CA1315635C - Stable liquid detergent compositions - Google Patents

Abstract

ABSTRACT
Heavy-duty liquid detergents containing sulfonate surfactant, ethoxylated nonionic surfactant, alkyl or alkenyl succinate and citrate builders, a neutralization system comprising potassium and sodium ions and, preferably, a low level of alkanolamine, and a solvent system comprising propylene glycol and water. The compositions are isotropic liquids providing a high level of detergency performance and good chlorine bleach compatibility. Preferred compositions also contain an alkyl amine-anionic surfactant ion pair complex as a fabric care agent, and are in the form of a stable homogeneous suspension.

Description

-~5qc) - ` 1315635 Ronald L. Jacobsen Robert Mermelstein Gregory S. Caravajal Technical Field The present invention relates to heavy-duty liquid detergent compositions containing sulfonate surfactant, ethoxylated nonionic surfactant, alkyl or alkenyl suc-cinate and citrate builders, a neutralization system comprising potassium and sodium ions and, preferably, a lO low level of alkanolamine, and a solvent system com-prising propylene glycol and water. The compositions are stable isotropic liquids providing a high level of detergency performance and good chlorine bleach com-patibility. The compositions preferably also contain an 15 alkyl amine anionic surfactant ion-pair complex which imparts fabric care (i~e., softening andtor static control) benefits through-the-wash without significantly impairing cleaning performance. Such compositions preferably are in the form of stable homogeneous 20 suspensions.
Background of the Invention There has been con~iderable demand for liquid detergents capable of providing superior cleaning under a wide variety of laundering conditions. Such composi 25 tions generally require a number of ingredients which tend to separate into discrete phases. Yet, isotropic liquid detergents are desired for both consistency of performance and aesthetic reasons. The compositions ` should be isotropic as made, e.g., at about 68F (20C), 30 and preferably remain isotropic during shipping and storage, where temperatures ranging from 90F (32.2C) or higher to 55F ll2.3C) or lower are often encount-ered. They should also be formulated to recover, after freezing and thawing, to an isotropic phase prior to 35 consumer use.

' ~ :
, ~ ~ . ' ' .

Liquid detergents often contain high levels of alkanolamines to enhance performance and product sta-bility. However, alkanolamines readily react with and destroy chlorine bleaches. Consumers who add chlorine 5 bleaches to wash solutions containing alkanolamine-based detergents consequently do not obtain optimum bleaching performance.
Heavy-duty liquid detergent compositions that are isotropic liquids providing a high level of detergency 10 performance and improved chlorine bleach compatibility are disclosed in U.S. Patent 4~507,219, Hughes, issued March 26, 1985. ~he compositions contain sulfonate and alcohol ethoxylate sulfate anionic surfactants, ethoxylated nonionic surfactant, optional quaternaxy 15 ammonium, amine or amine oxide surfactants, saturated fatty acid, polycarboxylate builder, a neutralization system comprising sodium, potassium and, preferably, low levels of alkanolamines, and a solvent system comprising ethanol, polyol and water.
Numerous attempts have also been made to formulate laundry detergent compositions which simultaneously provide good cleaning and fabric care performance.
Attempts have been made to incorporate cationic fabric softeners in anionic surfactant-based detergent 25 compositions employing various means of overcoming the natural antagonism between the anionic and cationic surfactants. For instance, U.S. Patent 3,936,537, Baskerville et al., issued February 3, 1976, discloses detergent compositions comprising organic surfactant, 30 builders, and, in particulate form~ a quaternary ammonium softener combined with a poorly water-soluble dispersion inhibitor which inhibits premature dispersion of the cationic in the wash liquor. Even in these compositions, some compromise between cleaning and 35 softening effectiveness has to be accepted.

1 31 563r~

Other laundry detergent compositions have employed tertiary amines along with anionic surfactants to act as fabric softeners. sritish Patent 1,514,276, Kengon, published June 14, 1978, employs certain tertiary amines 5 with two long chain alkyl or alkenyl groups and one short chain alkyl group. The amines are useful as fabric softeners in detergent compositions when their isoelectric point is such that they are present as a dispersion of negatively charged droplets in the 10 normally alkaline wash liquor, and are present in a more cationic form at the lower pH of a rinse liquor, and so become substantive to fabrics. The use of such amines, among others, in detergent compositions has also been previously disclosed in British Patent 1,286,054, 15 assigned to Colgàte-Palmolive, published August 16, 1972, British Patent 1,514,276, assigned to Unilever, published June-14, 1978, and in U.S. Patent 4,375,416, Crisp et all, issued March 1, 1983.
Another approach to pro~ide anionic detergent 20 compositions with fabric softening ability has been the use of smectite-type clays, as described in U.S. Patent 4,062,S47, Storm et al., issued December 13, 1977.
These compositions, although they clean welll require large contents of clay for effective softening. The use 25 of clay together with a water-insoluble cationic compound in an electrically conductive metal salt as a softening composition adapted for use with anionic, nonionic, zwitterionic and amphoteric surfactants has been described in British Patent 1,483,627, assigned to 30 Procter & Gamble, published August 24, 1977.
British Patent Applications 1,077,103 and 1,077,104, assigned to Bayer, published July 26, 1967, disclose amine-anionic surfactant ion~pair complexes useful as antistatic agents. The complexes are applied 35 directly to the fabric from an aqueous carrier. There is no suggestion in either of these references that such ' ~ .

