CA1317849C - Sugar esters as detergency boosters - Google Patents

Sugar esters as detergency boosters

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Publication number
CA1317849C
CA1317849C CA000588765A CA588765A CA1317849C CA 1317849 C CA1317849 C CA 1317849C CA 000588765 A CA000588765 A CA 000588765A CA 588765 A CA588765 A CA 588765A CA 1317849 C CA1317849 C CA 1317849C
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composition
fatty acid
detergency
heavy duty
nonionic
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French (fr)
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Regis Lysy
Guy Broze
Jean-Paul Delvenne
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Colgate Palmolive Co
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Colgate Palmolive Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3907Organic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004Non aqueous liquid compositions comprising insoluble particles

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Abstract

SUGAR ESTERS AS DETERGENCY BOOSTERS
ABSTRACT OF THE DISCLOSURE

A heavy duty detergent composition having incorporated therein a sugar ester which provides detergency boosting properties to the detergent composition, The sugar ester contains at least one long-chain fatty acid.

Description

1 31 7~49 SUGAR ESTERS AS DETERGENCY BOOSTERS

BACKGROUND OF THE INVENTION
_ ~ .
(1) Field of the Invention This invention relates to an improved heavy duty laundry detergent composition. More partlcularly, the invention is directed to a heavy daty detergent composition having incorporated therein a sugar ester which provides detergency boosting properties to the detergent composition. A preferred embodiment of the invention is directed to a non-aqueous liquid heavy duty laundry detergent compositlon having activated detergency.
(2) Description of the Prior Art The use of various sugar derivatives 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 useful 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 yenerally contain about 8 to 25 carbon atoms and preferably about 10 to 14 carbon atoms.
Long chain alkyl glycosides are commonly prepaeed from saccharides and long chain alcohols. However, unsubstituted saccharides such as glucose are insoluble in hi~her alcohols and thus do not react together easily. Therefore, it i8 common to first convert the saccharide to an intermediate, lower alkyl glycoside which is then reacted with the long chain alcohol.
Lower alkyl glycosldes are commercially available and are commonly prepared by reacting a saccharide with a lower alcohol in the presence of an acid ca~alyst. Butyl glycoside is often employed as the intermediary.
The use of long chain alkyl glycosides as a surfactant in detergent compositions and various methods of preparing alkyl glycosides is disclosed~ for example, in U.S.
Patents 2,974,134; 3,547,828; 3,59~,86S and 3,721,633. The use of lower alkyl glycosides as a viscosity reducing agent in aqueous liquid and powdered deter~ents is dlsclo~ed in U.S.
Patent 4,~8,981.
Acetylated sugar esters, such asl for example, gluco.~e penta acetate, glucose tetra acetate and sucrose octa ace~ate, have been known for years as oxygen bleach activators.
The use of acetylated sugar derivatives as bleach activators is disclosed in U.S. Patents 2,955,905; 3,901,819 and 4,0~6,090.
SUMMARY OF THE INVENTION
In accordance with the present invention, a highly detersive heavy duty nonionic laundry detergent composition is prepared by the incorporation of a sugar ester into a nonionic detergent composition. The sugar esters act as detergency boosters. The sugar esters may be incorporated into detergent compositions which may be formulated into liquid or powdered ~orm. Both powdered aqueous and non-agueous liquid ~ormulations may advantageously be produced although far greater benefits are derived when used in a non-aqueou~
detergent composition.
The inven~ion therefore provides a heavy duty laundry detergent composition comprising a nonionic sur~actant, a bleaching agent, a bleach actlvator and, as a detergency booster, a sugar ester esterifled with at least one fatty acid chain.

