JPS5833280B2 - Ekita Senjiyouzai Sobutsu - 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

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to concentrated heavy duty liquid detergent compositions.

By "liquid" herein is meant quasi-liquid or gel compositions, and more generally free-flowing compositions.

Compositions of this type include a nonionic surfactant component, an anionic surfactant mixture, and an ethanolamine component.

Heavy duty liquid detergent compositions are well known.

Compositions of this type are commonly used (e.g., U.S. Pat. No. 2.908
．． No. 681: 2.920.045: 3.272.
No. 753: No. 3,393.154 and Belgian Patents Nos. 613.165 and 665.532), synthetic organic detergent components (generally anionic, nonionic, or mixed anionic-nonionic). ); an inorganic builder salt; and a solvent (usually water and/or alcohol).

These ingredients often include hydrotropes or solubilizers so that sufficient amounts of surfactant and builder salt can be added to provide the appropriate dosage/performance ratio.

Although such liquid detergent compositions have been found to be effective for a few types of household laundry, if such compositions were to be used on a large scale, it would be Inorganic builder salts may be undesirable from an ecological point of view.

A few attempts have been made to formulate builder-free and hydrotrope-free liquid detergent compositions.

For example, in U.S. Pat. No. 3,528,925,
Substantially anhydrous liquid detergent compositions are described that include an alkylaryl sulfonic acid, a nonionic surfactant, and an alkanolamine component.

U.S. Pat. No. 2,875,153 also describes a liquid detergent composition that includes a nonionic surfactant component and a sodium soap detergent component.

U.S. Pat. No. 2,543,744 also discloses a low-foaming dishwashing composition comprising a non-ionic, water-soluble, synthetic detergent and a water-soluble soap in the form of an alkali metal, ammonium or amine salt. is mentioned.

Although all of these detergent compositions are effective for certain types of laundry operations, none of these commercially available compositions are suitable for cleaning natural and synthetic knitted fabrics as well as for heavy-duty cleaning. There are no highly effective detergents.

It is therefore an object of the present invention to provide a concentrated heavy duty liquid detergent composition that is highly effective as a stain treatment agent and as a laundry detergent for all types of textiles.

Another object of the invention is to provide a liquid detergent composition that is free of inorganic builders as well as conventional hydrotropes.

It is a further object of the present invention to formulate heavy duty liquid detergent compositions that are physically and chemically stable, relatively non-toxic and non-stinging.

According to the invention, the above object is achieved by using specific nonionic and anionic surfactants together with certain ethanolamine compounds in very specific proportions of these components. It has now been discovered that liquid detergent compositions can be formulated that are unexpectedly superior to liquid detergent compositions currently known in the art.

Summary of the Invention The present invention provides a nonionic surfactant formed by the condensation of an alkylene oxide and an organic hydrophobic compound.
% (by weight); b in an amount sufficient to provide a weight ratio of nonionic surfactant to anionic surfactant (in its capable acid form) of from about 2.5:1 to about 3.5:1; A liquid detergent composition is provided comprising an anionic surfactant mixture (described below); and ethanolamine in an amount sufficient to constitute at least one part (by weight) of the C composition.

The anionic surfactant mixture consists of two components: 1 mono-, di- or triethanolamine salt of an alkylbenzenesulfonic acid having about 9 to 15 carbon atoms in the alkyl chain; and 2 fatty acid moieties. A mono-, di- or tri-ethanolamine soap containing from about 8 to about 24 carbon atoms.

These two components are present in amounts sufficient to provide a weight ratio of the acid form of the sulfonate to the acid form of the soap from about 20=1 to about 1=1.

Detailed description of the invention Each component of this detergent composition will be explained in detail below.

About 30% to about 60% (by weight) of the liquid detergent composition of the present invention
consists of a nonionic surfactant formed by the condensation of an alkylene oxide (hydrophilic) with an organic hydrophobic compound (usually aliphatic or alkyl aromatic).

Easily adjust the length of the hydrophilic or polyoxyalkylene moiety that is condensed with a particular hydrophobic compound to yield a water-soluble compound with a desired balance between hydrophilic and hydrophobic components. I can do it.

