CA1323822C - Acetylated sugar ethers as bleach activators, detergency boosters and fabric softeners - Google Patents

Abstract

ACETYLATED SUGAR ETHERS AS BLEACH ACTIVATORS, DETERGENCY BOOSTERS AND FABRIC SOFTENERS

ABSTRACT OF THE DISCLOSURE
A heavy duty detergent composition having incorporated therein an acetylated sugar ether which provides bleach activation, detergency boosting and fabric softening properties to the detergent composition. The acetylated sugar ether contains at least two long chain alkyl groups. The acetylated sugar ether acts as a bleach activator by reacting with a bleaching agent, such as sodium perborate monohydrate, to generate peracetic acid. Following perhydrolysis, the compound acts as a detergency booster. The presence of a least two long chain alkyl groups induces absorption onto the fibers and a softening effect is obtained.

Description

13%3822 DETERGENCY BOOSTERS AND FABRIC SOFTENERS
BAC_GROUND_OF THE INVENTION
(1) Field of the Inventlon This lnvention relates to an improved heavy duty laundry detergent composition. More particularly, the invention is directed to a heavy duty detergent composition having incorporated therein an acetylated sugar ether which provides bleach activating, detergency boosting and fabric softening properties to the detergent composition. A preferred embodiment of the invention i8 directed to a non-aqueous liquid heavy duty laundry detergent composition having fabric softening properties as well as activated bleach and activated detergency.

(2) Description of the Prior Art The use of various sugar derlvatives in laundry detergent compositions is known.
It is well known in the art that certain alkyl glycosides, particularly long chain alkyl glycosides, are surface active and are u~eful as nonionic surfactants in detergent compositions. Lower alkyl glycosides are not as surface active as their long chain counterparts. Alkyl glycosides exhibiting the greatest surface activity have relatively long-chain alkyl groups. These alkyl groups generally contain about 8 to 25 carbon atoms and preferably about 10 to 14 carbon atoms.
Long chain alkyl glycosides are commonly prepared from saccharides and long chain alcohols. ~owever, unsubstituted saccharides such as glucose are insoluble in higher alcohols and thus do not react together easily. Therefore, it is common to ¦ first convert the saccharide to an intermediate, lower alkyl ¦ glycoside which is then reacted with the long chain alcohol.

~ 1323~22 Lower alkyl glycosides are commercially avallable and are l commonly prepared by reactlng a saccharide with a lower alcohol i in the presence of an acid catalyst. Butyl glycoside is often empIoyed as the intermediary, The use of long chain alkyl glycosides as a surfactant in detergent composltions and various methods of preparing alkyl 91ycogides i9 disclosed, for example, in U.S. Patents 2,974,134;

3,547,~28~ 3,598,865 and 3,721,633. The use of lower alkyl glycoside~ as a viscosity reducing agent in aqueous liquid and powdered detergents is disclosed in U.S. Patent 4,488,981.
Acetylated sugar esters, such aq, for example, glucose penta acetate, glucose tetra acetate and sucrose octa acetate, have been known for years as oxygen bleach activators. The use of acetylated sugar derivatives a~ bleach activators is disclosed in U.S. Patents 2,955,905~ 3,901,819 and 4,016,090.

SVMMARY OF THE INVENTION
In accordance with the present invention, a highly detersive heavy duty nonionic laundry detergent composition is prepared by the incorporation of an acetylated sugar ether into a nonionic detergent composition. The acetylated sugar ethers act as bleach activators, detergency boosters and fabric softeners. The acetylated sugar ethers may be incorporated into detergent compositions which may be formulated into liquid or powdered form. Both powdered aqueous and non-aqueous liquid formulations may advantageously be produced although far greater benefits are derived when used in a non-aqueous detergent composition.
There is no disclosure in the prior art of the use of sugar based surfactants, that i8, sugar esters and sugar ethers, ~ 1323822 as detergency boo9ters, of the use of sugar ethers as bleach stable detergency boosters or of the use of acetylated sugar ethers as detecgency boosters, bleach activators and fabric l softeners.
DETAILED DESCRIPTION OF THE INVENTION
Optimum grease/oil removal is achieved where the nonionic surfactant has an HL3 (hydrophilic-lipophilic balance) of from about 9 to about 13, particularly from about 10 to about 12, good detergency being related to the existence of rod-like micelles which exhibit a high oil uptake capacity. Optimal detergency for a given nonionic surfactant is obtained between the cloud point temperature, the temperature at which a phase rich in nonionic surfactant separates in the wash solution, ~CPT) and the phase inversion (coalescence) temperature (PIT). ~ithin this narrow temperature range or window there exists a water rich microemulsion domain containing a high oil/surfactant ratio.
This window varies from one nonionic detergent to another. It is about 30C (37-65C) for a C-13 secondary fatty alcohol ethoxylated with an average of 7 ethylene oxide chains and is much smaller, about 10C (33-37C) for an ethoxylated-propoxylated fatty alcohol. Ideally, since a heavy duty detergent must perform from low temperatures (30C) to high temperatures (90C), the CPT should not be above 30 to 40C and the PIT should not be below 90C.
The existence of both a CPT and a PIT are related to the unique character of the polyethylene oxide chain. The chain monomeric element can adopt two configurations, a trans-configuration, and a gauche, cis-type configuration. The enthalpy difference between both configurations is small, but the hydr tlon Is very d1fferent. The tranr-configuration is the mort ll I stable, and 19 easily hydrated. The gauche configuration is somewhat higher in energy and does not become hydrated to any significant extent. At low temperature the trans-configuration l is preponderant and the polymeric chain i8 soluble in water. As temperature rises kT becomes rapidly greater than the enthalpy difference between configuratlons and the proportlon of gua~he configurated monomeric un~t~ increases. Rapidly, the number of hydration water molecules drops, and the polymer solubility ecreases.
The nonionic surfactant whlch exhibits a PIT close to the CPT i~ accordingly very temperature sensitive. One way to reduce the temperature sensitivity is to use a nonionic surfactant with a hydrophilic part different from polyethylene oxide~ However, since commerclally available nonionic surfactants are based on polyethylene oxide, the only cost effective route is to add a cosurfactant which can co-micellize, giving less temperature sensitive mixed micelles.
Various types of cosurfactant systems are known in the prior art, some of which include nonionic detergents and tertiary amide oxides or amphoteric detergents. Amphoterics have been known for years for their detergency boosting properties. One amphoteric detergent used as a cosurfactant and which has particularly good detergency boosting activity in combination with a nonionic detergent are betaine detergents and alkyl bridged betaine detergents having the general formuli Rl-N -R4-C-o- and 1~ i l!
i!

