CA1049367A - Liquid detergent compositions having soil release properties - Google Patents

Abstract

LIQUID DETERGENT COMPOSITIONS HAVING
SOIL RELEASE PROPERTIES
ABSTRACT OF THE DISCLOSURE
Heavy duty liquid detergent compositions containing nonionic surfactants, ethanolamine-neutralized anionic surfactants, free ethanolamine and polyester soil release agents which are particularly suitable for laundering hydrophobic fibers such as polyester.

Description

BACKGROUND OF THE INVENTION
The present invention relates to heavy duty liquid detergent compositions containing nonionic surfactants, ethanolamine-neutralized anionic surfactants, free ethanolamine and a polymeric soil release agent. As used herein, the term "liquid" encompasses semi-liquid or gel compositions, as well as more conventional freely-flowing formulations.
Heavy duty liquid detergent compositions are well-known in the art. Usually such compositions (see, forexample, U.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 detergent component which is generally anionic, nonionic, or mixed anionic-nonionic in nature; an inorganic builder salt; and a solvent, usually water and/or alcohol. These compositions frequently contain a hydrotrope or solubilizing agent to permit the addition of sufficient quantities of surfactant and builder salt to provide a reasonable volume/usage performance ratio. While such liquid detergent compositions have been found effective for some types of home laundering, alternative compositions which do not contain inorganic builder salts are of current interest and are being developed to replace built compositions on a broad scale.
Attempts have been made to formulate builder-free, hydrotrope-free liquid detergent compositions. For example, U.S. Patent 3,528,925 discloses substantially anhydrous liquid detergent compositions which consist of an alkyl aryl sulfonic acid, a nonionic surface active agent and an alkanolamine component. U.S. Patent 10493~7

2,875,153 discloses liquid detergent compositions containing a nonionic surfactant component and a sodium soap component. U.S. Patent 2,543,744 discloses a low-foaming dishwashing composition comprising a nonionic, water-soluble, synthetic detergent and a water-soluble soap in the form of an alkali metal, ammonium or amine salt. U.S. Patent 3,663,445 pertains to liquid detergent compositions which contain anionic and nonionic sur-factants in combination with certain ethanolamime compounds.
Attempts have also been made to provide compounds capable of conferring soil release properties to fabrics woven from hydrophobic fibers, particularly polyester. These synthetic fabrics are frequently co-polymers of ethylene glycol and terephthalic acid, and are sold under a number of trademarks, e.g., Dacron ~ , Fortrel , Kodel ~ and Blue C Polyester ~ As a result of the hydro-phobic character of the~e fabrics, their laundering (particularly as regards oily soil and oil stains) is difficult because of the reduced wettability of the fibers. Since the inherent character of the fabric itself is hydrophobic, or oleophilic, once an oily soil or oily stain is deposited on the fabric, either by normal use or by accident, the oily soil or oily stain tends to be "attached" to the surface of the fiber.
As a result, the oily soil or stain is difficult to remove in the laundering process.
Due to the fact that synthetic polyester and poly-ester-blend fabrics (e.g. polyester-cotton blends) are sus-ceptible to oil staining and, once stained, are difficult to clean, manufacturers of synthetic fabrics and blends have sought to increase the hydrophilic character of the polyester to provide ease of laundering.
A number of approaches for enhancing the hydrophilic character of polyester fabrics and blends have been employed.
These methods often involve a process carried out by the textile-fiber manufacturer or the textile manufacturer; see Imperial Chemical, Netherlands Application 65/09456, published January 24, 1966; see also D. A. Garrett and P.N. Hartley, J. Soc.
Dyers and Colourists, 82, 7, 252-7 (1967) and Chem. Eng. News, - 44, 42-43 (October 17, 1966).
Other polyester fabric finishing techniques involving detergent compositions are described in : German Patent 1,194,734; Fiber Ind. Inc., Netherlands application 65/02428, published August 26, 1965; Belgian Patent 641,882; and French patent 1,.394,401. U.S. Patent 3,416,952 relates to a "- 1049367 modifying treatment for polyester fibers whereby a poly-ethylene terephthalate polymer is applied to the surface of said fabrics. Such polymers contain ethylene terephthalate and polyethylene oxide terephthalate units at a molar ratio from 2:1 to 6:1. British Patent 1,175,207 discloses a process for treating filaments and fibers by contacting same with polyesters containing from about 10% to about 50%
by weight of crystalline polyester segments which are identical with the repeat units forming the crystalline segment of the polyester fiber, and from about 90% to about 50~ by weight of water solvatable polyoxyalkylene ester segments. The polymers employed appear to be identical to those disclosed - in U.S. Patent 3,416,952, above. British patent 1,092,435, deals with a stable dispersion of water-insoluble graft polymers containing polyoxyethylene glycol and polyethylene terephthalate . These particular polymers have a ratio of ethylene terephthalate to polyoxyethylene terephthalate from about 2:1 to about 6:1. The teachings of British patent 1,119,367 and Imperial Chemical, Dutch Patent application 66/14134 published April 10, 1967 relate to the application of surface modifying agents to fibers as described in the ~-patents referred to hereinabove.
U.S. Patent 3,712,873 discloses the use of certain polyester polymers in combination with quaternary ammonium salts as fabric treatment compositions. Polymers having a molecular weight in the range from 1,000 to 100,000, and a molar ratio of terephthalic acid : polyglycol : glycol from 4.5 : 3.5 : 1, are disclosed. U.S. Patent 3,959,230, issued July 8, 1975, to Basadur, relates to compositions and pro-cesses for imparting renewable soil release finish to poly-ester-containing fabrics. Polymers based on terephthalic A