Suitable nonionic synthetic detergents include: (1) Polyethylene oxide condensates of alkylphenols.

These compounds are condensation products of alkylphenols containing about 6 to 12 carbon atoms with alkyl groups in a linear or branched configuration and ethylene oxide, where the ethylene oxide is Some are present in amounts of ~25 moles.

Alkyl substituents in such compounds may be derived from, for example, polymerized propylene, diisobutylene, octene or nonene.

Examples of this type of compound include nonylphenol 1
Nonylphenol condensed with about 20 moles of ethylene oxide per mole; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of dodecylphenol; dinonylphenol condensed with about 15 moles of ethylene oxide per mole of dinonylphenol; isooctylphenol 1
There are about 15 moles per mole of diisophylphenol condensed with ethylene oxide.

A commercially available nonionic activator of this type is "IKEPEARL" C available from GAF.
A and Co-based; "Triton JX-45, X-114°X-10" commercially available from Rohm and Haas
0 and X-102.

(2) Condensation product of aliphatic alcohol and ethylene oxide.

The alkyl chain of the aliphatic alcohol is either straight or branched and generally contains about 8 to about 22 carbon atoms.

Examples of such ethoxylated alcohols include about 15
A condensation product of 1 mole of ethylene oxide and 1 mole of tridecanol; myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myrityl alcohol; a condensation product of ethylene oxide and coconut oil fatty alcohol; The coconut oil alcohol is a mixture of aliphatic alcohols having an alkyl chain of 10 to 14 carbon atoms and the condensate thereof contains about 6 moles of ethylene oxide per mole of alcohol; and about 15 moles of ethylene oxide. There are condensation products of ethylene and the above-mentioned coconut oil alcohols.

Examples of commercially available nonionic surfactants of this type include Tergitol J15-8-9, available from Union Carbide; Cairo JEO, available from Brocter & Gamble.
There is "Neodoru J23-6.5" commercially available from Shell Chemical Company and Shell Chemical Company.

(3) A condensation product of ethylene oxide and a hydrophobic base produced by condensing propylene oxide with propylene glycol.

The hydrophobic portion of these compounds has a molecular weight of about 1500-1800 and exhibits thermal water insolubility.

Addition of polyoxyethylene groups to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole, until the polyoxyethylene content is about 50% of the total weight of the condensation product. Characteristics are reserved.

An example of this type of compound is the commercially available "Pluronic" active agent from Wyandotte Chemicals.

(4) A condensation product of ethylene oxide and a product produced by reacting propylene oxide with ethylenediamine.

The hydrophobic base of these products consists of the reaction product of ethylene diamine and excess propylene oxide and has a molecular weight of about 2,500 to about 3,000.

This base is prepared such that the condensation product contains from about 40 to about 80 weight percent polyoxyethylene and from about 5000 to about 1100 weight percent polyoxyethylene.
It is condensed with ethylene oxide to the extent that it has a molecular weight of 0.

An example of this type of non-ionic surfactant is the commercially available "Tetronic" compound from Wyandotte Chemicals.

Certain nonionic surfactants used in the detergent compositions of the present invention have a hydrophilic-lipophilic balance (H
LB).

A highly preferred nonionic surfactant within this range is 6
It is a condensation product of 1 mole of ethylene oxide and 1 mole of coconut fatty alcohol (HLB=12).

The presence of the nonionic surfactant at the specified concentration in the liquid detergent composition of the present invention provides the necessary oil stain removal properties both when used for mae treatment and when used in laundry water. be able to.

Nonionic surfactants of this type also aid in the physical stability of liquid detergent compositions.

Anionic Surfactant The anionic component of the detergent composition of the present invention is derived from a mixture of ethanolamine salts of alkylbenzene sulfonic acids (ethanolamine alkylbenzene sulfonates) and ethanolamine salts of fatty acids (hereinafter referred to as ethanolamine soaps). Become.

Both of these salts are made by neutralizing the corresponding anionic acid with an ethanolamine selected from the group consisting of monoethanolamine, jetanolamine and triethanolamine.