, 1323822 O IR+ 1l l-CH2-C-NH-(CH2)3-N -R4-C-O-respectively, wherein Rl is an alkyl radical containing from about 10 to about 14 carbon atoms R2 and R3 are each selected from the group consisting of methyl and ethyl radicalsJ and R4 is selected from the group consisting of methylene, ethylene and propylene radicals.
A suitable betaine surfactant i9 C12-H25-N+-CH2-C-o whereas a suitable alkylamidobetaine is C12-H25-C-NH(CH2)3-N+-CH2-C-o-Sulfobetaines, such as fH3 OH
C12-H25-C-NH-(CH2)3-N+-CH2-CH-CH2-SO3-have also been found to exhibit good detergency boosting properties when used in combination with nonionic detergents~
A betaine exhlbitl both a positive charge and l; l li , , I

negatlve charge. It ls electrlcally neutral as are nonionlc surfactants. The quaternary ammonium ls essential to maintain the positive charge even ln alkaline ~olution. It i8 well known that ions are easily hydrated and that the hydratlon does not vary much with temperature. Betalne surfactants can accordingly be used as a cosurfactant. In addition, although free amines react rapidly wlth peraclds to glve amlne oxldes whlch consume bleach moletles and surfactant molecules, a betaine is the only nitrogen containing ~tructure which is stable in the presence of an organic peracid (present as ls or generated by reactlon between perborate and a bleach actlvator such as T~ED).
The addltlon of betaine to a nonlonic detergent significantly improves olly soil removal. Although the most ælgnificant improvement is achleved at 90C, important beneflts are obtalned at 60C and especlally at 40C. However, on an lndustrlal scale, betaines are only available in aqueous solution and hence cannot be used as an addltive in non-aqueous liquid detergent compositlons.
Detergency boostlng propertles have not prevlously been dlsclosed for sugar esters and sugar ethers. Potentiating or synergestic effects between sugar esters and nonlonic surfactants have now been discovered and are disclosed in copending Canadian application Serlal No. 588,765 titled "Sugar Esters As Detergency Boosters". In addition, it has also now been discovered, as disclosed in copending Canadian application Serial No. 588,775 titled "Sugar Ethers As Bleach Stable Detergency Boosters", that sugar ethers may advantageously be used as a bleach stable detergency booster in a nonionic detergent compositlon. These sugar based surfactants have been found to be effectlve detergency boosters and can efflciently ~-, replace betaines, as a cosurfactant, ln nonionic detergents.
Sugar ethers and esters have been found to perform similar to betalnes ln both powdered and aqueous liquld heavy duty laundry detergents. However, unllke betalne detergents, sugar esters and sugar ethers may be advantageously employed ln non-aqueous liquid detergent composltions and have been found to have significant detergency boostlng efflclency in non-aqueous llquld laundry detergents. Non-aqueous liquid detergents are known as having poor detergency at hlgh temperatures due to the presence of low phase inversion temperature nonionic. Sugar esters and sugar ethers have been found to increase the detergency of non-aqueous liquid detergents, especlally at temperatures of 60C and above, a temperature range where non-aqueous detergent products are known to be less efflcient.
Such effects are due to the fact that the hydrophlllc part of the surfactant ~sugar) ls Dot slgniflcantly temperature sensltlve and remalns water soluble at higher temperatures.
Although the solubility ln water of the ethylene oxide chain diminishes as temperature rises, the presence of the -OH group in the sugar molety slgniflcantly decreases the whole surfactant temperature sensltivity so the mixed micelle (nonionic and sugar ester~ether) remains stable in a wider temperature range than the micelle of the nonionic detergent alone.
Food grade 100~ active sugar esters were tested for their detergency boosting propertles. Glucose ester S 1670, a stearic acid derivative having an HLB of 16 and glucose ester 3' 7 ~,,~

L 1570, a lauric acld derivative having an HL8 of 15 were each tested using EMPA and KREFELD as soils at isothermal wash temperatures of 40C, 60, and 90C. In the following test, soiled cotton fabric swatches were washed for a period of 30 minutes in a wash solution containing 1.5g TPP (sodium tripolyphosphate) and 2g of surfactant mixture ln 600 ml of tap water. The following surfactant mixtures A, B, and C were tested.