.

acid, ethylene glycol and polyethylene oxide and their use in acidic fabric rinses are disclosed. The polymers have a molecular weight in the range from 1,000 to 100,000, and the polyethylene oxide lin~ has a molecular weight of 1300 to 1800.
U.S. Patent 3,959,230, issued May 25, 1976 to Hugh R.
Hays, discloses terephthalate polymers composed of ethylene terephthalate and polyethylene oxide terephthalate capable of imparting soil-release properties to synthetic fibers treated with a dilute aqueous solution of said polymers. These polymers also fall within the broad class of polymeric soil release agents of the type used in the instant compositions.
In contrast with the prior art soil release polymers, the Hays' polymers are said to be especially useful in solid, dry detergent compositions; see Nicol and Hays, U.S. Patent

3,962,152, issued June 8, 1976.
While a variety of polymeric soil release agents are known, there seems to have been little or no attempt to optimize the detergent compositions used in conjunction with such agents. This is due to the heretofore unrecognized fact that certain types of soil release agents exhibit outstanding cleaning performance only when combined with specific detersive ingredients. It has now been found that, by selecting the proper detersive ingredients, liquid detergents containing any of the foregoing types of ester soil release polymers can be used to provide superior cloan-sing of oily soils and stains.
It is a primary object of this invention to provide heavy duty liquid dete~gent compositions which exhibit excellent cleanina performance while concurrently imparting soil release properties to hydrophobic fabrics treated therewith.

~A

~049367 It is another object of this invention to provide heavy duty liquid detergent compositions comprising mixtures of nonionic surfactants, anionic surfactants, and ethanolamines in combination with polymeric soil-release ingredients.
It is a further object of this invention to provide heavy duty liquid detergent compositions comprising soil-release polymers having various molar ratios of ethylene terephthalate to polyethylene oxide.
The above and other objects are met by formulating liquid detergent compositions containing mixtures of nonionic and anionic surface-active agents, free ethanol-amines and polymers composed of terephthalate esters, as described hereinafter.
The compositions herein are adapted for use both in a standard through-the-wash cleansing operation or as a pretreatment whereby the composition is applied directly to a heavily soiled fabric, which is subsequently laundered.

This invention encompasses heavy duty liquid detergent compositions capable of providing improved cleaning performance and simultaneously imparting soil release properties to fabrics treated therewith. Such compo-sitions comprise:
(a) from about 15% to about 65%, preferably about 30%
to about 60%, by weight of a water-soluble nonionic surfactant produced by the condensation of an alkylene oxide, preferably ethylene oxide, with an organic hydrophobic compound;
(b) from about 10% to about 40%, prefeLably 20% to -~

.~- . - - . , . ~ -30%, by weight of a water-soluble ethanolamine-neutralized anionic surfactant;
(c) at least 1%, preferably from about 3~ to about 15% by weight, of free ethanolamine, and (d) from about 0.15% ~o about 25~ by weight of a polymer comprising ethylene terephthalate and polyethylene oxide terephthalate, wherein said polymer comprises from about 25~ to about 50% by total weight ethylene terephthalate units, wherein said poly-ethylene oxide terephthalate contains polyethylene oxide units having a molecular weight of from about 300 to about 10,000, the total molecular weight of said polymer being in the range from about 5,000 to about 200,000.
Optionally, and in a preferred mode, the compositions herein contain a water-dispersible liquid carrier.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The compositions of the instant invention comprise (1) a nonionic surfactant; (2) an ethanolamine-neutralized anionic surfactant; (3) free ethanolamine; (4) a soil-release polymer composed of ethylene terephthalate and polyethylene oxide terephthalate; and preferably (5) a liquid carrier. Each of these ingredients is discussed in detail hereinafter.
Unless otherwise indicated, the term "%" as used herein represents percent-by-weight.
Nonionic Surfactant From about 15% to about ~5% of the liquid detergent comositions of the present invention comprise a nonionic surfactant produced by the condensation of an alkylene oxide, especially ethylene oxide (hydrophilic in nature) 104936'7 with an organic hydrophobic compound, which is usually aliphatic or alkyl aromatic in nature. The length of the hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties.
Examples of suitable nonionic surfactants herein include:
(1) The polyethylene oxide condensates of alkyl phenols.
These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol;
dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and 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 the GAF Corporation; and Triton ~ X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company.
(2) The condensation Froducts of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol can be either straight or branched and generally contains from about 8 to about 22 carbon atoms. ~xamples of such ethoxylated alcohols include the condensation product of about ~ moles o~ ethylene oxide with 1 mole of tridecanol;
myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol; the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyd chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol; and the condensa-tion product of about 9 moles of ethylene oxide with the above-described coconut alcohol. Examples of commercially available nonionic surfactants of this type Tergitol~
15-S-9 marketed by Union Carbide Corporation, Neodol~9 23-6.5 marketed by Shell Chemical Company and Kyr ~ EOB
marketed by The Procter & Gamble Company.
13) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and, of course, exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water-solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxy-ethylene content is about 50% of the total weight of the condensation product. Examples of compounds of this type include certain of the commercially available Pluronic@~
surfactants marketed by Wyandotte Chemicals Corporation.