This mixture of anionic surfactant salts comprises a nonionic surfactant and an anionic surfactant (
(on a free acid form basis) from about 2.5:1 to about 3.
．． A sufficient amount is used to give a ratio of 5:1.

The non-soap component of the anionic surfactant mixture emanates from mono- or triethanolamine salts of straight-chain or branched-chain alkylbenzene sulfonic acids 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 chains are linear and have an average length of about 12 carbon atoms.

Examples of the ethanolamine salt of alkylbenzenesulfonic acid used in the present invention include monoethanolamine decylbenzenesulfonate, jetanolamine undecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate, monoethanolamine tridecylbenzenesulfonate. , triethanolamine tetradecylbenzenesulfonate, and jetanolamine tetrapropylenebenzenesulfonate.

Examples of commercially available alkylbenzene sulfonic acids used to produce the ethanolamine sulfone salt of the present invention include "Conoco JSA515. 5A597. and 5A69.
7 (all sold by Continental Oil Company) and Calsoft JLAS99 (all sold by Continental Oil Company).
(Sold by Pilot Chemical Company).

The soap component of the anionic surfactant mixture ranges from about 8 to about 2
4, preferably from about 10 to about 20 carbon atoms, fatty acid mono-, di-, and triethanolamine soaps.

Suitable fatty acids are derived from natural sources, such as vegetable or animal esters such as palm oil, coconut oil, babassu oil, soybean oil, safflower oil, tall oil, castor oil, tallow, whale oil and fish oil, greases, lard and the like. can be obtained from a mixture of

Fatty acids can also be synthesized (for example, by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process).

Examples of suitable soaps for use in the present invention include monoethanolamine caproate, jetanolamine laurate, triethanolamine myristate, triethanolamine myristate, monoethanolamine stearate and diethanolamine palmitoleate. .

Preferred soaps are mono-, di- and triethanolamine soaps of fatty acid mixtures derived from coconut oil and tallow.

A particularly preferred soap for use in the present invention is ethanolamine oleate.

Examples of commercially available fatty acids used in the production of the ethanolamine soap of the present invention include C-105, ClO3, C-110
, T-10, T-11 and 0L910 (all the
Brocter & Gamble Company) and ``Hifatsk'' (a hydrogenated fish oil fatty acid sold by Emery Industries, Inc.).

In the anionic surfactant mixture, the two components have a weight ratio of about 20:1 of the sulfonate acid form (alkylbenzene sulfonic acid) to the soap acid form (fatty acid).
present in an amount sufficient to provide a ratio of from about 1:1 to about 4:1 to about 8:1.

It has been discovered that anionic mixture component ratios within this range exhibit unexpectedly high soil and stain removal properties, while providing excellent laundering and laundering suds control.

As mentioned above, the anionic surfactant mixture as a whole in the composition of the invention has a weight ratio of nonionic surfactant to anionic surfactant (based on free anionic acid) of about 3=1, or about The ratio should be between 2.5:1 and about 3.5:1.

The reasons why such weight ratio restrictions are important will be discussed in more detail below.

Ethanolamine The third essential component of the liquid composition of the present invention is an ethanolamine compound.

Ethanolamines suitable for use in the present invention include:
selected from the group consisting of monoethanolamine, jetanolamine, triethanolamine and mixtures thereof.

A mixture of these three ethanolamine compounds is made by the reaction of ethylene oxide and ammonia.

The pure compound can be separated from this mixture by standard distillation methods.

The ethanolamine fraction of the present invention serves two purposes.

As discussed in further detail below, in a preferred method of making the compositions of the present invention, the ethanolamine neutralizes the free acid form of the anionic surfactant mixture to form the corresponding component, which is a major component of the compositions of the present invention. Produces ethanolamine salt.

Furthermore, the excess ethanolamine in excess of the amount required to form the anionic surfactant salt by the method of the present invention contributes to detergency and also increases the wash water pH of the compositions of the present invention from about 7 to 7.
Serves as a buffer to keep it in the range of about 9.