Surfactant A ~ nonionic surfactant (ethoxylated-propoxylated C13-Cls fatty alcohol) Surfactant B - Surfactant A + L 1570 Surfactant C - Surfactant A + S 1670 ~323822 Table 1 shows the detergency results of various nonionic surfactant:sugar ester ratios.
l TABLE 1 SUGAR ESTER DETERGENCY

Surfactant Ratio of nonionic Isothermlc wash temperature Mixtureto sugar ester 40C 60C 90~C

Soil - EMPA on cotton lC Delta Rd Value A 18.2 17.7 6.4 . 8 9:1 18.8 17.1 10.2 8:2 19.6 16.6 16.7 7:3 20.1 20.5 16.9 C 9:1 19.2 20.1 16.2 8:2 7.3 13.4 14.2 .._ ._ Soil - RREFELD on cotton Delta Rd Value A 4.6 11.4 11.4 9:1 4.5 11.9 12.0 8:2 4.9 13.2 13.6 7:3 5.9 13.3 14.3 C 9:1 5.5 11.5 13.2 8:2 7.3 13.4 14.2 ._ Table 2 shows the detergency results for different nonionic surfactant/glucose ether (alkyl glucoside) ratios wherein the alkyl glucoside, a 100~ active powder, is a C12-C14 glucose ether (mixture of mono- and dialkyl).
The surfactant mixture was tested using, as soils, MPA and KREFELD, ae Isothermr11 wash temperatures of 40C, 60C

and 90C. In the following test, so11ed cotton fabric swatches were washed for a period of 30 minutes in a wash solution contalning 1.59 TPP and 29 of the ~urfactant mixture in 600 ml of tap water.

SUGAR ETHER DETERGENCY
_ ._ SurfactantRatio of nonionic Isothermal wash temperature Mixtureto sugar ether 40C 60C 90C
. _ _ Soil - EMPA on cotton Delta Rd Value nonionic 18.5 20.6 15.6 nonionic/alkyl 9sl 18.4 22.6 22.0 glucoside 8:2 20.4 23.4 24.4 7:3 21.6 22.5 26.9 .._ Soil - KREPELD on cotton Delta Rd Value nonionic a . 1 13.1 12.2 nonionic/alkyl 9:1 9:4 13.2 15.5 glucoside 8:2 10.0 14.9 16.4 7:3 10.7 15.8 17.5 ... ._ _ .