.

complexes could be added to detergent composition to impart fabric care benefits through-the-wash. In fact, such complexes could not be deliJered through-the-wash.
Fatty acid-amine ion-pair complexes in granular 5 detergents are disclosed in European Patent Application 0,133,804, Burckett-St.Laurent et al., published June 3, 1985. While these compositions delivex fabric conditioning, the alkyl amine-anionic surfactant complexes of the present invention deliver superior lO antistatic performance.
It is therefore an object of the present invention to provide a heavy-duty liquid detergent composition in a stable isotropic form which exhibits good cleaning performance and bleach compatibility.
It is another object of the present invention to provide a heavy-duty liquid detergent composition in the form of a stable homogeneous suspension comprising the above composition and an alkyl amine-surfactant ion-pair complex which delivers through-the-wash fabric care 20 benefits without significantly impairing cleaning performance.

Summary of the I~vention The present invention encompasses a heavy-duty 25 liquid detergent composition comprising, by weight:
(a) from about 10% to about 30~, on an acid basis, of a sulfonate surfactant containing a C10-Cl6 alkyl or alkenyl group;
(b) from about 1% to about 15~ of an ethoxylated 30 nonionic surfactant of the formula R (OC2H4)nOH, wherein R1 is a ClO-Cl6 alkyl group or a C8-C12 alkyl phenyl groupt n averages from about 3 to about 9, and said nonionic surfactant has an HLB of from about 10 to about 13;

(c) from about 7~ to about 20~, on an acid basis, of a C12-C14 alkyl or alkenyl succinate ~uilder material;
(d) from about 1% to about 7~, on an acid basis, of a citrate builder material;
(e) from about 0 to about 0.04 moles per 100 gxams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine and triethanolamine;
(f) potassium and sodium ions in a molar ratio o potassium to sodium of from about 1.4 to about 5.0;
Ig) from about 5~ to about 20~ of propylene glycol; and (h) from about 15~ to about 45% water;
15 said composition containing from about 15% to about 40%
of (a) and (b); from about 10~ to about 25% of (c~ and ~d); from about 30% to about 55% of (a), (b), (c) and (d); and from about 30~ to about 55% (g) and (h); the weight ratio of (a) to (b) being from about 1 to about 20 10; and all of said components being selected to provide an isotropic liquid at 20C having an initial pH of from about 6.0 to about 10.0 at a concentration of about 10 by weight in water at 20C.
Preferred compositions further comprise an alkyl 25 amine-anionic surfactant ion-pair complex that provides fabric care benefits, and optional detergent ingredients, and are in the form of a stable homogeneous suspension.
Detailed Description of the Inventio_ The liquid detergents of the present invention contain sulfonate anionic surfactant, ethoxylated nonionic surfactant, alkyl or alkenyl succinate and citrate builders, a neutralization system comprising potassium and sodium ions and, preferably, a low level 35 of alkanolamine, and a solvent system comprising propylene glycol and water.

: ~
.
. : ' . ~ :

The compositions herein are formulated to provide a high level of detergency performance under a wide vari-ety of laundering conditions. They also provide good chlorine bleach compatibility due to the limited amount 5 of alkanolamine. Since the compositions con~ain a relatively high level of active components and little or no alkanolamine to enhance product stability, the types, lev~els and ratios of the components must be carefully balanced to provide isotropic liquids as made, and 10 preferably at storage temperatures as high as 90F
(32.2C) and as low as 55F (12.8C). They preferably also recover, after freezing and thawing, to an isotropic form by 55F (12.8C), more preferably by 50F
(10C).
~15 In order to meet these stability constraints, the present compositions require a neutralization system comprising potassium and sodium ions in a specified molar ratio. Greater sodium neutralization than required results in gelling of the product during the 20 addition of the succinate builder material, whereas greater potassium neutralization results in an unacceptably hazy product. The total level of organic and inorganic bases must also be selected to provide a sufficiently high product pH to obtain a wash pH desired ~5 for detergency performance, without the pH being so high that pH sensitive stain removal and enzyme stability are compromised.
The compositions also require a solvent system comprising propylene glycol and water, in an amount 30 sufficient to prevent organic phase separation (i.e., keep poorly-soluble surfactants in solution).
Sulfonate Surfactant The detergent compositions herein contain from about 10% to about 30%, preferably from about 15% to 35 about 25%, by weigh~ (on an acid basis) of a water soluble anionic sulfonate surfactant containing a ....,.. .. .. ., ...