A

1 3 1 7 ~ ~ q 62301-1536 The invention also provides a non-aqueous heavy duty laundry composition comprisiny a suspension of insoluble particles of builder salt, a bleaching agent, a bleach activator and, as a detergency booster, a sugar ester containlng at leas~ one fatty acid chain, dispersed in liquid nonionic surfactant.
There ls no disclosure in the prior art of the use of sugar based surfactants as detergency boosters.
DETAILED DESCRIPTION OF THE INVENTION
Optimum grease/oil removal is achieved where the nonionic surfactant has an HLB (hydrophilic-lipophlic balance) 2a 1 3 1 7~9 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 2. pnase rich in nonionic surfactant separates in the wash solution, (CPT) and the phase inversion (coalescence) temperature (PIT). Within 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, ~ince 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 charac~er of the polyethylene oxide chain. The chain monomeric element can adopt two configurations, a trans-configur~tion, and a gauche, cis-type configuration. The enthalpy difference between both configurations is small, but the hydration is very different. The trans-configuration is the most s~able, and is easily hydrated. The gauche configuration is somewhat higher in eneryy and does not become hydrated to any significant extent. At low temperature the trans-configuration is preponderant and the polymeric chain is soluble in water. As temperature rises kT becomes rapidly greater than the enthalpy difference between configurations and the proportion of guache configurated monomeric units increases~ Rapidly, the number of 1 31 7~9 hydration water molecules drops, and the polymer solubility decreases.
The nonionic surfactant which exhibits a PIT close to the CPT is 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 commercially 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 Qf cosurfactant sy~tems 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 boo~tlng properties. One lS 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 formoli 12 1l Rl~N+-R4-c-o- and O 1 2 il Rl-CH2-C-NH-(CH2)3-N+-R4-C-O-respectively, wherein Rl is an alkyl radical containing from about l0 to abo~t 14 carbon atoms R2 and R3 are each selected from the group cons tlng of methyl and ethyl rad1cals~ and R4 is selected frcm ¦

the group consisting of methylene, ethylene and propylene radicals.
A suitable betaine surfactant ls +
5Cl~-H2~-N -CH2-C-O~

whereas a suitable alkylamidobetaine i9 e IH3 8 C12-H25-C-NH(CH2)3-N+-CH2-C-o-Sulfobetaines, such as o CH3 OH

12-H25-C-NH-(CH2)3-N+-CH2-CH-CH2-S

: ~: : :

have also ~een found to exhibit good detergency boosting properties when used in combination wlth nonionic detergents.
A betaine exhibits both a positive charge and a negative charge. It is electrically neutral as are nonionic surfactants. The quaternary ammonium is essential to maintain the positive charge even in alkaline ~olution. It is well known that ions are easily hydrated and that the hydration does not vary much with temperature. ~etaine surfactants can accordingly be used as a cosurfactant. In addition, although free amines react rapidly with peracids to give amlne oxides which consume 1317~49 bleach moieties and surfactant molecules, a betaine is the only nitrogen containing structure which is stable in the presence of an organic peracid Ipresent as is or generated by reaction between perborate and a bleach activator such as TAED).
The addition of betaine to a nonionic detergent significantly improves oily soil removaL. Although the most significant improvement is achieved at '30C, important benefits are obtained at 60C and especially at 40C. However, on an industrial scale, betaines are only available in aqueous solution and hence cannot be used as an additive in non-aqueous liquid detergent compositions.
Detergency boosting properties have not previously been disclosed for sugar esters. Potentiating or synergestic effects between sugar esters and nonionlc surfactants have now been discovered and are herein claimed. Sugar esters have been found to be effective detergency boosters and can efficiently replace betaines, as a cosurfactant, in nonionic detergents. Sugar esters have been found to perform ~imilar to betaines in both powdered and aqueous liquid heavy duty laundry detergents.
However, unlike betaine detergents, sugar esters may be advantageously employed in non-aqueous liquid detergent compositions and have been found to have significant detergency boosting efficiency in non-aqueous liquid laundry detergents.
Non~aqueous liquid detergents are known as having poor detergency at high temperatures due to the presence of low phase inversion temperature nonionic. Sugar esters have been found to increase the detergency of non-aqueous liquid detergents, especially at temperatures of 60C and above, a temperature range where non-aqueous detergent products are known to be less efficient.
Such effect~ are due to the Eact that the hydrophilic 13178~') part of the surfactant ~sugar) is not significantly temperature sensitive and remains water soluble at higher temperatures.
Although the solubility in water of the ethylene ox~Lde chain diminishes a9 temperature rises, the presence of the -OH group in the sugar moiety significantly decreases the whole surfac~ant temperature sensitivity so the mixed micelle (nonionic and sugar ester) 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 properties. Glucose ester S 1670, a stearic acid derivative having an HLB of 16 and glucose ester L
1570, a lauric acid derivative having an HL8 of 15 were each tested using EMPA and ~REFELD as soils at isothermal wash temperatures o 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 1.59 TPP (sodium tripolyphosphate) and 2g of surfactant mixture in 600 ml of tap water. The following surfactant mixtures A, B, and C were tested.