From the above table~, the excellent performances of sugar esters and sugar etherq as a cosurfactant with a nonionic surfactant i8 clearly evidenced. Although delivering a benefit at 40C, detergency is greatly increased at 90C. Since the detergency of non-aqueous liquid detergents based on ethoxylated-propoxylated fatty alcohol nonionic surfactants drop at high temperatures due to the reduced solubility of the surfactant as temperature rises, the additlon of a sugar fatty l ester or ether as a cosurfactant greatly increa~es detergency.
Any sugar ester or sugar ether may be used as a potential detergency booster. It i8 to be understood that the nature of the hydrophilic head group can be extended to any sugar derivative ~uch as, for example, glucose or sucrose and variations and optimizations will be apparent to those skilled in the art. Unlike polyethyleneoxide based nonionic surfactants, the HLB oE sugar derivatives is ad~usted by the number of hydrocarbon chains per sugar _nit rather than by the hydrophilic chain length. Sugar esters and ethers may be incorporated into any detergent composition, liquid or powdered, containing a high level of nonionic surfactant.
In terms of chemical stability, sugar esters are sub~ect to hydcolysis under alkaline conditions although saponification has not been evidenced in the washing medium in the presence of 2.5g/liter TPP, even at 90C. In addition, the ester bond is not stable in the presence of bleaching agents.
The use of bleaching agents as aids in laundering is well known. Of the many bleaching agents used for household applications, the chlorine-containing bleaches are most widely used at the present time. However, chlorine bleach has the serious disadvantage of being such a powerful bleaching agent that it causes measurable degradation of the fabric and can cause localized over-bleaching when used to ~pot-treat a fabric unde~irably stained in some manner. Other active chlorine bleaches, such as chlorinated cyanuric acid, although somewhat ¦ safer than sodium hypochlorite, also suffer from a tendency to damage fabric and cau~e localized over-bleachlng. Foe these reasons, chlorine bleaches can seldom be used on amide-containing fibers such as nylon, silk, wool and mohair. Furthermore, chlorine bleaches are partlcularly damaging to many flame retardant agents which they render ineffective after aA little as five launderings.
Of the two major types of bleaches, oxyqen-releasing and chlorine-releasing, the oxygen bleaches, sometimes referred to as non-chlorine bleaches or ~all-fabric~ bleaches, are more advantageous to use in that oxygen bleaching agents are not only hiqhly effective in whitening fabrics and removing stains, but they are also safer to use on colors. They do not attack fluorescent dyes commonly used as fabric brlghteners or the fabrics to any serious degree and they do not, to any appreciable extent, cause yellowing of resin fabric finishes as chlorine bleaches are apt to do. Both cblorine and non-chlorine bleaches use an oxidizing agent, such as sodium hypochlorite in the case of chlorine bleaches and sodium perborate in the case of non-chlorine bleaches, that reacts with and, with the help of a detergent, lifts out a stain.
Among the various substances which may be used as oxygen bleaches, there may be mentioned hydrogen peroxide and other per compounds which give rise to hydrogen peroxide in aqueous solution, such as alkali metal persulfates, perborates, percarbonates, perphosphates, persilicates, perpyrophophates, peroxides and mixtures thereof.
Although oxygen bleaches are not, as deleterious to fabrics, one major drawback to the use of an oxygen bleach is he high temperature and high alkality necessary to efficiently activate the bleach. Because many home laundering facilities, ~ 1323822 particularly in the United States, employ qulte moderate washing temperatures ~20C, to 60C), low alkalinity and short soaking times, oxygen bleaches when u~ed in such systems are capable of only mild bleaching action. Thece i5 thus a great need for substances which may be used to activate oxygen bleach at lower temperatuees.
Various activating agents for improving bleaching at lower temperatures are known. These activatlng agents are roughly divided into three groups, namely (1) N-acyl compounds such as tetracetylethylene diamine (TAED), tetraacetylglycoluril and the llke; (2) acetic acid esters of polyhydric alcohols such as glucose penta acetate, sorbitol hexacetate, sucrose octa acetate and the like~ and (3) organic acid anhydrides, such as phthalic anhydride and succinic anhydride. The preferred bleach activator being TAED. Oxygen bleach activators, such as TAED
function non-catalytically by co-reaction wlth the per compound to form peracids, such as peracetic acid from TAED, or salts thereof which react more rapldly with oxidizable compounds than the per compound itself.
As stated above, sugar esters are not stable in the presence of oxygen bleaches. When sodium perborate dissolves in water, hydrogen peroxide appears rapidly. Due to the alkalinity (pH 9.5-10), hydrogen peroxide, which is much more acidic than water, is ionized to a significant extent. In addition, the perhydroxyl anion i~ much more nucleophilic than the hydroxyl ion. During the wash cycle, the ester bond, stable enough to hydroxyl ion, even at 90C, is rapidly perhydrolyzed at low temperatures by the hydrogen peroxide coming from perborate.
Fatty peracid (e.g. perstearic acid in the above stearic acid based sugar ether) is generated but the detergency benefit is lost. This mechanism is the same as the production of peracetic acld at low temperature from ~AED and sodium perborate. Thus, as dlsclosed ln the prior art, sugar e~ters are bleach activators although the result of bleach activation by sugar esters is much less than that with TAED because the activated bleachlng molety ls perstearlc acid rather than peracetlc acid. Thus, sugar esters are most advantageously employed as a detergency booster in a non-aqueous liquid laundry detergent compocltlon only when sodlum perborate 1~
removed. However, the use of a non-aqueous llquld detergent without bleach ls not reallstlc, even if its detergency ls outstandlng.
As dlsclosed ln copendlng Canadian appllcatlon Serlal No. 588,775 sugar ethers not only have detergency boosting properties, but are stable in the presence of bleach. As with sugar esters, sugar ethers provide actlvated detergency when incorporated lnto both powdered and llquid detergent compositions. However, the use of sugar ethers are particularly advantageous when incorporated into non-aqueous liquid formulations. It has been discovered that alkyl glycosldes te.g. glucose ether) exhibit very efficlent detergency boostlng properties especially with low foam surfactants, such as ethoxylated-propoxylated fatty alcohols.
The ether bond being perfectly stable agalnst hydrolysis and perhydrolysis.
Although sugar ethers are similar to sugar esters in detergent performance, they are, unlike sugar esters, stable against alkallnity and hydrogen peroxide. Any sugar ether can potentially deliver this type of benefit. In addltlon, any stable llnk between the sugar molety and the fatty acld chaln can be used. Such llnkages include, but are not limlted to, amlde, thloether and urethane llnkages whlch may be formed by conventlonal reactlons. In additlon to thelr very hlgh efflciency, sugar ethers are very stable agalnst chemlcal degradation. The lncorporatlon of a 8ugar ether ln a llquld or powdered heavy duty detergent efflclently replaces betalneæ or sugar esters as the cosurfactant wlth a nonlonlc detergent.
A heavy duty deterqent composltlon havlng both actlvated bleach and actlvated detergency ba~ed on the lncorporatlon wlthln the detergent compo~ltlon of acetylated sugar ethers of the general formula ~0 OA\~
OA
whereln R represents a fatty chaln contalnlng at least 10 carbon atoms and A repre~ent~ -CO-CH3, has been dlscovered as dl6closed in copendlng Canadlan appllcatlon Serial No. 588,764 tltled ~Acetylated Sugar Ethers AB Bleach Actlvators and Detergency Boostersn.
The lncorporation of the above acetylated sugar ether in a liquld or powdered detergent efflclently replaces both TAED as a bleach activator and the cosurfactant betaine or sugar ester/ether a6 the detergency booster.
Appllcantæ have now dlscovered and herein clalm the u~e of acetylated sugar ethers in nonionic detergent compo61tlon. The acetylated sugar ethers act as detergent boosters, bleach actlvators and fabrlc softeners. The co~pound has the general formula ~.,, ~ 1323822 ~ CH2-OR