(4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic moiety of these products consists of the reaction product of ethylene .. ~ . .
. . . . .

diamine and excess propylene oxide, said moiety having a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to ahout 11,000.
Examples of this type of nonionic surfactant include certain of the commercially available Tetronic@~ com-pounds marketed by Wyandotte Chemicals Corporation.
In the detergent compositions of the instant invention it is preferred that the particular nonionic surfactants employed have a hydrophilic-lipophilic balance (HLB) of from about 8 to about 15. A highly preferred nonionic surfactant within this range is the condensation product of 6 moles of ethylene oxide with coconut fatty alcohol (HLB = 12).
Another preferred nonionic surfactant herein com-prises a mixture of "surfactant" and "co-surfactant" as described in Canadian application Serial No. 210,835, filed October 7, 1974.
The term "nonionic surfactant as employed herein encompasses these preferred mixtures of Collins.
The presence of the nonionic surfactant in the instant liquid detergent compositions provides oily stain removal in both pre-treatment application and wash water utiliza-tion of the instant compositions. The nonionic surfac-tants also contribute to the physical stability of the liquid detergent compositions herein.
Anionic Surfactant Another essential component of the instant composi-tions is an ethanolamine-neutralized anionic surface-active ~049367 agent. This anionic component is used in an amount from about 10% to about 40% of the total compositions herein.
The ethanolamine salts are prepared by neutralizing the corresponding anionic detergent acids with an ethanolamine selected from the groùp consisting of monoethanolamine, diethanolamine and triethanolamine.
Examples of anionic detergent acids suitable for use in the compositions of this invention, after neutraliza-tion with ethanolamine, include higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms.
Suitable fatty acids can be obtained from natural sources such as plant or animal esters (e.g. , palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. Resin acids are suitable, such as rosin and those resin acids in tall oil. Naphthenic acids are also suitable. Particularly useful are mixtures of fatty acids derived from coconut oil and tallow. The ethanolamine salts can be made by direct saponification of the fats and oils or by direct neutralization of the free fatty acids which are prepared in a separate manufacturing process.
The ethanolamine salts of organic sulfuric reaction products having in their molecular structure an alkyl moiety containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical can also be used. (Included in the term "alkyl" is the alkyl portion of higher acyl radicals.) Preferred are the ~0493~7 anionic acids obtained by sulfating higher alcohols (8 - 18 carbon atoms) produced by reducing glycerides of tallow or coconut oil, and alkyl benzene sulfonic acids in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain config-uration. Especially useful are linear straight chain alkyl benzene sulfonic acids in which the average of the alkyl groups is about 12 carbon atoms; alkyl glyceryl ether sulfonic acids, especially those ethers of higher alcohols derived from tallow and coconut oil; coconut oil fatty acid monoglyceride sulfonic acids and sulfuric acid esters; and akyl phenol ethylene oxide ether sulfuric acid esters with about 1 to about lO units of ethylene oxide per molecule and in which the alkyl groups contain about 8 to about 12 carbon atoms.
Ethanolamine-neutralized anionic phosphate surfactants containing an oxyacid of phosphorus as the anionic solubilizing group are also useful. The more common solubilizing groups, of course, are -SO4H, -SO3H, and -CO2H.
Alkyl phosphate esters such as (R-O)2PO2H and ROP03H2 in which R represents an alkyl chain con-taining from about 8 to about 20 carbon atoms are useful.
These esters can also be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units. Formulae for these modified phosphate anionic acids are , [ R

: .

::

o ( 2 2 )n]
O-H
in which R resresents an alkyl group containing from about 8 to 20 carbon atoms, or an alkylphenyl group in which the alkyl group contains from about 8 to 20 carbon atoms, and in which n is an integer from 1 to about 40.
Another class of suitable anionic detergent acids particularly useful in this invention when ethanolamine-neutralized includes the 2-acyloxy-alkane-1-sulfonic acids.

These compounds have the formula O

Rl - CH - CH2SO3H
where Rl is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); and R2 is alkyl of 1 to about 8 carbon atoms.
Specific examples of beta-acyloxy-alkane-l-sulfonic acids (also known as 2-acyloxy-alkane-1-sulfonic acids) utilizable herein include 2-acetoxy-tridecane-1-sulfonic acid; 2-propionyloxytetradecane-1-sulfonic acid; 2-butanoyloxy-tetradecane-l-sulfonic acid; 2-pentanoyloxy-pentadecane-1-sulfonic acid; 2-acetoxy-hexadecane-1-sulfonic acid; 2-octanoyloxy-tetradecane-l-sulfonic acid; 2-acetoxy-heptadecane-l-sulfonic acid; 2-acetoxy-octadecane-1-sulfonic acid; 2-acetoxy-nonadecane-1-sulfonic acid; 2-acetoxy-eicosane-l-sulfonic acid; and 2-propionyloxy-docosane-1-sulfonic acid.
Preferred beta-acyloxy-alkane-l-sulfonic acids correspond to the above formula wl~erein Rl is an alkyl of about 12 to about 16 carbon atoms.