It is important that the compositions of the present invention contain at least one part (by weight) of total free ethanolamine.

Compositions containing the nonionic, anionic and ethanolamine components described above can be formulated by making each component separately and thoroughly mixing them together in any order.

Also, in a preferred method of making the compositions of this invention, the anionic and ethanolamine components are combined simultaneously by overneutralizing the appropriate mixture of sulfonic acid and fatty acid with ethanolamine.

This process can produce the required ethanolamine alkylbenzene sulfonate and ethanolamine soap in situ, as well as the free ethanolamine component of the composition of the invention.

When using this preferred formulation, the total amount of ethanolamine used will vary depending on the nature and proportions of the respective alkylbenzenesulfonic acids and fatty acids, and the specific ethanolamine used.

Preferred ethanolamine concentrations for use in formulating the anionic-ethanolamine portion of the compositions of the invention include anionic surfactant mixtures (on a free acid basis) in detergent compositions.
This is the concentration at which there is approximately the same amount of ethanolamine.

By adding this preferred amount of ethanolamine, ethanolamine is always present in greater than the stoichiometric amount required for complete neutralization of the acidic mixture, and no matter what ethanolamine is used, and within the limits of the present invention. Any anionic acid mixture can be used to generate the required excess amount of free ethanolamine.

Optional IngredientsAlthough the liquid detergent compositions of the present invention need only contain the three ingredients listed above (i.e., no worries), highly preferred compositions of the present invention contain, in addition to the three active ingredients, water. and water
and a solvent selected from the group consisting of alcohol mixtures.

Generally, this type of solvent is about 1 φ to about 4 φ of the total amount of the detergent composition.
It can be added at a ratio of 5 factors (weight).

In preferred compositions, the solvent ranges from about 25 parts to about 45 parts by weight.

The addition of such solvents exhibits several advantages.

First, the addition of such solvents lowers the clearing point of the composition, improves its physical stability, and prevents clouding at low temperatures, such as that seen during shipping or storage of commercial detergent compositions. A composition with no

Second, when adding a solvent, especially a water-alcohol mixture,
This helps control the tendency of detergent compositions of this type to gel when diluted with water.

Finally, detergent compositions of the present invention containing such solvents are desirable from a few safety points of view.

Diluted solutions are less toxic and less irritating to the eyes than concentrated or anhydrous detergent compositions containing three active ingredients.

When using an alcohol-water mixture as the solvent, the weight ratio of water to alcohol is greater than or equal to about 3:1, preferably about 4:1.
~ about 7:1.

If the concentration of alcohol (especially ethanol) is higher than the above in the water-alcohol mixture of the present invention, there is a problem of ignition, so it is desirable to avoid this.

When using water-alcohol mixtures in the compositions of the present invention, any alcohol containing from 1 to about 5 carbon atoms can be used.

Examples of alcohols that can be used include methanol 1, ethanol, propatool, isopropanol, butanol, isobutanol, and pentanol.

From a toxicological point of view, ethanol is highly preferred.

A second optional component that can be added into the detergent compositions of the present invention is an electrolyte salt.

The addition of electrolyte salts can reduce the gel formation that tends to occur upon dilution of the compositions of the invention.

By using an electrolyte salt in the range of about 0.51 to 5 (by weight) with a hydroalcoholic solvent, gel formation can be completely prevented without using alcohol levels that exceed flammable safety standards as described above.

Suitable electrolyte salts include alkali metal chlorides, sulfides and carbonates, and salts formed by the reaction of ethanolamine with formic, acetic, propionic, butyric, citric and sulfuric acids.

Examples of this type of salt are sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate,
These include sodium sulfate, triethanolamine sulfate, triethanolamine citrate, triethanolamine acetate, triethanolamine formate, monoethanolamine propionate, and jetanolamine butyrate.

Potassium chloride is particularly preferred and is preferably added in an amount ranging from about 1% to 3% (by weight) to the compositions of the present invention.

The use of solvents and electrolytes as described above helps control and tune gel formation in the liquid detergent compositions of the present invention.