1\ O ~

wherein Rl and R2, independently, repre~ent a fatty acid chain containing 10 or more carbon atoms, preferably 12 to 22 carbon atoms, more preferably 18 to 20 carbon atoms and A represents -CO-CH3.
rn the preparation of the above molecule a classical alkyl glycoside (sugar ether) containing at least two fatty acid chains, produced by methods known in the art, is acetylated by react$on with acetic anhydrlde. Followlng purification, the product can be incorporated into the detergent composition.
When water is added (i.e. the composition is added to the wash water), the compound reacts first with perborate and generates peracetic acid. After reactlon with hydrogen peroxide, the compound acts as a detecgency boo~ter. The presence of at least two fatty acid chains containing 14 carbon atoms or more induces absorption onto the fibers and a softening effect is obtained.
Although acetylated dialkyl glucose ether is represented in the above general formula, it is to be understood that any sugar ether, mono- or polyglycoside, etherified with two more fatty acid chains and finally acetylated can deliver these properties. In addition, any stable bond between the fatty chain and the sugar can be used. Such bond~ include, but are not limited to, amide, thioether and urethane bonds, formed by conventional reactions. Also, instead of being acetylated, the remaining hydroxyl groups can be reacted with any reagent able to generate a labile bond. 16 132~822 The acetylated sugar ether of thls embodiment ls able to slmultaneously deliver three ma~or functlons in a detergent composition, namely ~1) bleach activation, (2) actlvated detergency and (3) fabric softenlng. It læ thu~ advantageous not only from a cost basls but also because it allows for an increase in formula concentratlon.
Although the acetylated sugar ethers of this invention can advantageously be employed in both powdered and aqueous llauid detergent compositions, other ob~ects of the lnventlon will become more apparent from the following detailed descrlptlon of a preferred emhodiment wherein a detergent composltion is provided by adding to a non-aaueous liquld suspenslon an amount of acetylated sugar ether effective to provide the needed bleach actlvating, detergency boosting and fabric softening properties.
The nonionic synthetic organic detergents employed in the practlce of the invention may be any of a wide variety of such compounds, which are well known and, for example, are described at length in the text $urface Active Aaents, Vol. II, by Schwartz, Perry and ~erch, published in 1958 by Interscience Publishers, and in McCutcheon's Deteraents and Emulsifiers, 1969 Annual. Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol wherein the alkanol is of 10 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide ~of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred ~' ., .

¦to employ those wherein the higher alkanol is a highec fatty ¦alcohol of 10 to 11 or 12 to 15 carbon atoms and which contain ¦from 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, l the lower alkoxy is ethoxy but in some instances, it may be dectirably mixed wlth propoxy, the latter, if present, often being a minor (less that 50~) proportlon. Exemplary of such compound~
are those wherein the alk~nol i9 of 12 to 15 carbon atoms and whlch contain about 7 ethylene oxlde groups per mole e.g. Neodol*
25-7 and Neodol 23-6.5, whlch products are made by Shell Chemical Company, Inc. The former i9 a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a correspond1ng mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5. The higher alcohols are primary alkanol~. Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corporation.
The former i~ a mixed ethoxylation product of an 11 to 15 carbon atom linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.
Also useful in the present composition as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are¦
also made by Shell Chemical Company.
An especially useful class of nonionics are represented ~ ' ~/"raJe -~77a~

by the commercially well known class of nonionics sold under the trademark Plurafac. The Plurafacs are the reaction product o~ a higher linear alcohol and a mixture of ethylene and propylene oxides, containlng a mixed chain of ethylene oxide and propylene oxide, teeminated by a hydroxyl group. Examples include Plurafac RA30, Plurafac RA40 (a C13-Cls fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), Plurafac D25 (a C13-Cls fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide), Plurafac B26, and Plurafac RA50 (a mixture of equal parts Plurafac D25 and Plurafac RA40).
Generally, the mixed ethylene oxide-propylene oxide fatty alcohol condensation products can be represented by the general formula Ro(c2H4o)p(c3H6o)qH