.
, Clo~C16 alkyl or alkenyl group. Anionic sulfonate surfactants useful herein are d1sclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,91~,678, Laughlin et alt issued December 30, 1975 Preferred sulfonate surfactants are the water-soluble salts, particularly thP alkali metal, and alka-nolammonium (e.~., monoethanolammonium or triethanolam-monium) salts of alkylbenzene sulfonates in which the 10 alkyl group contains from about 10 to about 15 carbon atoms, in straight chain or branched chain configura-tion, e.g., those of the type described in U. S. Patents 2,220,0g9 and 2,477,383 Especially valuable are linear straigh~ chain 15 alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to about 13.
Also useful herein are the water-soluble salts of paraffin sulfonates, olefin sulfonates, alkyl glycéryl 20 ether sulfonates, esters of ~-sulfonated fatty acids containing from about 1 to 10 carbon atoms in the ester group, 2-acyloxy-alkane-lAsulfonates containing from about 2 to 9 carbon atoms in the acyl group, and ~-alkyloxy alkane sulfonates containing fxom about 1 to 25 3 carbon atoms in the alkyl group.
Mixtures of the above-described sulfonates, partic-ularly with the Cll_l3 linear alkylbenzene sulfonates, can also be used.
~thoxylated Nonionic Surfactant The compositions also contain from about 1% to about 15%, preferably from about 5% to about 12~, by weight of an ethoxylated nonionic surfactant of the formula R (OC2H4)nOH, wherein R is a C10-Cl6 alkyl group or a C8-C12 alkyl phenyl group, n averages from 35 about 3 to about 9, and said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about 10 to ~ r - - ' , , ,:

about 13. These surfactants are more fully described in U.S. Patents 4,285,~41, Barrat et al, issued August 25, 1981, and 4,284,532, Leikhim et al, issued August 18, 5 1981. Particularly preferred are condensation products of cl2-C14 alcohols with from about 3 to about 7 moles of ethylene oxide per mole of alcohol, e.g., c12-c13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
Succinate Builder The detergent compositions herein also contain from about 7% to about 20%, preferably from about 10% to about 15%, by weight on an acid basis, of a succinate builder of the general formula R-CH(COOH)CH2(COOH), 15 wherein R is C12-C14 alkyl or alkenyl group.
These succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts (eOg., mono-, di-, or tri-ethanolammonium~.
Specific examples of succinate builders include:
lauryl succinate, myrlstyl succinate, 2-dodecenyl succinate (preferred) and 2-tetradecenyl succinate.
Citrate Builder The compositions further contain from about 1% to 25 about 7%, preferably from about 2% to about 5.5%, by weight on an acid basis, of a citrate tpreferably in the form of an alkali metal or alkanolammonium salt) builder material. This material is generally added to the compositions herein as citric acid, but can be added in 30 the form of a fully neutralized salt.
Neutralization System The present compositions can contain from about 0 to about 0.04 moles, preferably from about 0.01 to about 0.035 moles, more preferably from about 0.015 to about 35 0.03 moles, per 100 grams of composition of an alkanol-amine selected from the group consisting of - .

1 3 1 56~5 g monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof. L~w levels of the alkanolamines, particularly monoethanolamine, are preferred to enhance product stability and detergency performance. However, the amount of alkanolamine should be minimized for best chlorine bleach compatibility.
In addition, the compositions contain potassium and sodium ions, in a molar ratio of potassium to sodium of from about 1.4 to about 5.0, preferably from about 1.5 10 to about 2.5, and at a level sufficient to neutralize the anionic species and provide the desired product pH.
Solvent System The solvent system fox the compositions is com-prised of propylene glycol and water.
The propylene glycol ~1,2-propane diol is particu-larly preferred) represents from about 5~ to about 20%, preferably from about 8% to about 18%, by weight of the composition.
The compositions also contain from about 15% to 20 about 45~, preferably from about 20% to about 40%, by weight of water.
In addition, the propylene glycol and water represent from about 30% to about 55~, preferably about 35% to about 50~, by weight of the composition.
The compositions of the present invention are further constrained by the following limits, in which all percentages and ratios are calculated on an acid basis where anionic materials are involved. The sulfon-ate and ethoxylated nonionic surfactantsj together, 30 represent from about lS% to about 40%, preferably from r about 20% to about 35%, by weight of the composition.
The weight ratio of the sulfonate surfactant to the ethoxylated nonionic surfactant should also be from about 1 to about 10, preferably from about 1.5 to about 35 5.

