18ΟΟ, or reaction product of propylene oxide and ethylenediamine, having a molecular weight of 2500-3000, (b) a mixture of anionic surfactants in such an amount that the weight ratio of the -ionic and the free acidic anionic surfactant is 2.5: 1 - 3.5 + 1, wherein the mixture of the anionic surfactants consists of (i) an ethanolamine alkylbenzenesulfonate having a straight alkyl group and having an average of 1 2 carbon atoms, and (ii) an ethanolamine moiety having from 10 to 20 carbon atoms in the fatty acid moiety, wherein the ethanolamine portion of the sulfonate and the moiety consists of monoethanolamine, diethanolamine or triethanolamine and the mixture of the anionic surfactants contains sulfonate and sulfur in such amounts; the weight ratio of the acid portion of the sulfonate to the acid portion of the dopant is 1+: 1 - 8: 1, and (c) an ethanolamine, namely monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, present in a sufficient amount to constitute at least 1 weight - / in free ethanolamine of the total weight of the composition, (d) 25-1 + 5 wt. of a solvent which consists of a mixture of water and ethanol, the weight ratio of water / ethanol being 1+: 1 - 7: 1, and (e) 0.5-5 wt-Ji of an electrolyte salt, namely of sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanolamine citrate, triethanolamine acetate, triethanoamine informate, monoethanolamine propionate or diethanolamine butyrate. A composition according to claim 7, characterized in that