wherein R is a straight or branched, primary or secondary aliphatic hydrocarbon, preferably alkyl or alkenyl, especially preferably alkyl, of from 6 to 20, preferably 10 to 18, especially preferably 14 to 18 carbon atoms, p i9 a number of from 2 to 12, preferably 4 to 10, and q is a number of from 2 to 7, preferably 3 to 5. These surfactant~ are advantageously used where low foaming characteristics are desired. In addition they have the advantage of low gelling temperature.
Another group of liguid nonionics are available from Shell Chemical Company, Inc. under the Dobanol trademark:
Dobanol 91-5 is an ethoxylated Cg-Cll fatty alcohol with an average of 5 moles ethylene oxide~ Dobanol 25-7 is an ethoxylated C12-Cls fatty alcohol with an average of 7 moles ethylene oxide.
In the preferred poly-lower alkoxylated higher alkanols, to obtain the best balance of hydrophilic and lipophilic moieties, the number of lower alkoxles will ususally be from 40~ to 100% of the number of carbon atoms in the higher alcohol, preferably 40~ to 60~ thereof and the nonionic detergent will preferably contain at lea~t 50~ of such poly-lower alkoxy higher alkanols. The alkyl groups are generally linear although branching may be tolerated, such as at a carbon next to or two carbons removed from the terminal carbon of the straight chain and away from the ethoxy chain, if such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branched configuration will be minor rarely exceeding 20~ of the total carbon atom content of the alkyl. Similarly, although linear alkyls which are terminally joined to the ethylene oxide chains are highly preferred and are considered to result in the best combination of detergency and biodegradibility medial or secondary ~oinder to the ethylene oxide in the chain may occur. It ls usually in only a minor proportion of such alkyls, generally le~s than 20% but, as is in the cases of the mentioned Tergitols, may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, it will usually be less than 20% thereof and preferably less than 10% thereof.
When greater proportions of non-terminally alkoxylated alkanols, propylene oxide-containinq poly-lower alkoxylated alkanols and less hydrophile-lipophile balanced nonionic , detergent than mentioned above are employed and when other nonionic detergents are used instead of the preEerred nonionics recited herein, the product resulting may not have as good detergency, stability, and viscosity properties as the preferred compositions. In some cases, as when a higher molecular weight poly-lower alkoxylated higher alkanol 18 employed, often for its detergency, the proportion thereof will be regulated or limited in accordance with the results of routine experiments, to obtain the desired detergency. Al~o, it has been found that it is only rarely necessary to utilize the higher molecular welght nonlonlcs for their detergent propertles qince the preferred nonionics described hecein are excellent detergents and additionally, permit the attainment of the desired viscosity in the liquid detergent. Mixtures of two or more of these liquid nonionics can also be used.
Furthermore, in the composltions of this invention, it may often ~e advantageous to include compounds which function as viscosity control and gel-inhibiting agents for the liquid nonionic surface active agents such as low molecular weight ether compounds which can be considered to be analogous in chemical structure to the ethoxylated an/or propoxylated fatty alcohol nonionic surfactants but which have relatively short hydrocarbon chain lengths ~C2-Cg) and a low content of ethylene oxide (about 2 to 6 ethylene oxide units per molecule).
Suitable ether compounds can be represented by the following general formula RO(CH2CH20)nH

wherein R is a C2-Cg alkyl group, and n is a number of from about l to 6, on average.
Specific example~ of suitable ether compounds include ethylene glycol monoethyl ether (C2Hs-0-CH2CH20H), diethylene glycol monobutyl ether (C4Hg-0-(CH2CH20)2H), tetraethylene glycol monobutyl ether (C~Nl7-0-(CN2CN20)4N), etc. Dlethylene glycol 1323822 6230l-l535 monobutyl ether ls especlally preferred.
Further improvements in the rheologlcal propertie~ of the liquid detergent compositions can be obtained by including in the composltion a small amount of a nonlonlc sur~actant whlch has been modlfied to convert a free hydroxyl group thereof to a molety havlng a free carboxyl group. As dlsclosed in commonly asslgned Canadlan application Serial No. 478,379 the free carboxyl group modlfied nonlonlc surfactants, whlch may be broadly characterized as polyether carboxylic aclds, function to lower the temperature at whlch the liquld nonionlc forms a gel with water. The acldlc polyether compound can also decrease the yleld stress of such dlsperslons, aldlng ln their dispensability without a corresponding decrease ln their stability against settling.
The lnvention detergent composltions also include water soluble and/or water lnsoluble detergent builder salts.
Typlcal sultable bullders lnclude, for example, those dlsclosed ln U.S. Patents 4,316,812; 4,264,466 and 3,630,929. Water ~- soluble lnorganic alkaline builder salts which can be used along with the detergent compound or in admixture wlth other bullders are alkall metal carbonates, borates, phosphates, `~ polyphosphates, bicarbonates and sillcates. Ammonium or .:..
. substituted ammonium salts can also be used. Specific examples :-~
.
of such salts are sodium trlpolyphosphate, sodlum carbonate, .
sodium tetraborate, sodlum pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, and potasslum blcarbonate. Sodlum trlpolyphosphate (TPP) is especlally . --preferred. The alkali metal silicates are useful bullder salts whlch also functlon to make the compositlon antlcorroslve to washing machlne parts. Sodium slllcates of Na20/S102 ratlos of from 1.6/1 to 1/3.2, especlally ~j about 1/2 to 1/2-8 are preferred. Potassium ~ilicates of the same can also be used.
Another class of builders highly useful herein are the water insoluble aluminosilicates, both of the crystalline and amorphous type. Various crystalline zeollte~ (i.e.
aluminosilicates) are described in British Patent 1,504,168, U.S.
Patent 4,409,136 and Canadlan Patents 1,072,835 and 1,087,477.
An example of amorphous zeolites useful herein can be found in Belgium Patent 835,351. The zeolites generally have the formula (M2)x'(A123)y~(SiO2)Z-WH2o where x is 1, y i~ from 0.~ to 1.2 and preferably 1, z is from l.S to 3.5 or higher and preferably 2 to 3 and w is from O to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, with type 4A
particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400 meq/g.
Other materials such as clays, particularly of the water insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hydrated aluminum silicate in which about 1/6th of the aluminum atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified form (i.e. free from grit, sand, etc.) suitable for detergents invariably contains at least 50~ montmorillonite and thus its cation e~change capaclty is at least abo;t 50 to 75 meq per 100 g of ~ 1323822 62301-1535 bentonite. Partlcularly preferred bentonites are the Wyoming or Western U.S. bentonites whlch have been sold as Thlxo-jels*
1, 2, 3 and 4 by Ceorgla Kaolln Co. These bentonites are known to soften textlles as described in British PatentR 401,413 and 461,221.
Examples of organic alkaline sequestrant builder salts whlch can be used along wlth the detergent or in admlxture wlth other organic and lnorganlc bullders are alkali metal, ammonlum or substltuted ammonlum, amlnopolycarboxylates, e.g. sodlum and potasslum nltrilotriacetates (NTA) and trlethanolammonlum N-(2-hydroxyethyl)nltrllodlacetates. Mlxed , salts of these polycarboxylates are also suitable.
; Other sultable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of .- special value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are ` descrlbed in 4,144,226; 4,315,092 and 4,146,495. Other U.S.
Patents on similar builders include 4,141,676; 4,169,934;