- ' ' - ,' , .

-- ~o --The succinate and citrate builders together represent from about 10~ to about 25%, preferably from about 13g to about 20%, by weight of the composition.
In addi~ion, the above builders and surfactants represent a total of from about 30% to about 55%, preferably from about 40% to about 50%, by weight of the composition.
Finally, all of the above components are selected to provide an isotropic liquid detergent at 68F ~20DC), 10 and preferably at 90F (32.2C) and at 55F (12.8C).
The components are also selected to provide an initial pH of from about 6.0 to about 10.0, preferably from about 7.0 to about 9.0, at a concentration of 10% by weight in water at 68F (20C).
Optional Components The liquid detergents herein can contain other surfactants and builders, and other components known for use in detergent compositions, including enzymes, enzyme stabilizing agents, polyacids, soil removal agents, 20 antiredeposition agents, suds regulants, hydrotropes, opacifiers, antioxidants, bactericides, dyes~ perfumes, and brighteners, such as Athose described in the U.S.
Patent 4,285,841, Barrat et al, issued August 25, 1981!
and in U.S. Patent 4,507,219, Hughes, issued March 26, 25 1985 Such optional components generally represent less than about 15%, preferably from about 2~ to about 10%, by weight of the composition.
Particularly preferred compositions herein contain 30 rom about 0.1% to about 10~, preferably from about 0.5%
to about 8~, more preferably from about 1% to about 6%, by weight of relatively water-insoluble particles comprising an alkyl amine-anionic surfactant ion-pair complex as a fabric care agent.
The complex can be represented by the following formula:
.~

1 3 1 563~

5 wherein R1 and R2 can independently be C16 to C20 alkyl or alkenyl groups. Preferred amines used to form these complexes are water-insoluble and include hydrogenated or unhydrogenated ditallow amine. A represents an anionic surfactant selected from the group consisting of 10 alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates, and paraffin sulfonates. Preferred anionic surfactants are C1 to C20 linear alkylbenzene sulfonates and Cl2 to Cl~ paraffin sulfonates. Mixtuxes of these ion pairs can also be used.
lS It has been found that in order for these ion-pair complex particles to impart their fabric care benefits they must have an average particle diameter of from about 10 to about 300 microns, preferably from about 10 to about 250 microns, more preferably from about 10 to 20 about 200 microns, and most preferably from about 10 microns to ahout 150 microns. The term "average particle diametern represents the mean particle size diameter of the actual particles of a given material.
The mean is calculated on a weight percent basis. The 25 mean is determined by conventional analytical techniques such as, for example, laser light diffraction or microscopic determination utilizing a scanning electron microscope. Preferably, greater than 50% by weight, more preferably greater than 60% by weight, and most 30 preferably greater than 70~ by weight, of the particles have actual dimaters which fall within the range of from about lO to about 300 microns, preferably from about 10 to about 250 microns, more preferably from about 10 to about 200 microns, and most preferably from about 10 35 microns to about 150 microns.
Starting alkyl amines are of the formula:

.~ . . ' `
,: - .

Rl~
/ N ~ H
R~

5 wherein Rl and R2 are Cl6 to C20 y groups, preferably Cl6 to C18 alkyl or alkenyl, and most preferably C16 to C1~ alkyl. Suitable non-limiting examples of starting amines include hydrogenated di~allow amine, unhydrogenated ditallow amine, 10 dipalmityl amine, distearyl amine, diarachidyl amine, palmityl stearyl amine, palmityl arachidyl amine and stearyl arachidyl amineO Most preferred are the hydrogenated and unhydrogenated forms of ditallow amine.
The anionic surfactants ~A) useful in the ion-pair 15 complex of present invention are the Cl to C20 alkyl sulfonates, aryl sulfonates, C1 to C20 alkylaryl sulfonates and C12 to C1~ paraffin sulfonates. These classes of anionic surfactants have been fully described above.
Particularly preferred are the linear Cl to C20 alkylaryl sulfonates and more particularly preferred are the linear C~-C13 alkylbenzene sulfonates. Most preferred are the linear C6 to C13 alkyl benzene sulfonates.
Non-limiting examples of ion-pair complexes suitabl~ for use in the present invention include:
ditallow amine Ihydrogenated or unhydrogenated) complexed with a linear C1 C20 alkyl benzene sulfonate ~LAS), 30 dipalmityl amine complexed with a C1-C20 LAS, distearyl amine complexed with a C1-C20 LAS, diarachidyl amin4 complexed with a C~-C20 LAS, palmityl stearyl amine complexed with a C1 C20 LAS, parlmityl arachidyl amine complexed with a ~l-C20 LAS, 35 stearyl arachidyl amine complexed with a Cl-C20 LAS, - ~:

.
' . ~ ' ' . , :

ditallow amine (hydrogenated or unhydrogenated) complexed with a Cl-C20 alkyl sulfonate (AS), dipalmityl amine complexed with a C1-C20 AS, distearyl amine complexed with a Cl-C20 AS, 5 diarachidyl amine complexed with a Cl-C20 AS~
palmityl stearyl amine complexed with a C1-C20 AS, palmityl arachidyl amine complexed with a Cl-C20 AS, stearyl arachidyl amine complexed with a Cl-C20 AS, ditallow amine (hydrogenated or unhydrogenated) 10 complexed with a C12 C1~ paraffin sulfonate (PS), dipalmityl amine complexed with a C12-C18 PS, distearyl amine complexed with a C12-C18 P5, diarachidyl amine complexed with a C12-C18 PS, palmityl stearyl amine complexed with a C12-C18 PS, 15 palmityl arachidyl amine complexed with a C12-C18 PS, stearyl ara~hidyl amine complexed with a C12-C18 PS, and mixtures of these ion-pair complexes.
More preferred are complexes formed from the combination of ditallow amine (hydrogenated or 20 unhydrogenated) complexed with Cl-C20 LAS, C1-C20 AS~ or C12-C18 PS. Even more preferred are those complexes formed from ditallow amine ~hydrogenated or unhydrogenated) ccmplexed with a C1-C20 LAS. Most preferred are complexes formed from ditallow amine 25 (hydrogenated or unhydrogenated) complexed with C6-C13 LAS.
The amine-surfactant complexes herein are prepared separately from the balance of the composition, and are preferably then added to the detergent ingredients in 30 such a way as to insure that the complexes are homogeneously dispersed therein. The amine and surfactant components are combined in a molar ratio of alkyl amine to surfactant ranging from about 1:10 to about 10:1, preferably from about 1:1 to about 9:1.
35 This can be accomplished by any of a variety of means, including but not limited to, preparing a melt of the ~ .
~, . . . . . . .

~' 1 31 563C) anionic surfactant and the amine and then dispersing the molten complex into the balance of the detersive ingredients, with constant agitation.
Alternatively, the above molten complex can be 5 allowed to cool, preferably while stirring the molten mixture.
Other methods of forming ~he ion-pair complex include dissolving the components in an organic solvent, or by heating the amine to a liquid state and then 10 adding this molten amine component to a heated acidified aqueous solution of the anionic surfactant, and then extracting the ion-pair complex by using a solvent, such as chloroform.
The complexing of the amine and the anionic 15 surfactant res-ults in an entity (ion-pair) which is chemically distinct from either of the two starting materials.
The desired particle sizes can be achieved by, for example, mechanically grinding the resulting ion-pair 20 complex in blenders (e.g., an OsterR blender) or in large scale mills (e.g~, a Wiley R Mill) to the desired particle size range.
Such factors as the type of amine employed and the ratio of the amine-surfactant components can affect the 25 physical properties of the resulting complex. Complexes which are gelatinous at room temperature can be mechanically ground to achieve the desired particle size after flash freezing by using, for example, liquid nitrogen.
The complexes are further characterized by their melting points, which generally lie in the range of from about 10C to about 75C. A particularly preferred complex, which comprises a hydrogenated ditallow amine complexed with a linear C6 to C13 alkyl benzene 35 sulfonate surfactant in a 1:1 molar ratio has a melting point of a~OUt 20C.

i,. ..

' 131563';

It has been found that these fabric care agents, unlike those of the prior art, can be incorporated into the detergent compositions of the present invention with little, if any, detrimental effect on cleaning. These detergent compositions provide fabric care benefits across a variety of laundering conditions, that is, machine or hand washing and machine drying, and also machine or hand washing and line drying. Additionally~
these same fabric care agents can be used with a variety 10 of surfactant systems.
Preferaby, the compositions of the present invention contain a stabilizing agent to maintain the fabric care agent uniformly dispersed in the liquid detergent. Otherwise, density differences between the 15 insoluble particles and the liquid base detergent can cause eventual particle settling or creaming.
The choice of the stabilizing agent for the present compositions depends upon factors such as the type and level of solvent ingredients in the composition.
Suitable suspending agents include various clay materials, such as montmorillonite clay, quaternized montmorillonite clays ~e.g. Bentone 14, available from NL Industries), polysaccharide gums (e.g. xanthan gum available from Kelco Division of Merck & CoO, Inc.), any 25 of several long-chain acyl derivative materials or mixtures of such materials, diethanolamide of a long-chain fatty acid (e.g., PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide (such as Pluronic F88 offered by BASF Wyandotte), sodium 30 chloride, ammonium xylene ~ulfonate, sodium sulfate, and polyvinyl alcohol. Other suspending agents found useful are alkanol amides of fatty acids, having from about 16 to about 22 carbon atoms, preferably from abou~ 16 to about 18 carbon atoms. Preferred alkanol amides are 35 stearic monoethanolamide, stearic diethanolamide, -i stearic monoisopropanolamide and stearic ~., 1 3 1 5~3S