`- 1049367 Belgium Patent 650,323 discloses the preparation of certain 2-acyloxy alkanesulfonic acids.
Anotner class of anionic detergent acids which are useful herein as the ethanolamine salts include the beta-alkyloxy alkane sulfonic acids. These compounds have the following formula:
OR H

R - f c So3H
H H
where Rl is a straight chain alkyl group having from 6 to 20 carbon atoms and R2 is a lower alkyl group having from 1 to 3 carbon atoms.
Specific examples of beta-alkyloxy alkane sulfonic acids or alternatively 2-alkyloxy-alkane-1-sulfonic acids, utilizable herein to provide superior cleaning and whitening levels under household washing conditions include:
; beta-methoxydecanesulfonic acid, beta-methoxy-tridecanesulfonic acid, beta-ethoxytetradecanesulfonic acid, beta-isopropoxyhexadecanesulfonic acid, beta-tert-butoxytetradecanesulfonic acid, beta-methoxyoctadecanesulfonic acid, and beta-n-propoxydodecanesulfonic acid.
Other anionic detergènt acids which, when ethanolamine neutralized, are preferred for use in the compositions of the instant invention include alkyl ether sulfuric acid esters and "olefin sulfonic acids".
The preferred alkyl ether sulfuric acid esters have the formula (C2 4 )xS3H
wherein R is alkyl or alkenyl of about 10 to about 20 carbon __ .. . . . .. _ .

atoms, and x is 1 to 30.
Es~ecially preferred are those alkyl ether sulfuric acid esters wherein R has from about 14 to about 1~ carbon atoms and wherein x has an average value of about 1 to about 6. Specific examples of especially preferred species include: coconut alkyl ethylene glycol sulfuric acid ester;
tallow alkyl trioxyethylene sulfuric acid ester; tallow alkyl pentaoxyethylene sulfuric acid ester; tetradecyl pentaoxyethylene and lauryl hexaoxyethylene sulfuric acid esters.
The preferred "olefin sulfonic acids" for use herein in ethanolamine neutralized form have from about 12 to abou-t 24 carbon atoms in the alkyl portion of the molecule.
Such materials can be produced by sulfonation of ~-olefins by means of uncomplexed sulfur dioxide followed by neutraliza-tion with ethanolamine under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy-alkane sulfonates. The ~-olefin starting materials preferably contain from 14 to 16 carbon atoms. The preferred ~-olefin sulfonates are described in great detail in U.S. Patent 3,332,880, Adriaan Kessler, et al., patented July 2S, 1~67.
Examples of preferred ~-olefins include l-tetradecene, l-hexadecene, l-octadecene and mixtures thereof. As noted, the anionic acids are neutralized with an ethanolamine neutralizing agent selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof.
Triethanolamine is the preferred ethanolamine herein;
hence, the triethanolamine salts of tne foregoing surfactant acids are preferred in the present compositions.

~ree Ethanolamine Component The liquid detergent compositions of the present invention contain from about 3% to about 15%, preferably from about 5~ to about 15%, of free ethanolamine. The ethanolamine useful herein is selected from the group con-sisting of monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof. Triethanolamine is preferred.
Mixtures of these ethanolamine compounds are produced by the reaction of ethylene oxide with ammonia. T;le pure compounds can be separated from this mixture by standard distillation procedures. The free ethanolamine contributes to detergency performance and serves as a buffering agent which maintains wash water pH of the instant compositions within the range of from about 7 to about 9.
Soil Release Polymer As a further essential ingredient, the compositions of the instant invention contain from about 0.15% to about 25% preferably from about 1% to about 15%, more preferably from about 5~ to about 10%, of a soil release polymer containing ethylene terephthalate groups having the formula:

[OCH2CH2OC ~ C -] ; and polyethylene oxide terephthalate groups having the formula:

[ (OCH2CH2) nOC ~ 1C--]

wherein total weight of the ethylene terephthalate units in 104~367 the polymer (i.e., including those from the polyethylene oxide terephthalate) is from about 25% to 50% and preferably from about 30% to 40% of the polymer. The molecular weight of the polyethylene oxide linking unit is in the range from about 300 to about lO,000, preferably from about 400 to about 4,000, i.e., n in the above formula is an integer of from about 7 to about 220. The polymers have an overall molecular weight in the range from about 5,000 to about 200,000, preferably from about 25,000 to about 70,000. The polymers are also characterized by a random polymer structure, i.e., all possible combinations of ethylene terephthalate and polyethylene oxide terephthalate can be present.
Examples of the polymers which are useful herein appear in Table I.

~04g367 ~D o oo~ oo OD O
C~o n OD .0 ~ I a~ ~ ~
o . .
:
'~ ' ~

~ H . .

~ ml 1~~ 1n ~ Ln O ' ~
- In , .
.
CO
~1 o ~ o . ~1 ' ' ' .' . ~
X o d~
O-- ~ W
o W-lW~l O
o ~ ~ ~ X W