However, if gel formation is desired, the alcohol and electrolyte salts can be omitted, and the concentration of water as a solvent can be chosen to yield a gelled composition (as mentioned earlier, the gel composition is (a “liquid” for purposes of the invention).

That is, the above three active ingredients and the solvent are about 15 to 3
A composition containing 5 liters of water becomes a gel composition unless alcohol or electrolytes are present.

Other optional, non-interfering ingredients can be added to the compositions of the present invention to improve their performance and appearance.

Preferred compositions according to the invention are those with added color stabilizers such as citric acid.

These compositions exhibit surprising stability against the tendency to redden during storage.

Additionally, the presence of citric acid indicates that the composition of the present invention may be spilled or leached onto the outside surface of the plastic container, or that the composition may be exposed to the outside surface of the container by handling the container with a hand that has previously been exposed to the composition. This is advantageous from the viewpoint of preventing stains from forming on the skin.

When citric acid is added to a composition of the invention containing an excess amount of ethanolamine, it forms ethanolamine citrate, similar to an anionic surface active acid.

However, for convenience, this ethanolamine citrate concentration in the composition is expressed as the free acid form of citric acid, ie, the weight percent of the citric acid added to the composition.

To obtain this color stabilizing effect, citric acid is generally added to about 1 part (by weight) of the composition.

The most preferred range of citric acid added is about 0% of the composition.
．． The range is from 0.05% to about 0.10φ (weight).

Other optional ingredients are Prydona, fluorescent agents, enzymes, Bleach-9 antimicrobial agents, corrosion inhibitors, and colorants.

These ingredients are included in about 3 parts (by weight) or less of the total ingredients.

When formulating detergent compositions with unexpected performance and stability properties according to the present invention, an excess of free ethanolamine is used and a mixture of nonionic and anionic surfactants (on a free acid basis) 2.5:1 to about 3.5:
It is most important to adopt a ratio of 1.

Mixed micelles made using this particular nonionic surfactant/anionic surfactant ratio according to the present invention result in unexpected detergent performance that is insensitive to water hardness.

The use of an ethanolamine salt and an excess of ethanolamine also contributes to the effectiveness of the compositions of the present invention.

For example, a composition of this type containing a counterion of ethanolamine together with an excess of free ethanolamine may be compared to a corresponding composition containing a conventional sodium or potassium salt of an anionic surface-active acid and free of free ethanolamine. It has far superior cleaning power than polyester/cotton.

The compositions of the invention can be used in two different ways for cleaning cotton fabrics.

The compositions of the present invention can be applied in concentrated form directly onto stains on textiles as a matting agent prior to laundering the textiles.

The compositions of the invention can also be used as detergents in conventional textile laundering processes.

Stain removal and soil removal can be achieved by dissolving the compounds of the present invention in laundry solutions to the extent of about 0.10% (by weight) (approximately T cups per 17 to 19 gallons of wash water). ).

With regard to the effectiveness of mae treatment, the compositions of the present invention containing the above-mentioned components in the above-mentioned proportions are capable of removing oil-based stains from polyester or polyester/cotton fabrics, and the effect is similar to that of conventional builder-containing (built) anionic detergents. higher than similar mae treatment efficiencies obtained using the composition;
It is also comparable in practical terms to the efficiency obtained using nonionic surfactants for the removal of such mae-treated stains.

On the other hand, certain compositions of the invention are superior to conventional nonionic surfactant-based products for soil removal in wash water (stain removal from certain cotton fabrics) under standard domestic laundry conditions. It's much better than that.

The cleaning power is practically comparable to that obtained with conventional built granular anionic detergent compositions.

The invention will now be explained by some examples.

Example 1 Heavy duty liquid detergent composition 10 having the following composition:
Prepare 0g.