Surfactant A = nonionic surfactant (ethoxylated-; propoxylated C13-C15 fatty alcohal) Surfactant B = Surfactant A ~ L 1S70 Surfactant C = Surfactant A ~ S 1670 - 13178'~q Table 1 shows the detergency results of various nonionic surfactant:sugar ester ratios .
TABL~ 1 SUGAR ESTER DETERGENCY
_ . . . .
Surfactant Ratio of nonionic Isothermic wash temperature Mixture to sugar ester 40C 60C 90C

Soil - EMPA on cotton : 10 Delta Rd Value A 18.2 17.7 6.4 B 9:1 18.8 17.1 10.2 8:2 19.~ 16.6 16.7 7:3 20.1 20.5 16.9 C ~:1 19.2 20.1 16.2 . 8:2 7.3 13~4 14.2 : Soil - ~R~FELD on cotton Delta Rd Value A 4.6 11.4 11.4 B 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 B:2 7.3 13.4 14.2 i From the above table, the excellent performance of sugar esters as a cosurfactant with a nonionic surfactant is cleaely evidenced. Although dellvering a benefit at 40C, detergency is greatly increased at 90C. Since the detergency of non-aqueous lilluld detergents ba ed on ethoxy1ated-pcopoxylated 1 31 ~49 fatty alcohol nonionic surfactants drop at high temperatures due to the reduced solubility of the surfactant as temperature rlses the addition of a sugar fatty ester as a cosurf2ctant greatly increases detergency.
Any sugar, esterified with at least one long ch~in fatty acid, may be used as a potential detergency booster.
Fatty acids having at least 10 carbon atoms or more being preferred. More preferable are fatty acids having 12 to 22 carbon atoms. Stearic acid (C18) is especially preferr~d. It is to be understood that the nature of the hydrophilic head group can ~e extended to any sugar derivative such as, for example, glucose or sucrose and variations and op~imizations will be apparent to those skilled in the art. Unlike polyethyleneoxLde based nonionic surfactants, the HLB of sugar derivatives is adjusted by ; 15 the number of hydrocarbon chains per sugar unit rather than by the hydrophilic chain length. Sugar esters may be incorporated into any detergent composition, liquid or powdered, containin~ a high level of nonionic surfactant.
Although the sugar esters of this invention can advantageously be employed in both powdered and aqueous liquid detergent compositions, other objects of the invention will become more apparent from the following detailed description of a preferred embodiment wherein a detergent composition is provided by adding to a non-aqueous liquid suspension an amount of sugar ester effective to provide the needed detergency boosting properties.
The nonionic synthetic organic detergents employed in the practice 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 tex~ Surface Active A~ents, Vol. II, by Schwartz, Perry and ~erch, published ln 1958 by Interscience Publlshers, and in McCutcheon's Deterqents and_Emulsifiers, 1969 Annual. Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the deslred 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 hi0her 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 material~ it is preferred to employ those whereln the higher alkanol is a hiqher 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, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, often being a minor (less than 50%) proportion.
~xemplary o~ such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole e.g. Neodol 25-7 and Meodol* 23-6.5, whlch products are made by Shell Chemical Company, Inc. The former i9 a condensation product of a mixture of hlgher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higher fatty al~ohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5. The higher alcohols are primary alkanols.
Other examples of such detergents include Tergitol* 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylate~ made by Union Carbide ~orporatlon. The former is a mixed ethoxylation product o~ an 11 to 15 carbon A *Trade-mark 10 1 31 7~9 atom linear secondary alkanol with ~even moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene o~ide being reacted.
Also useful in the present composition as a component of the nonionic detergent are higher molecular weight no~ionics, such as Neodol 45-11, which are ~imilar 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 e~pecially useful clas of nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac. The Plurafacs are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples~include Plurafac /
RA30, Plurafac RA40 (a C13~C15 fatty alcohol ~ondensed with 7 moles propylene oxide and 4 moles ethylene oxide), Plurafac D25 (a C13-C15 atty alcohol condensed with 5 moles propylene oxide and lO moles ethylene oxide)j 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 ormula :
~ 25 Ro(c2H4o)p~c3H6o)9H
: .
wherein R i5 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, 1 31 7~