5 ~ 5 E~ E~ 5 0 ' ~ 1049367 The soil release polymers herein are substantive to hydrophobic fabrics, particularly polyesters, under laundry rinse conditions, apparently because of the presence of the hydrophobic ethylene oxide terephthalate groups.
The soil release polymers used in this invention can be prepared by conventional polymerization processes known in the art. As an example, the process described in the specification of British Patent 1,119,367 can be used for preparing operable polymers herein by selecting the proper monomer precursors. Preferred polymers for use herein are prepared according to the following technique: 194 g.
dimethyl terephthalate, 67 g. etnylene glycol, 420 g.
polyethylene oxide (molecular weight 600); 0.44 g. 2,6-di-tert-buty1-4-methylphenol; 0.0776 g. antimony trioxide;
and 0.3024 g. calcium acetate are mixed in a suitable reaction vessel and heated to 210C with stirring over a 1.5 hour period. During this time, methanol and some dimethyl terephthalate are distilled from the reaction vessel. The reaction temperature is then raised to 280C
and maintained at this temperature for two hours. Following addition of 0.282 g. of a 24.8% solution of phosphorous acid in ethylene glycol to the foregoing reaction mixture, a stream of nitrogen is blown over the reaction mixture and allowed to exhaust for two hours. Dispersions of the polymer prepared in this manner can be made by mixing the molten polymer with water in a Waring blender.
In the preparation of the above polymers the nitrogen exhaustion preferably lasts from about two hours to about 2 1!2 hours. Lowering the nitrogen exhaustion to about 1.5 hours or increasing it to about 3.0 hours adversely affects the soil-release characteristics of the operable polymers.

~04C~367 Processin~
The present compositionscan be formulated by preparing each component separately and thoroughly mixing them to-gether in any order. In a preferred method for preparing the instant compositions, the anionic detergent and tne ethanolamine components are formulated simultaneously by over-neutralizing mixtures of the anionic detergent acid with the ethanolamine. This method forms the requisite ethanolamine-neutralized anionic surface-active agent in situ and also provides the free ethanolamine component of the instant composition.
When this preferred composition formulation method is utilized, the total amount of the ethanolamine employed will vary with the nature and proportion of the particular anionic detergent acid and with the particular ethanolamine employed. A highly preferred ethanolamine concentration for formulation of the anionic-ethanolamine portion of the composition is that ethanolamine weight percentage which is approximately equal to the weight percent of anionic surfactant mixture (on a free acid basis) present in any given detergent compositions of the instant invention.
By adding this preferred amount, the ethanolamine will always be present in greater than stoichiometric amount for com~lete neutralization of the acid mixture and will provide the requisite excess free ethanolamine no matter which ethanolamine and which anionic acid mixture is used, within the limits of the present invention.
Liquid Carrier Although the present liquid detergent compositions need only contain the above-described components (i.e., anhydrous compositions), and are liquid in this form due to the fluidity of the nonionics and ethanolamines, highly preferred compositions of tne present invention contain, in addition to these active components, a liquid carrier selected from the group consisting of water and water-alcohol mixtures. Generally, sucn liquid carriers can be employed to the extent of from about 1% to 4~% by weight of the total detergent compositions. Preferred compositions comprise from about 25% to 45% by weight of a liquid carrier.
The carriers herein are solvents for the active ingredients, and use of such solvents provides several advantages. First, the physical stability of the detergent compositions is improved since clear points can thereby be lowered to provide compositions which do not cloud at lower temperatures which might be encountered during shipping or storing of commercially marketed detergent compositions.
Secondly, addition of solvents, especially water-alcohol mixtures, serves to regulate the gelling tendency wnich liquid detergent compositions of the instant type exhibit upon dilution with water.
- 20 When an alcohol-water mixture is employed as a solvent, the weight ratio of water to alcohol preferably is maintained above about 3:1, more preferably from about 4:1 to about 7:1.
Alcohol (particularly ethanol) concentrations higher tnan this in water-alcohol mixtures used in the instant invention are preferably avoided because of flammabi~ity problems which arise at higher alcohol levels.
Any alcohol containing from 1 to about 5 carbon atoms can be employed in the water-alcohol carrier mixture when such mixtures are utilized in the instant detergent com-positions. Exam~les of operable alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and : .

pentanol. From a toxicological standpoint, ethanol is hi~hly preferred.
Anti-Gelling A~ent Another o~tional component which can be added to tne detergent compositions of the instant invention comprises an electrolyte salt. Addition of an electrolyte salt serves to lessen gel formation which tends to occur upon dilution of the instant detergent compositions with water. When used in combination with a water-alconol solvent, from about 0.5% to 5~ by weight of an electrolyte salt completely eliminates gel formation without the need for alcohol levels which exceed flammability safety levels.
Suitable electrolyte salts include the alkali metal, chlorides, sulfates and carbonates, and the salts formed from the reaction of ethanolamines with formic, acetic, propionic, butyric, citric or sulfuric acid. Specific examples of such salts include sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, potassium sulfate, sodium sulfate, triethanolamine sulfate, triethanol-amine citrate, triethanolamine acetate, triethanolamineformate, monoethanolamine propionate and diethanolamine butyrate. Potassium chloride is highly preferred as an anti-gellant when employed in the instant compositions at concentrations of from about 1% to 3% by weight.
As noted, the employment of a liquid carrier solvent and electrolyte controls gel formation in the instant liquid detergent compositions. If, however, gel formation is desired, it is possible to select particular concentrations of a water carrier which yield gelled compositions in the absence of alcohol and electrolyte salt. (As noted, a gel composition is a "liquid" for purposes of this invention.) iO49367 Thus, compositions containing the three active components in the above-specified concentrations and a water solvent comprising from about 15% to 35% by weight can be gelled, provided no alcohol or electrolyte is present.
Adjunct Com~onents Other optional non-essential, non-interfering com~onents can be added to the instant compositions to provide improved performance or aesthetic appeal. Preferred compositions of the invention are those to which a color stabilizing agent such as citric acid has been added. These compositions - exhibit surprising stability against the tendency of such ;~ compositions to develop a reddening upon storage. In addition, the presence of citric acid in the compositions of the invention has a beneficial effect from the standpoint of preventing the development of the stains observed on the outer surfaces of plastic bottles and occasioned by spillage, seepage, or handling of bottles with hands previously con-tacted with the compositions of the invention. As with the anionic surfactant acids, the citric acid forms ethanolamine citrate when added to the instant compositions containing excess ethanolamine. For convenience, this ethanolamine citrate concentration in the compositions is expressed as a weight percentage of the free acid form of the citrate, i.e., citric acid, added to the compositions. An amount of citric acid of up to about 1% by weight of composition is generally added to obtain these color benefits. A highly preferred range for the added citric acid is from about 0.05% to about 0.10~ by weight of composition.
Other optional components include brighteners, fluores-cers, enzymes, bleaching agents, anti-microbial agents, corrosion inhibitors and coloring agents. Such components '.