Ingredients Condensation product of ethylene oxide and coconut fatty alcohol with a weight factor of 6 moles 33. Triethanolamine salt of a linear alkylbenzenesulfonic acid with an average chain length of O alkyl chain of 12 carbon atoms 161 Triethanolamine salt of oleic acid 2.3 Free triethanolamine 5.3 Ethanol
5.5 Potassium chloride
2.5 Triethanolamine Citrate 0.17 Brightna,
Fragrance, dye 1.2 water
Remainder: In the above composition, the weight ratio of nonionic surfactant to anionic surfactant (based on free acid) is 2.64:1, and the weight ratio of the acid form of the sulfonate to the acid form of the soap is The ratio is 7.35:1.

The anionic surfactant-ethanolamine portion of this composition comprises 11 g of C1□alkylbenzene sulfonic acid;
It is made by mixing 1.5g of oleic acid and 11g of triethanolamine.

Such compositions are stable, clear liquid detergents that do not gel when diluted with water and are relatively non-toxic (L D 50 = 8 ml/kg: E
D 50 < 1 ml 7 kg), is also freeze stable and relatively non-flammable (Tagliaview Open Cup Flashpoint - approx. 70°
C (approximately 157 degrees Fahrenheit)), it also produces consistent, medium-height suds in wash waters of various temperatures and hardnesses, and exhibits excellent mae treatment detergency and wash water detergency.

This composition has excellent color stability.

Several heavy duty liquid detergent compositions are prepared having the compositions shown in Table 1 below.

The combination of anionic and ethanolamine components in these compositions are all made as described in Example 1 by neutralizing the acid form of the anionic surfactant with ethanolamine.

Adding 0.05 g of citric acid to the composition significantly improves its color stability.

Examples 1-M above are various detergent compositions within the spirit of the present invention.

Examples ■, ■, ■, ■, and X are highly reduced liquid detergent compositions.

Examples ■, ■, ■ and M have low active detergent content.

Example X shows a detergent gel.

All these compositions showed excellent mae treatment performance when applied directly to textile stains and also showed excellent stain treatment performance in washing water (17
It exhibits excellent washing power when used in amounts of about ±1 cup per gallon (~19 gallons).

Wash-Wear Test The wash water detergency of a few compositions of the present invention was compared with a commercially available built granular detergent in a wash-wear test.

The test was conducted as follows: a white dress shirt, cotton T-shirt, or other fabric was divided among several people.

Each shirt and T-shirt was worn under normal conditions for one working day, and the other products were used for their respective purposes.

The soiled clothes and fabrics were washed in a self-agitating washing machine for 10 minutes with a detergent solution at about 41'C (105'F).

The detergents used were the compositions of Examples ■, ■, ■, and
As a control, Tide, a commercially available built granular detergent sold by The Procter & Gamble Company, was used at concentrations of 17 cups and 1 cup per 17 gallons of fishing rod.

Wash water using the liquid detergent solution of the present invention has a pH of about 7.2.
The water in the control Tide solution had a pH of about 9.5.

The water hardness was 3.81 (approximately 7 grains per gallon).

After washing, the clothes were washed in water (6 spray washes and 1 deep wash) and then dried.

The ratings for each group of shirts and clothing that had been worn by the same person were compared by looking directly at them.

Whiteness and cleanliness of dress shirts, T-shirts, and other clothing were rated, with particular attention paid to the collar and cuffs of the dress shirt.

As used herein, "cleanliness" or "cleanliness" refers to
It refers to the ability of a detergent composition to remove stain lines or stain deposits, such as those found in deeply soiled collars or creases on cuffs.

Whiteness, on the other hand, is a broader concept that describes the ability of a detergent to whiten slightly or moderately soiled areas.

The relative cleaning power of each part of each detergent composition was rated visually on a 9-point scale under artificial lighting, with the highest grade corresponding to the best performance.

Based on such comparisons, all liquid detergent compositions of the present invention were found to have a cleaning power equivalent to 17 cups of Tide.

Furthermore, all detergent compositions of the present invention are
It showed a degree of associative whitening corresponding to 7 cups.

Only the diluted compound (1) showed a degree of combined whitening equivalent to one cup of "Tide".

Oil Stain Removal Test Representative compounds of the present invention were compared to commercially available detergent compositions for their ability to remove various oil stains from polyester/cotton (65%/35%) fabrics.