monoethanolamide stearate. Other long-chain acyl derivatives i~cl~de long-chain esters of long-chain alkanol amides ~e.g., stearamide DEA distearate, stearamide MEA stearate).
s The most preferred suspending agent for use in the present invention is the quaternized montmorillonite clay.
This suspending agent is preferably present at a level of from about 0.1% to about 10.0~, preferably from 10 about 0.5% to about 1.5~, by weight of the detergent composition.
The compositions herein can also contain polymeric soil release agents, including cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric 15 blocks of ethylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate, and cationic guar gums, and the like.
The cellulosic derivatives that are functional as soil release agents are commercially available and 20 include hydroxyethers of cellulose such as MethocelR
(Dow) and cationic cellulose ether derivatives such as Polymer JR-124R, JR-400R, and JR-30MR (Union Carbide).
See also U.S. Patent 3,928,213 to Temple et al.l issued December 23, 1975.
Other effective soil release agents are cationic guar gums such as Jaguar PlauR (Stein Hall) and Gendrive 458 (General Mills).
Preferred cellulosic soil release agents for use herein are selected from the group consisting of methyl 30 cellulose; hydroxypropyl methylcellulose; hydroxybutyl methylcellulose; or a mixture thereof, said cellulosic polymer having a viscosity in aqueous solution at 20C
of 15 to 75,000 centipoise.
A more preferred soil release agent is a copolymer 35 having random blocks of ethylene terephthalate and r~ polyethylene oxide (PEO) terephthalate. More -` 1 31 5635 specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ration of ethylene terephthalate units ~o PEO
terephthalate units of from about 25:75 to about 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued lO May 25, 1976, which is incorporated by reference. See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 which discloses similar copolymers. Surprisingly, it has been found that these pol~meric soil release agents balance the distribution 15 of the fabric care agent of the present invention against a broad range of synthetic fabrics such as polyesters, nylons, polycottons and acrylics. This more uniform distribution of the fabric care agent can result in improved fabric care qualities. .
Another preferred polymeric soil release agent is a crystalizable polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived 25 from a polyoxyethylene glycol of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthala~e units in the crystalliæable polymeric compound is between 2:1 and 6:1. Examples of this polymer include 30 and commercially available material ZelconR 5126 (from Dupont) and Milease (from ICIj.
Particularly preferred polymers herein and methods of their preparation are more fully described in European Patent ~pplication 185,417, Gosselink, 35 published June 25, 1986 .
. .
~ ' 1 3 1 5~3~

If utilized, these soil release agents will generally comprise from about 0.05% to about 5.0~ by weight of the detergent compositions herein, more preferably from about 0.2% to about 3.0% by weight of such compositions.
While the above compositions con~aining the ion-pair complex can contain other detergent surfactants, they preferably contain less than about 5%, preferably less than about 3~, most preferably less than lO about 1%, by weight of anionic sulfate and ethoxy sulfate surfactants, for example, those of the formula RO~C2H4O~mSO3M, where R is a C10-Cl6 alkyl or hydroxyalkyl group, m is 0 or averayes up to about 4, and M is a compatible cation. Most preferably, the 15 compositions are substantially free of such sulfate surfactants, which inhi~it deposition of the above fabric care active.
The compositions herein can contain up to about 2~
by weight of ethanol as an additional solubilizing 20 agent. However, the compositions do not require ethanol for phase stability, and preferably contain little or no ethanol (e.g., less than about 1% by weight) for compatibility with the above fabric care active, which can be solubilized by ethanol. They preferably are 25 substantially free of ethanol.
The following examples illustrate the compositions of the present invention.
All parts, percentages and ratios used herein are by weight unless otherwise specified.
EXAMPLE I
The following composition is prepared by adding the components to a mixing tank in the order listed with continuous mixing.