~04936~7 usually comprise no more than about 3~ by weight of the total composition.
Employment of ethanolamine salts and excess ethanolamine contributes to the effectiveness of the instant detergent compositions. For example, these compositions containing the ethanolamine counterion in combination with excess free ethanolamine are much superior in cleaning polyester/cotton than corresponding compositions containing the more conven-tional sodium or potassium salts of the anionic surfactant acids and no free ethanolamine.
Preferred Surfactant Compositions .
As can be seen from the foregoing, a wide variety of nonionic surfactants can be combined with a wide variety of ethanolamine-neutralized anionic surfactants and a free ~'.

ethanolamine, most preferably in combination with a liquid carrier, and employed with the soil-release polymers herein to provide highly improved heavy-duty liquid detergent compositions. Remarkably, the compositions herein provide excellent cleaning performance without the need for deter-gency builders, such as the phosphates, nitrilotriacetates, and the like. While there are various useful combinations of nonionic/ethanolamine-neutralized anionic/ethanolamine detergent compositions, the compositions disclosed in Canadian patent 1,020,039, issued November 1, 1977 and in Canadian Patent 992,835, issued July 13, 1976, are particularly adapted for use in combination with the soil-release polymers herein.
More specifically, these preferred compositions are as follows. The first type of composition contains certain specific C14 to C16 ethoxylated nonionic surfactants which provide stable compositions particularly adapted for either through-the-wash or pretreatment fabric cleansing. In general, such compositions comprise from about 25% to about 40% by weight of a nonionic surfactant derived by the con-densation of from 5 to 10 moles of ethylene oxide with an alcohol containing from 14 to about 16 carbon atoms. Such compositions additionally contain an ethanolamine-neutralized anionic surfactant of the type disclosed herein-above in an amount sufficient to provide a 2~

weight ratio of nonionic surfactant to anionic surfactant within the range o~ from about 1.8:1 to about 3.5:1, based on the free acid form of the anionic surfactant. The compositions additionally contain ethanolamine material, preferably triethanolamine, in an amount sufficient to provide at least 1% by weight of the composition of free ethanolamine.
The second type of composition particularly useful herein comprises from about 30% to about 60% by weight of a nonionic surfactant of the type disclosed hereinabove, and is not particularly limited to the nonionic sur-factants produced from the C14-C16 alcohols employed in the compositions hereinabove. These compositions additionally contain an anionic surfactant mixture present in a quantity sufficient to provide a weight ratio of nonionic surfactant to anionic surfactant mixture in its free acid form of from about 2.5:1 to about 3.5:1. Such anionic surfactant mixtures comprise an ethanolamine-neutralized alkyl benzene sulfonate having from about 9 to about 15 carbon atoms in the alkyl chain and an ethanolamine-neutralized soap (i.e., fatty acid salt) containing from about ~ to about 24, preferably from about 10 to about 22, carbon atoms in the fatty acid moiety of said soap. The anionic surfactant mixture containing the sulfonate and soap is formulated to provide a weight ratio of the acid form of the sulfonate to the acid form of the soap of from about 20:1 to about 1:1. Such compositions additionally contain a free ethanolamine, preferably triethanolamine, in an amount which comprises at least 1%
by weight of the total composition.
As noted, these preferred compositions contain the essential mixture of nonionic, ethanolamine-neutralized .

~049367 anionic and free ethanolamine compound now found to be particularly useful in combination with polymeric ester soil-release agents herein. The major difference between the two types of preferred compositions herein is that, in the first, proper selection of the relatively long-chain nonionic surfactants within a narrow range permits the formulation of storage-stable compositions without the need for the presence of fatty acid (soaps). In the second type of preferred composition, the fatty acid is present to provide long-term storage stability.
The compositions of this invention are used in two different ways for fabric cleaning. 1hey can be used as pre-treatment agents which are applied in concentrated form directly onto fabric stains prior to laundering in an aqueous bath. The compositions are also useful as detergents for conventional fabric laundering operations.
Stain removal, soil removal and soil release properties are attained when the instant compositions are employed in an aqueous laundering liquor at a concentration of about 0.10% by weight (approximately 1/4 cup per 17-19 gallons of wash water).
The compositions of the instant invention are far superior to similar liquid detergent compositions which do not contain the soil release polymer, and are especially useful for removing oil from hydrophobic fibers in the wash water of a standard home laundering process. Deter-gency performance is also superior to that attained with conventional built granular anionic detergent compositions.
The following examples illustrate the liquid detergent compositions of the instant invention:
A liquid detergent composition is prepared by mixing the following components:

~ EXAMPLE I
_ .
Component Wt %
Condensation product of coconut alcohol with 6 moles of ethylene oxide 33 Triethanolamine linear dodecyl benzene 16.5 sulfonate - Oleic acid triethanolamine salt 1,5 Free triethanolamine 5 Ethanol 6 10 Potassium chloride 2 Soil Release Polymer A* 5 Water and minor ingredients Balance to 100 * From Table I
Desized 4 inch square polyester swatches (Dacron ) either prewashed with the compositions of this invention or untreated are soiled hy depositing 0.1 ml. liquid soil (bacon grease, CriscoR oil or dirty motor oil) in the center of the swatch. The soiled swatches are allowed to wick for 18 hours at ambient conditions, whereafter they are washed 20 in an automatic washer for 10 minutes in 7 grain, 105F
water containing 1000 ppm of the above composition. The oily stain removal i5 substantially greater than that achieved under identical washing conditions using analogous liquid compositions which do not contain the soil release polymer.
Substantially the same results are achieved when soil release polymers B through E set forth in Table I are used in the above composition in levels of 5% and 10% (wt.) -Improved release of oily soil is also achieved at levels of the above polymers of 0.2% and 25%, by weight.
Substantially similar results are obtained when the .

~049367 free triethanolamine is replaced by an equivalent amount of free monoethanolamine and free diethanolamine, respectively.
Substantially comparable results are also obtained when the triethanolamine linear dodecyl benzene sulfonate is replaced by an equivalent amount of the triethanolamine salts of: coconut alkyl ethylene glycol sulfuric acid ester; tallow alkyl pentaoxyethylene sulfuric acid ester;
tetradecyl pentaoxyethylene and lauryl hexaoxyethylene sulfuric acid esters, respectively.
The foregoing composition is stable on storage. Equally stable compositions are secured by replacing the oleic acid triethanolamine salt by an equivalen~ amount of the mono-, di- and triethanolamine salts of lauric acid, myristic acid, palmitic acid, stearic acid and mixed tallowalkyl acids, respectively.
EXAMPLE II
One hundred grams of a heavy duty liquid detergent composition are formulated having the following composition:
Component Wt.%
C14_15 (EO)7 * 33.0 Triethanolamine salt of linear alkyl benzene sulfonic wherein the alkyl chain averages 12 carbon atoms in length ** - 24.2 Triethanolamine (free) 3.7 Ethanol 2.0 Potassium chloride 2.5 Soil Release Polymer A *** 5.0 Brightener, perfume, dye 0.2 Water Balance * Commercially available as Neodol 45-7 ** Prepared by admixing 16.5 g. of C alkylbenzene sulfonic acid and 11.0 g. trietha~olamine.
*** From Table I.

1~19367 The weight ratio of nonionic surfactant to anionic surfactant (on a free acid basis) in the foregoing composi-tion is 2.00:1.
The foregoing composition is a stable (i.e., does not separate or otherwise degrade on storage and is satisfactory for use after being subjected to a freeze-thaw cycle) clear liquid detergent which does not gel upon dilution with water. The composition provides level medium-high sudsing in wash water of varying temperature and hardness. The foregoing composition provides improved pre-treatment and through-the-wash fabric detergency.
The foregoing composition is modified by the addition of 0.05~ of citric acid. The color stability of the composition containing citric acid is markedly improved over similar compositions without citric acid.
In the above composition the triethanolamine-neutralized anionic surfactant is replaced by the mono-ethanolamine- and diethanolamine-neutralized anionic surfactant, respectively, and good overall detergency is secured.
In the above composition the free triethanolamine is replaced by free monoethanolamine and free diethanolamine, respectively, and good overall detergency is secured.

EXAMPLE III
Component Wt.%
Condensation product of average 7 moles of ethylene oxide with C14_15 synthetic alcohol 40.0 Triethanolamine salt of linear alkylbenzene sulfonic acid wherein the alkyl chain averages 12 carbons in length 19.8 Free triethanolamine 5.0 10 Ethanol 5.0 Potassium chloride 2.5 Minors (brighteners, color stabilizers, perfume, coloring agents) 0.9 Soil Release Polymer B * 0.9 Water Balance Weight ratio of nonionic surfactant to anionic surfactant (on an anionic free acid basis) 3~03 * From Table I
The foregoing composition is stable and provides excellent fabric cleaning when used either full strength as a pre-treatment or for through-the-wash detergency at a level of 1/4 cup/17 gallons of wash water.

: 31 ~.

~049367 EY~MPLE IV
Component % Wt.
Condensation product of average 7 moles of ethylene oxide with C~4_15 synthetic alcohol 33.0 Triethanolamine salt of linear alkylbenzéne sulfonic acid wherein the alkyl chain averages 12 carbons in length 19.8 Free triethanolamine 5.0 10 Ethanol 5.0 Potassium chloride 2.5 Minors (brighteners, color stabilizers, perfume, coloring agents) 0.9 Soil Release Polymer C * 1.2 Water Balance Weight ratio of nonionic surfactant to anionic surfactant (on an anionic free acid basis) 2.50 * From Table I
The foregoing composition is stable and provides excellent fabric cleaning when used either full strength as a pre-treatment or for through-the-wash detergency at a level of 1/4 cup/17 gallons of wash water.