especially preferably 14 to 18 carbon atoms, p is a number o~
from 2 to 12, preferably 4 to 10, and q is a number of from 2 to 7, preferably 3 to 6. The~e surfactants are advantageously used where low foaming characteristics are desired. In addition they have the advantage of low gelling temperature.
Another group of liquid nonionics are available from Shell Chemical Company, Inc. under the Dobanol trademark:
Dobanol 91-S 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 alkoxies wi:ll 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 least 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 chaln, 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 blodegradibility medial or secondary joinder to the ethylene oxide in the chain may occur. It is usually in only a minor proportion of such alkyls, generally less than 20~ but, as is in the cases of the mentioned Tergitols, may be greater. Alsol ~31784~

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.
~hen greater proportlons of non-terminally alkoxylated alkanols, propylene oxide-containing 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 preferred 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 ~olecular weight poly-lower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof wlll be regulated or limited in accordance with the results of routine experiments, to obtain the desired detergency. Also, it has been found that it is only rarely necessary to utilize the higher molecular weight nonionics for their detergent properties since the preferred nonionics described herein are excellent detergents and additionalIy, permit the attainment of the desired viscos}ty in the liquid detergent. Mixtures of two or more of these liquid nonionics can also be used.
Furthermore, in the compositions of this invention, it may often be 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-C~) and a low content of ethylene oxide (about 2 to 6 ethylene oxide units per molecule).

131784q Suitable ether compounds can be repre~ented by the followiny general formula RO(CH2CH20~nH
wherein R is a C'2-C~ alkyl group, and n i5 a number of ~rom about 1 to 6, on average.
Specific examples of suitable ether compounds include ethylene glycol monoethyl ether ~C2H5-0-CH2CH20H~, diethylene glycol monobutYl ether (C4Hg-0-(CH2CH20)2H)~ tetraethylene glycol monobutyl ether (C8H17-0-(CH2CH20)4H), etc. Diethylene glycol monobutyl ether is especially preferred.
Further improvements in the rheological properties of the liquid detergent composition6 can be obtained by inc]uding in the composition a small amount of a nonionic surfactant whlch has been modified to covert a free hydroxyl group thereof to a moiety having a free carboxyl group. As disclosed in Canadian patent application Serial No. 478,379, the free carboxyl group modified nonionic surfactants, which may be broadly characterized as polyether carboxylic acids, function to lower the temperature at which the liquid nonionic forms a gel with water. The acidic polyether compound can also decrease the yield stress of such dispersions, aiding in their dispensibility without a corresponding decrease in their stability against settling.
The invention detergent compositions also include water soluble and/or water insoluble detergent builder salts.
Typical suitable builders include, for example, those disclosed in U.S. Patents 4,316,812; 4,264,466 and 3,630,929. Water soluble inorganic alkaline builder salts which can be usad along `! ~