1 31 5G3~) Wt.% in % Actual Wt. Wt.~ Finished Components Assayl Added (lb) Added Product Water100.00 115.83 5.26 24.11 1,2~Propanediol100.00 318.78 14.49 14.49 Sodium hydroxide50.00 106.48 4.84 2.42 Potassium hydroxide 45.00 262.4611.93 5.802 C12_13 alcohol poly- 2 ethoxylate (6.5)* 100.00 147.40 6.70 8.70 10 Sodium diethylene-triamine penta-acetate41.00 15.56 0.71 0.29 C12 alkenyl succinic anhydride100.00 246.62 11.21 11.21 15 Calcium formate10.00 22.00 1.00 0.10 Sodium formate30.00 36.67 1.67 0.50 C11 4 linear aikyl~
benzene sulfonic acid 96.00 3g4.17 17.92 17.20 20 Citric acid50.00 153.12 6.96 3.48 Monoethanolamine100.00 20.46 0 93 1.932 Brightener3.90,114.47 5.20 0.20 TEPA 15-18 80.0039.88 1.81 1.45 (Base prQduct 25total) (1993~88) (90.63) Potassium hydroxide45.0021.10 0.96 (Total molar K :Na ) (1.7) Soil release 30polymer*** 100.0021.34 0.97 0.97 Protease enzyme - 12.76 0.58 (2.5 AU/g) Amylase enzyme - 6.60 0.30 (155 AMU/m~) 35 Bentone 14 clay100.0015.84 0.72 0.72 DTA/LAS complex 100.00 116.82 5.31 5.31 1 31 563'~

Dye 1.00 6060 0.30 0.01 Perfume 100.00 5.06 0.23 0.23 (Finished product total~ (2~00.00) (100.00~

lBalance to 100% is water unless otherwise noted.
From more than one source.
3Balance also includes 19.23~ monoethanolamine and 38-46% C12-13 alcohol polyethoxylate (6.5)*.
*Alcohol and monoethoxylated alcohol removed.
**T~traethylene pentaimine ethoxylated with 15-18 moles (avg.) of ethylene oxide at each hydrogen site on each nitrogen.
***Poly(terephthalate propyleneglycol ester~
ethoxylated with about 30 moles of ethylene oxide.
The composition has a pH of about 14 and a temperature of about 37.8C when the C12 alkenyl succinic anhydride is added. (The anhydride is used because it is easier to handle and provides lighter colored product than the corresponding acid.) The 20 temperature is allowed to rise up to about 71.1C with moderate agitation. The high temperature, high pH and substantial water availability are designed to drive ths hydrolysis and neutralization of the anhydride to completion. This is accomplished prior--to the addition 25 of the monoethanolamine to avoid reaction between the monoethanolamine and the anhydride and the formation of the corresponding amide, which is not effective as a builder. The composition is then cooled to about 26.7C
by the time the Bentone 14 clay is added.
The DTA/LAS ion-pair complex is made by mixing hydrogenated ditallow amine (available from Sherex Chemical Corp., Dublin, OH as Adogen R240, which has been topped to reduce the monotallow amine content from about 5~ to less than about 1~ by weight, e.g., 0.9~, to 35 improve particle integrity and physical stability~ with Cl1 4 linear alkylbenzene sulfonic acid, in a weight '' :

-" 1 31 5635 ratio of 90:10DTA:LAS, at 71.1-76.7C to form a smooth syrupy liquid. The complex, at a temperature of 65.6-76.7C, is slowly added ~o the 26.7C composition under high shear mixing conditions. This causes the 5 complex to disperse into fine droplets that fxeeze as particles having an average size of about 40-50 microns, and a median size of about 20 microns, as measured using a Malvern 2600 particle size analyzer. Moreover, about 69~ of the particles have a size between 9 and 160 10 microns.
The base product is a stable isotropic liquid at 20C and has an initial pH of about 8.2 at a concentration of 10~ by weight in water at 20C. The finished product is a stable homogeneous dispersion at 15 20C and has an initial pH of about ~.6 at a concentration of 10~ by weight in water at 20C.
Other compositions of the present invention are obtained when the above molar ratio of potassium to sodium is adjusted to about 2.85; when the levels of C12 20 alkenyl succinic anhydride and citric acid are adjusted to 14% and 2%, respectively; and when the levels of C12 13 alchol polyethoxylate and 1,2-propanediol are adjusted to 5% and 18.5%, respectively.
Other compositions of the present invention are 25 obtained when the above DTAtLAS ion-pair complex is replaced, in whole or in part, with an equivalent amount of ditallow amine (hydrogenated or unhydrogenated) complexed with C6, C8, C10 or C13 linear alkylbenzene sulfonic acid.

B

.