4,201,858; 4,204,852; 4,224,420; 4,225,685; 4,226,960;
4,233,422; 4,233,423; 4,302,564 and 4,303,777. Also relevant are Canadlan Patents 1,148,831; 1,131,092 and 1,174,934.
~;, Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any . phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as a polymeric carboxyllc acld having high calclum binding capacity to inhibit incrustation which could otherwise be caused by formation of an insoluble calcium phosphate. Such auxiliary builders are also well known in the art. For example, mention can be made of Sokalan* CP5 which is a copolymer of about equal *Trade-mark 24 ~, . ,.~.

moles of methacrylic acid and maleic anhydride, completely neutralized to form the sodium salt thereof.
In addition to detecqent builders, various other detergent additives or ad~uvants may be present in the detergent S product to give it additional desired peoperties, either of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or antiredepo~ition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl alcohol methyl cellulose; optical brightener~, e.g. cotton, polyamide and polyester brighteners, for example, stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., most preferred are stilbene and triazole combinations.
Bluing agents such as ultramarine blue; enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type enzymes, lipase type enzymes, and mixtures thereof; bactericides, e.g.
tetrachlorosalicylanilide, hexachlorophene; fungicides; dyes;
pigments (water dispersible); preservatives; ultraviolet absorbers; anti-yellowing agents, such as sodium carboxymethyl cellulose (CMC), complex of C12 to C22 alkyl alcohol with C12 to Clg alkylsulfate; pH modifiers and pH buffers; perfume; and anti-foam agents or suds-suppressors, e.g. silicon compounds can also be used.
As described hereinabove, bleaching agents are classified broadly for convenience as chlorine bleaches and oxygen bleaches. Oxygen bleaches being preferred. The perborates, particularly sodium perborate monohydrate, are ~ 1323822 ¦espec~ally preferred. In accordance wlth this invention, the peroxygen compound is used in admixture wlth an acetylated sugar ether which functions as an activator therefor. In additLon, detergency properties of the nonionic detergent i9 improved and a ¦ softening effect is obtained by the presence of the acetylated sugar ether of the invention containing at least two fatty acid chains.
In a preferred form of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, e.g.
to an average particle size of 2 to 10 microns or even lower ~e.g. 1 micron). Preferably less than about 10~, especially less than about 5~ of all the suspended particles have particle sizes greater than 10 microns, compositions whose dispersed particles are of such small size have improved stability against separation or settling on storage.
In tbe grinding operation, it is preferred that the proportion of solid ingredients be high enough (e.g. at least about 40% such as about 50~) that the solid particles are in contact with each other and are not substantially shielded from one another by the nonionic surfactant liquid. Mills which employ grinding balls (ball mills) or similar mill grinding elements have given very good results. Thus, one may use a laboratory batch attritor having 8 mm diameter steatite grindinq balls. For larger scale work a continuously operating mill in which there are 1 mm or 1.5 mm diameter grinding balls working in a very small gap between a stator and a rotor operating at a relatively high speed (e.g. CoBall mill) may be employed. When 30 ~ UJl ~I such ~ mill, it iJ deJirable to pasJ the blend oE nonionic ~ 1323822 surfactant and solids flrst through a mill which does not effect such fine grinding (e.g. a colloid mill) to reduce the particle size to leRs than 100 micronR ~e.g. to about 40 micron~) prior to the step of grinding to an average particle diameter below about 10 microns in the continuous ball mlll.
In the preferred heavy duty liquid detergent compositions of the invention, typical peopoetions (based on the total composition, unless otherwise speclfied) of the ingredients are as follows:
Suspended detergent builder, within the range of about 10 to 60~ such as about 20 to 50~, e.g. about 25 to 40%.
Liquid phase comprising nonionic surfactant and optionally dissolved gel-inhibiting ether compound, within the range of about 30 to 70~, such a~ about 40 to 60~; this phase may also include minoe amounts of a diluent ~uch as a glycol, e.g.
polyethylene glycol ~e.g. "PEG 400n), hexylene glycol, etc. such as up to 10%, preferably up to 5%, for example, 0.5% to 2%. The weight eatio of nonionic suefactant to ether compound when the latter i9 peesent is in the range of feom about 100:1 to 1:1, preferably from about 50:1 to about 2:1.
Acetylated -qugar ether of this invention, from about 4 to about 15%, preferably about 6 to about 8~.
Polyether carboxylic acid gel-inhibiting compound, up to an amount to supply in the range of about 0.5 to 10 parts (e.g. about 1 to 6 parts, such as about 2 to 5 parts) of -COOH
(M.W. 45) per 100 paets of blend of such acid compound and nonionic surfactant. Typically, the amount of the polyether carboxylic acid compound is in the range of about 0.05 to 0.6 part, e.g. about 0.2 to 0.5 part, per part of the nonionic surfactant. 27 . .' 132~822 Acidic organic phosphoric acid compound, as anti-settling agentS up to 5~, for example, ln the range of 0.01 to 5%~ such as about 0.05 to 2a, e.g. about 0.1 to 1~.
Suitable ranges of the optional detergent additive~
are: enzymes - 0 to 2%, especially 0.7 to 1.3~s corrosion inhibitors - about 0 to 40~, and preferable 5 to 30~S anti-foam agents and suds-suppressors - 0 to 15~, preferably 0 to 5~, for example 0.1 to 3~t thickening agent and dispersants - 0 to 15~, for example 0.1 to 15~, for example 0.1 to 10%, preferably 1 to 5~S soil suspending or anti-redeposition agentc and anti-yellowing agents - 0 to 10~, preferably 0.5 to 5~5 colorants, perfumes, brighteners and bluing agents total weight 0~ to about 2~ and preferably 0~ to about 2~ and preferably 0% to about l~s pH modifiers and pH buffers - 0 to 5~ preferably 0 to 2%S
bleaching agent - 0~ to about 40~ and preferable 0~ to about 25~, for example 2 to 20~. In the selections of the adjuvants, they will be chosen to be compatible with the main constituents of the detergent composition.
In this application, all proportions and percentages are by weight unless otherwise indicated. In the examples, atmospheric pressure is used unless otherwise indicated.
Example A concentrated non-aqueous built liquid detergent composition is formulated from the following ingredients in the amounts specified. The composition is prepared by mixing and finely grinding the following ingredients to produce a liquid suspension. In preparing the mixture for grinding the solid ingredients are added to the nonionic surfactant, with TPP being added last.