1317~
with the detergent compound or in admixture with other builders are alkali ~etal carbonates, borates, phosphates, polyphosphates, bicaebonates, and silicates. Ammonium or substituted ammonium salts can also be used. Speclfic examples of such salts are sodium tripolyphosphate, sodium carbonate, ~odium tetrabofate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, and potassium bicarbonate. Sodium tripolyphosphate ~TPP) is especially p~eferred. The alkali metal silicates are useful builder salts which al50 function to make the composition anticorrosive to washing machine parts. Sodium silicates o Na2O/SiO2 ratios of from 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same can also be used.
Another class of builders highly useful herein are the water insolub:Le aluminosilicates, both of the crystalline and amorphous type. Various crystalline zeolites (i.e.
aluminosilicates) are described in British Patent 1,504,168, U.S.
Patent 4,409,136 and Canadian Patents 1,Ot2,835 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 ( M 2~ ) x ( A1 23 ) y - ( 5 i2 ) z - WH 2 :
where x is 1, y is from 0.8 to 1.2 and preferably 1, z is fcom 1.5 to 3.5 or higher and preferably 2 to 3 and W is from o to 9, preferably 2.5 to 6 and M i~ pre~erably sodium. A typical zeolite is type A or similar structure, with type 4A
particularly preferred. The pre~erred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400 meq/g~

1 31 7~9 ¦ 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 purlfied form (i.e. free ¦from grit, sand, etc.) suitable for detergents invariably ¦ contains at least 50~ montmorillonite and thus its cation ¦ exchange capacity is at least about 50 to 75 meq per 100 g of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1, 2, l 3 and 4 by Georgia Kaolin Co~ These bentonites are kno~n to ¦ soften textiles as described in ~ritish Patents 401,413 and 461,221.
I Examples of organic alkaline sequestrant builder salts ¦ which can be used along with the detergent or in admixture with other organic and inorganic builders are alkali metal, ammonium ¦ or sustituted ammonium, aminopolycarboxylates, e.g. sodium and ¦ potassium nitrilotriacetates (NTA) and triethanolammonium N-(2-¦ hydroxyethyl)nitrileodiace~ates. Mixed salts of these polycarboxylates are also suitable.
l Other su;table builders of the organic type include 2S ¦ carboxymethylsuccinates, tartronates and glycollates~ Of ¦ special value ar~ the polyacetal carboxylates. The polyacetal ¦ carboxylates and their use in detergent compositions are ¦ described 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 4,224,420î 4,225,6B5; 4,226,960; 4,233t422 1 3 ~ 7849 4,233,423; 4,302,564 and 4,303,777. Also relevant are Canadian Patent Nos. 1,148,831; 1,131,092 and 1,174,934.
Since the compositions of this invention are generally hlghly concen~rated, 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 carboxylic acid having high calcium 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 Solcolan* CP5 which is a copolymer o~ about equal moles of methacrylic acid and maleic anhydride, completely neutralized to form the sodium salt thereof.
In addition to detergent builders, various other detergent additives or adjuvants may be present in the detergent product to give i~ additional desired properties, either of functional or aesthetic nature. Thus, there may be included in the formulation, mlnor amounts of soil suspending or antiredeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl alcohol methyl cellulose; optical brighteners, e.g. cotton, polyamide and polyester brighteners, ~or example, stilbene, triazole and benzidine sulfone composition , 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 subtilisln, bromelin, papain, trypsin and pepsin, as well as amylase type enzymes, lipase type enzymes, and mixtures thereo~t bacterlcides, e.g.