EXAMPLE V
Component ~ wt.
Condensation product of average 9 moles of ethylene oxide with C14 15 synthetic alcohol 28.0 Triethanolamine salt of linear alkylbenzene sulfonic acid wherein the alkyl chain averages 12 carbons in length 19.2 Free triethanolamine 3.7 10 Ethanol 5.0 Potassium chloride 2.5 Minors (brighteners, color stabilizers, perfume, coloring agents) 0.9 Soil Release Polymer D * 10.0 Water Balance Weight ratio of nonionic surfactant to anionic surfactant (on an anionic free acid basis) 2.0 * From Table I
The foregoing composition is stable and provides excellent fabric cleaning when used either full strength : as a pre-treatment or for through-the-wash detergency at ~ a level of 1/4 cup/17 gallons of wash water.

~: 33 EXAMPLE VI
Component % Wt.
Condensation product of average 6 moles of ethylene oxide with C14 15 synthetic Triethanolamine salt of linear alkylbenzene sulfonic acid wherein the alkyl chain averages 12 carbons in length 16.5 Free triethanolamine 6.0 10 Ethanol 5.0 Potassium chloride 2.5 Minors (brighteners, color stabilizers, perfume, coloring agents) 0.9 Soil Release Polymer E * 2.0 Water Balance Weight ratio of nonionic surfactant to anionic surfactant (on an anionic free acid basis) 3.0 *From Table I
The foregoing composition is stable and provides excellent fabric cleaning when used either full strength as a pre-treatment or for through-the-wash detergency at a level of 1/4 cup/17 gallons of wash water.

~ . .

Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A liquid detergent composition containing a soil release polymer especially useful for aiding in the removal of oily stains and soils and for imparting soil release properties to fabrics, comprising:
(a) from about 15% to about 65% by weight of a water-soluble nonionic surfactant produced by the condensation of alkylene oxide with an organic hydrophobic compound;
(b) from about 10% to about 40% by weight of a water-soluble ethanolamine-neutralized anionic surfactant;
(c) at least 1% by weight of a free ethanolamine; and (d) from about 0.15% to about 25% by weight of a soil release polymer comprising ethylene terephthalate and poly-ethylene oxide terephthalate comprising from about 25% to about 50% by total weight ethylene terephthalate units, the polyethylene oxide in the polyethylene oxide tere-phthalate having a molecular weight of from about 300 to about 10,000, the total molecular weight of said polymer being in the range from about 5,000 to about 200,000.

2. A composition according to Claim 1 wherein the nonionic surfactant has an HLB in the range of from about 8 to about 15.

3. A composition according to Claim 1 wherein the nonionic surfactant comprises the condensation product of ethylene oxide with an aliphatic alcohol.

4. A composition according to Claim 1 wherein the ethanolamine-neutralized anionic surfactant is triethanol-amine-neutralized.

5. A composition according to Claim 1 wherein the free ethanolamine is triethanolamine.

6. A composition according to Claim 1 wherein the molecular weight of the polyethylene oxide in the soil release polymer is from about 400 to about 4000.

7. A composition according to Claim 6 wherein the total molecular weight oE the soil release polymer is from about 25,000 to about 70,000.

8. A composition according to Claim 1, comprising:
(a) from about 25% to ahout 40% by weight of a nonionic surfactant which is the condensation product of from about 5 moles to about 10 moles of ethylene oxide with a C14 to C16 alcohol;
(b) a water-soluble ethanolamine-neutralized anionic surfactant, the weight ratio of nonionic surfactant:
anionic surfactant being within the range of from about 1.8:1 to about 3.5:1;
(c) at least 1% by weight of free ethanolamine; and (d) from about 0.15% to about 25% by weight of a soil release polymer comprising ethylene terephthalate and polyethylene oxide terephthalate comprising from about 25%
to about 50% by total weight ethylene terephthalate units, the polyethylene oxide in the polyethylene oxide tere-phthalate having a molecular weight of from about 300 to about 10,000, the total molecular weight of said polymer being in the range from about 5,000 to about 200,000.

9. A composition according to Claim 8 wherein the ethanolamine-neutralized anionic surfactant is a triethanolamine-neutralized anionic surfactant.

10. A composition according to Claim 8 wherein the free ethanolamine is triethanolamine.

11. A composition according to Claim 1, comprising:
(a) from about 30% to about 60% by weight of a nonionic surfactant;
(b) an anionic surfactant mixture consisting essentially of:
(i) an ethanolamine-neutralized alkyl benzene sulfonate having from about 9 to about 15 carbon atoms in the alkyl group;
(ii) an ethanolamine-neutralzied soap containing from about 8 to about 24 carbon atoms in the fatty acid moiety, at a weight ratio of the acid form of the sulfonate to the acid form of the soap of from about 20-1 to about 1:1, the weight ratio of nonionic surfactant to anionic surfactant mixture being from about 2.5:1 to about 3.5:1;
(c) at least 1% by weight of a free ethanolamine;
(d) from about 0.15% to about 25% by weight of a soil release polymer comprising ethylene terephthalate and polyethylene oxide terephthalate comprising from about 25%
to about 50% by total weight ethylene terephthalate units, the polyethylene oxide in the polyethylene oxide tere-phthalate having a molecular weight of from about 300 to about 10,000, the total molecular weight of said polymer being in the range from about 5,000 to about 200,000.