26crrLX 28crfL (11"X 1 r'
) olive-colored polyester/cotton fabrics were stained with a drop of each of Crisco cooking oil, bacon grease, mineral oil, stained bean oil, French dressing, and tanning oil and aged for 16 to 20 hours.

Four pieces of cloth were used for each test product.

The first strip applied 1 cc of product directly to each stain; the second strip applied 2 cc of product to each stain; the third strip applied 3 cc of product to each stain. A fourth cloth was applied to each stain; and a fourth piece of cloth applied 4 cc of product to each stain.

After applying the product to the fabric strips, each stain was rubbed horizontally for 10 seconds and vertically for 5 seconds to simulate home mae treatment methods.

The products tested were: (1) the citric acid-containing liquid detergent composition of Example 1 above; (2) the commercially available built heavy duty liquid detergent; and (3) the commercially available unbuilt heavy duty liquid detergent. ;0) was a 50% water-product paste made from the granular built detergent "Tide".

Four pieces of cloth for each product were washed in an automatic washing machine.

This washing machine runs 7 grains/3 at approximately 53°C (125°F).
．． Contains 69.77 (18.5 gallons) of hardened water and a standard household detergent charge.

Each detergent charge contains the "recommended" use concentration in the laundry solution, i.e.
゛″°′°′Unbuilt liquid tup; Also, “Tide” is 1
It contained approximately enough test product to form a cup (including the amount rubbed into the four cloth pieces).

Two graders rated each stain on each piece of cloth on an O to 10 scale.

0 is stain removal TL. 10 corresponds to complete stain removal.

Add up the grades of the six stains and divide by 60.

This quotient is multiplied by 100 to yield a composite stain removal index for each piece of fabric.

The test results are shown in Tables 2 and 3 below.

As is clear from the foregoing results, it is clear that the compositions of the present invention are generally superior to other components in removing oil stains from polyester-containing fabrics.

Foaming Performance Test The very high foaming consistency of the heavy duty liquid detergent compositions of the present invention is demonstrated in the Foam Height Test as follows.

The composition of Example I was washed at a standard concentration of 647 (17 gallons) in a top-load automatic washer under various water temperature and water hardness conditions. It was used for loading laundry.

After about 10 minutes, the foam height was measured in inches and 24 measurements were averaged for each condition combination.

The results are shown below.

Conditions Average bubble height (CrrL (inch)) 20°C (700F); 7gL, -76,6 (2,6)
38°C (100°F); 2 grains 8.7 (
3A') 38°C (100'F)'7 grains
8.7 (3,4) 38°C (1000F)'14 grains 6.4 (2,5) 52°C (125°F);
7 grains 6.6 (2,6) 600C (140
'F); 2 grains 7.1 (2,8) 60°C
(140°P); 7 grains 7.9 (3,1) As is clear from the foregoing tests, in various warm and cold conditions, the composition of the present invention has an average foam height of 1 inch or more. You can see that it hasn't changed.

Embodiment (2) In the composition according to the claims, further about 10
The solvent is a mixture of water and an alcohol of 1 to about 4 carbon atoms; the weight ratio of water to alcohol of the mixture is about 3:1 or more.

2. In the composition according to item 1 above, the alcohol is ethanol.

3. The composition according to item 2 further contains an electrolyte salt having a diameter of about 0.5φ to about 5 (by weight).

4. In the composition according to item 3 above, the electrolyte salt is potassium chloride.

5. In the composition according to item 4 above, the anionic surfactant mixture contains a sufficient amount of sulfonic acid such that the weight ratio of the acid form of the sulfonate to the acid form of the soap is about 4=1 to 8:l. Contains soap; and the solvent has a water to ethanol weight ratio of approximately 4.
:1 to about 7:1 by weight; the solvent comprises about 25 fO to about 45 fO of the composition; and the potassium chloride electrolyte salt comprises about 1 to about 3 fO of the composition. Includes rice cake (weight).

6. A groove detergent composition mainly consisting of the following: (a) A nonionic surfactant produced by condensation of alkylene oxide and an organic hydrophobic compound from about 35 parts to about 60 parts (by weight).