~Trade-mark 17 A'l`

1 31 78~q tetrachlorosalicylanilide, hexachlorophene fungicidess dyes pigments (water dispersible); preservativesS 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; a~d anti-foam agents or suds-suppressors, e.g. silicon compounds can also be used.
sleaching agents are classified broadly for convenience as chlorine bleaches and oxygen bleaches. 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 spot-treat a fabric undesirably stained in some manner. Other active chlo~ine bleaches, such as chlorinated cyanuric acid, although somewhat safer than sodium hypochlorite, also suffer from a tendency to damage fabric and cause localized over-bleaching. For these reasons, chlorine bleaches can seldom be used on amide-containing fibers ~uch as nylon, silk, wool and mohair. Furthermore, chlorine bleaches are par~icularly damaging to many flame retardant agents which they render ineffective after as little as five launderings.
Of the two major ~ypes of bleaches, oxygen-releasing and chlorine-relea~ing, the oxygen bleaches, sometimes re~erred to as non-chlorine bleaches or "all-fabric" bleaches, are more advantageous to use in that oxygen bleaching agents are no~ only highly effective in whitening fabrics and removing stains, but they are also safer to use on colors. They do not attack 1317~49 fluorescent dyes commonly used as fabric brighteners or the fabrics to any serious degree and they do not, to any appreciable extent, cause yellowing of resin fabric finishes as chlorine bleache~ are apt to doO Both chlorine 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.
A~ong 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, particularly in the United States, employ quite moderate washing ¦ temperatures (20C, to 60C), low alkalinity and short soaking ¦ times, oxygen bleaches when used in such systems are capable of only mild bleaching action. There is thus a great need for substances which may be used to activate oxygen bleach at lower temperatures.
Various activating agents for improving bleaching at lswer temperatures are known. These activating aqents are roughly divided into three groups, namely ~l) N-acyl compounds such as tetracetylethylene diamine (TAED), tetraacetylglycoluril and the like; (2) acetic acid esters of polyhydric alcohols such as glucose penta acetate, sorbitol hexacetate, sucrose octa i 31 7849 ¦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 with the per compound to form peracids, such as peracetic acid from TAED, or sa~ts thereof which react more rapidly with oxidizable compounds than the per co~pound itself. In accordance with this invention, the peroxygen compound is used in admix~ure with an activator therefor.
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 l 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 lS ¦ (e.g. 1 micron). Preferably less than about 10%, especially less l than about 5% of all the suspended particles have particle sizes ¦ greater than 10 ~icrons, compositions whose dispersed particles are of such small size have improved stability against separation I or settling on storage.
¦ In the 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 ea~h 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 grinding : balls. For larger scale work a continuously operating mill in which there are 1 mm or 1.5 mm diameter grinding balls wockinq in 30 a very small gap between a stator and a rotor operating at a 13178-~9 relatively high speed ~e.g. CoBall mill) may be employed. When using such a mill ! it is desirable to pass the blend of nonionic suefactant and solids first through a mill which does not effect such fine grinding (e.g. a colloid mill) to reduce the particle size to less than 100 microns ~e.g. to about 40 micron ) prior to the step of grinding to an average part~cle diameter below about 10 microns in the continuous ball mill.
In the preferred heavy duty liquid detergent compositions of the invention, typical proportions (based on the total composition, unless otherwise specified) 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 as about 40 to 60~ this phase may also include minor amounts of a diluent such as a glycol, e.g.
polyethylene glycol (e.g. "PEG 400"), hexylene glycol, etc. such ~; as up to 10%, preferably up to 5%, for example, 0.5~ to 2~. The weight ratio of nonionic surfactant to ether compound when the latter is present is in` the range o from about 100:1 to l:lr preferably from about 50:1 to about 2:1.
Sugar ester of this invention, ~eom about 4~ to about 15~, preferably about 6 to about 8~.
Polyether carboxylic acid gel-inhlbiting 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 l00 parts 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 13178~