Claims (20)

1. A heavy-duty liquid detergent composition com-prising, by weight:
(a) from about 10% to about 30%, on an acid basis, of a sulfonate surfactant containing a C10-C16 alkyl or alkenyl group;
(b) from about 1% to about 15% of an ethoxylated nonionic surfactant of the formula R1(OC2H4)nOH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, n averages from about 3 to about 9, and said nonionic surfactant has an HLB of from about 10 to about 13;
(c) from about 7% to about 20%, on an acid basis, of a C12-C14 alkyl or alkenyl succinate builder material, (d) from about 1% to about 7%, on an acid basis, of a citrate builder material, (e) from about 0 to about 0.04 moles per 100 grams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine and triethanolamine;
(f) potassium and sodium ions in a molar ratio of potassium to sodium of from about 1.4 to about 5.0;
(g) from about 5% to about 20% of propylene glycol, and (h) from about 15% to about 45% water;
said composition containing from about 15% to about 40%
of (a) and (b); from about 10% to about 25% of (c) and (d); from about 30% to about 55% of (a), (b), (c) and (d); and from about 30% to about 55% of (g) and (h); the weight ratio of (a) to (b) being from about 1 to about 10; and all of said components being selected to provide an isotropic liquid at (2G°C) having an initial pH of from about 6.0 to about 10.0 at a concentration of 10%
by weight in water at 20°C.

2. The composition of Claim 1 wherein the sulfonate surfactant is a C11-C13 linear alkylbenzene sulfonate, and in the ethoxylated nonionic surfactant, R is a C12-C14 alkyl group and n averages from about 3 to about 7.

3. The composition of Claim 2 comprising from about 15% to about 25%, on an acid basis, of the sulfonate surfactant, and from about 5% to about 12% of the ethoxylated nonionic surfactant.

4. The composition of Claim 3 comprising from about 10% to about 15%, on an acid basis, of the sùccinate builder, and from about 2% to about 5.5%, on an acid basis, of the citrate builder.

5. The composition of Claim 4 wherein the molar ratio of potassium to sodium is from about 1.5 to about 2.5.

6. The composition of Claim 5 comprising from about 8%
to about 18% of 1,2-propanediol.

7. The composition of Claim 6 having a pH of from about 7 to about 9.0 at a concentration of 10% by weight in water at 20°C.

8. The composition of Claim 1 wherein the succinate builder material is added to the composition in its anhydride form.

9. The composition of Claim 8 wherein the anhydride is substantially hydrolyzed and neutralized prior to the addition of the alkanolamine.

10. The composition of Claim 1 further comprising from about 0.1% to about 10% of water-insoluble particles having an average diameter of from about 10 to about 300 microns, said particles comprising an alkyl amine-anionic surfactant ion-pair complex having the formula:

A?

wherein R1 and R2 can independently be C16 to C20 alkyl or alkenyl groups, and A is an anionic surfactant selected from the group consisting of alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates and paraffin sulfonates, and mixtures of such ion-pair complexes.

11. The composition of Claim 10 wherein the particles have an average diameter of from about 10 to about 150 microns.

12. The composition of Claim 10 wherein the particles comprise an ion-pair complex of hydrogenated ditallow amine and C6-C13 linear alkylbenzene sulfonate.

13. The composition of Claim 10 further comprising from about 0.5% to about 1.5% of a quaternized montmorillonite clay.

14. The composition of Claim 10 being substantially free of alkyl sulfate and alkyl ethoxy sulfate surfactants of the formula RO(C2H4O)mSO3M, where R is a C10-C16 alkyl or hydroxyalkyl group, m is o or averages up to about 4, and M is a compatible cation.

15. The composition of Claim 10 being substantially free of ethanol.

16. The composition of Claim 9 further comprising from about 0. 5% to about 8% of water-insoluble particles having an average diameter of from about 10 to about 300 microns, said particles comprising an alkyl amine-anionic surfactant ion pair complex having the formula:

A-wherein R1 and R2 can independently be C16 to C20 alkyl or alkenyl groups, and A is an anionic surfactant selected from the group consisting of alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates and paraffin sulfonates, and mixtures of such ion-pair complexes.

17. The composition of Claim 16 wherein the particles have an average diameter of from about 10 to about 150 microns and comprise an ion-pair complex of hydrogenated ditallow amine and C6-C13 linear alkylbenzene sulfonate.

18. The composition of Claim 17 comprising an ion-pair complex of hydrogenated ditallow amine and C11.4 linear alkylbenzene sulfonate.

19. The composition of Claim 17 further comprising from about 0.5% to about 1.5% of a quarternized montmorillonite clay.

20. The composition of Claim 17 wherein the ditallow amine contains less than about 1% monotallow amine.