The nonionic surfactant has a hydrophobic-hydrophilic balance of about 8 to about 15; (b) the nonionic surfactant and anionic surfactant mixture (as its free acid form) has a weight ratio of about 2.5: 1
an anionic surfactant mixture in an amount sufficient to provide a ratio of ~35:1; the anionic surfactant mixture comprises: (1) an alkylbenzene having an average linear alkylbenzene chain length of about 12 carbon atoms; Ethanolamine salt of sulfonic acid.

(ii) an ethanolamine soap containing from about 10 to about 20 carbon atoms in the fatty acid moiety: the ethanolamine portion of the sulfonate and soap is selected from the group consisting of monoethanolamine, jetanolamine, and triethanolamine; ( C) an ethanolamine selected from the group consisting of monoethanolamine, jetanolamine, triethanol and mixtures thereof; free ethanolamine comprises at least about 1% of the composition;
(d) from about 25% to about 45% (by weight) of the solvent.

The solvent has a weight ratio of water to ethanol of 4:1 to about 7:1.
and (e) sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanolamine citrate, triethanolamine acetate, triethanolamine formate. 0.5% to about 5% (by weight) of an electrolyte selected from the group consisting of , monoethanolamine propionate, and jetanolamine butyrate.

7. In the composition according to item 6 above, (a) the nonionic surfactant is a condensation product of ethylene oxide and coconut fatty alcohol, and the condensation product contains about 6 moles of ethylene oxide per mole of coconut fatty alcohol. (b) the ethanolamine moiety of the sulfonate and soap is triethanolamine; (c) the free triethanolamine is triethanolamine; and (d) the electrolyte salt is about 1 to about 3 weight of the composition. ) is potassium chloride present in the range.

8. In the composition of item 7 above, triethanolamine citrate is further added in an amount of about 0.05% of the composition based on the citric acid form.
Contains ~0.10% (by weight).

9. In the composition according to the claims, further about 15
The composition is free of alcohol and electrolyte salts and has a tendency to form gels.

Claims (1)

[Scope of Claims] 1. A liquid detergent composition consisting essentially of the following ingredients: (a) a nonionic surfactant having an HLB of about 8 to 15, produced by the condensation of ethylene oxide and an organic hydrophobic compound; are straight-chain or branched alkylphenols with alkyl groups having about 6 to 12 carbon atoms, straight-chain or branched aliphatic alcohols having about 8 to 22 carbon atoms, propylene oxide and Condensation products with a molecular weight of about 1500 to 1800 with propylene glycol and about 250 with propylene oxide and ethylenediamine
selected from the group consisting of reaction products having a molecular weight of 0 to 3000; (b) an anionic surfactant mixture, the anionic surfactant having a weight ratio of nonionic surfactant to anionic surfactant mixture (in its free acid form) of about 2.
5:1 to 3.5:1, the mixture comprising: (1) an alkylbenzenesulfonic acid ethanolamine salt having an average of about 12 carbon atoms in the linear alkyl chain;
and (11) an ethanolamine soap containing about 10 to 20 carbon atoms in the fatty acid moiety of the soap, wherein the sulfonate salt and the ethanolamine moiety of the soap are
selected from the group consisting of monoethanolamine, jetanolamine and triethanolamine, and said anionic surfactant mixture has a weight ratio of sulfonate in acid form to soap in acid form of about 4=1 to 8:1. Contains sufficient sulfonate and soap to (c) Ethanolamine The ethanolamine is selected from the group consisting of monoethanolamine, jetanolamine, triethanolamine and mixtures thereof, and the free ethanolamine is sufficient to provide at least about 1 weight φ of the composition. Exist in quantity. (d) about 1 to 3 weight grams of solvent. The solvent is a water-ethanol mixture with a water to ethanol weight ratio of about 4=1 to 7:1. (e) about 1 to 3 weight φ of potassium chloride, and (f
) ethanolamine citrate. The ethanolamine citrate is present in the citric acid form in about 0.05 to 1 weight percent of the composition.