A~ount Wei Nonionic surfactant (ethoxylated-propoxylated 23 Cl3-C15 fatty alcohol) S Dowanol DB - nonlonic surfactant 21 di (C18) alkyl glucose ether, triacetyl 6 Sodium tripolypho~phate (TPP) - builder salt 33.8 Sokalan CPS - anti-encrustation agent 2 Deguest 2066 - sequestering agent Sodium perborate monohydrate - bleachlng agent 9 Urea - stabilizer Sodium carboxymethylcellulose (CMC) - antl-yellowing agent Esperase - enzyma 0.8 Termamyl - enzyme 0.2 Tinopal ATS-X - optical brightener 0.4 TiO2 - whitening agent 0.2 Perfume 0.6 The above composition is stable in storage, dispenses readily in cold wash water and exhibits excellent detersive ffects and imparts fabric softening properties to the wash load.
It is to be understood that the foregoing detailed escription is given merely by way of illustration and that ariations may be made therein without departing from the Spiit nd scope of the invention.

~ ~al~k

Claims (20)

1. A heavy duty laundry detergent composition comprising a nonionic surfactant, a bleaching agent and, as a bleach activator, detergency booster and fabric softener, an acetylated sugar ether containing at least two fatty acid chains.

2. The composition of claim 1 wherein the acetylated sugar ether is a triacetyl sugar ether.

3. The composition of claim 1 wherein the acetylated sugar ether is acetylated dialkyl sugar ether.

4. The composition of claim 1 wherein the acetylated sugar ether is acetylated glucose ether.

5. The composition of claim 4 wherein the acetylated glucose ether is triacetyl dialkyl glucose.

6. The composition of claim 1 wherein the bleaching agent is sodium perborate monohydrate.

7. The composition of claim 1 wherein said fatty acid chains contain at least 10 carbon atoms.

8. The composition of claim 7 wherein said fatty acid chains contain 18 to 20 carbon atoms.

9. The composition of claim 1 wherein the heavy duty laundry detergent composition is in powdered form.

10. The composition of claim 1 wherein the heavy duty laundry detergent composition is in liquid form.

11. The composition of claim 10 wherein the heavy duty liquid composition is an aqueous liquid composition.

12. The composition of claim 10 wherein the heavy duty Liquid composition is a non-aqueous liquid composition.

13. A non-aqueous heavy duty laundry composition comprising a suspension of insoluble particles of builder salt, a bleaching agent and, as a bleach activator, detergency booster and fabric softener, an acetylated sugar ether containing at least 2 fatty acid chains dispersed in liquid nonionic surfactant.

14. The composition of claim 13 wherein the acetylated sugar ether is a triacetyl sugar ether.

15. The composition of claim 13 wherein the acetylated sugar ether is acetylated dialkyl sugar ether.

16. The composition of claim 13 wherein the acetylated sugar ether is acetylated glucose ether.

17. The composition of claim 16 wherein the acetylated glucose ether is triacetyl dialkyl glucose.

18. The composition of claim 13 wherein the bleaching agent is sodium perborate monohydrate.

19. The composition of claim 13 wherein each of said fatty acid chains contain at least 10 carbon atoms.

20. The composition of claim 19 wherein each of said fatty acid chains contain 18 to 20 carbon atoms.