part, e.g. about 0.2 to 0.5 part, per part of the nonionic surfactant.
Acidic organic phosphoric acid compound, as anti-settling agent; up to 5%, for example, in the range of 0.01 to 5~, such as about 0.05 to 2~, e.g. about 0.1 to 1%.
Suitable ranges of the optional detergent additives are: enzy~es - O to 2~, especially 0.7 to 1.3%; corrosion inhibitors - about O to 40~, and preferable 5 to 30~; anti-foam agents and suds-suppressors - O to 15~, preferably O to 5%, for example 0.1 to 3~; thickening agent and dispersants - O to 15~, for example 0.1 to 15%, for example 0.1 to 10%, preferably 1 to 5%; soil suspending or anti-redeposit~on agents and anti-yellowing agents O to 10~, preferably 0.5 to 5%; colorants, ¦ perfumes, brighteners and bluing agents total weight 0~ to about 1 2~ and preferably 0~ to about 2~ and preferably 0% to about 1 pH modifiers and pH buffers - O to 5% preferably O to 2%:
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 o~ the detergent composition.
In this application, all proportions and peecentages are by weight unless otherwi~e indicated. In the examples, atmospheric pressure is used unless otherwise indicated.
Example 2S A concentrated non-aqueous built liquid detergent cOmposition is formulated from the followlng ingredients in the amounts specified. The composition is prepared by mixing and finely grinding the following ingredient~ to produce a liquid suspension. In preparing the mixture for grinding the solid ingredient~ are added to the nonionic surfactant, with TPP being 1317~9 added last.

Wei~ht Nonionic surfactant (etho~ylated-propoxylated 21 C13-C15 fatty alcc,hol) Dowanol DB - nonionic surfactant 21 / , Glucose ester S 1670 (stearic acid deri.vative) : Sodium tripolyphosphate (TPP) - builder salt 31.3 Sokalan CP5 - anti-encrustation agent 2 Dequest 2066 - sequestering agent 1 Sodium perborate monohydr~te - bleaching agent 9 Tetraacetylethylenediamine (TAED) - bleach acti~ator 4.5 Urea - stabilizer Sodium carboxymethylcellulose (CMC) - anti-yellowing agent 1 Esperase enzym~ 0.8 Termamyl~ enzyme 0.2 : : Tinopal ~TS-X - optical brightener 0~4 : ~ Tio2 - whitening agent Q.2 : Perfume 0.6 : : : ` :

The above composition is stable in storage, dispenses readily in cold wash water and imparts excellent detersive : effects to:the wash load~
It i~ to be understood that the foregoing detailed description is given merely by way of illustration and that : 25 variations may be made therein without departing from the spirit and scope of the invention.

~ r~

Claims (18)

1. A heavy duty laundry detergent composition comprising a nonionic surfactant, a bleaching agent, a bleach activator and, as a detergency booster, a sugar ester esterfied with at least one fatty acid chain.
2. The composition of claim 1 wherein the sugar ester is a glucose ester.
3. The composition of claim 1 wherein the fatty acid is stearic acid.
4. The composition of claim 1 wherein the fatty acid is lauric acid.
5. The composition of claim 1 wherein the bleaching agent is sodium perborate monohydrate and the bleach activator is tetraacetylethylenediamine.
6. The composition of claim 1 wherein said fatty acid chain contains at least 10 carbon atoms.
7. The composition of claim 6 wherein said fatty acid chain contains 12 to 22 carbon atoms.
8. The composition of claim 1 wherein the heavy duty laundry detergent composition is in powdered form.
9. The composition of claim 1 wherein the heavy duty laundry detergent composition is in liquid form.
10. The composition of claim 9 wherein the heavy duty liquid composition is an aqueous liquid composition.
11. The composition of claim 9 wherein the heavy duty liquid composition is a non-aqueous liquid composition.
12. A non-aqueous heavy duty laundry composition comprising a suspension of insoluble particles of builder salt, a bleaching agent, a bleach activator and, as a detergency booster, a sugar ester containing at least one fatty acid chain, dispersed in liquid nonionic surfactant.
13. The composition of claim 12 wherein the sugar ester is glucose ester.
14. The composition of claim 12 wherein the fatty acid is stearic acid.
15. The composition of claim 12 wherein the fatty acid is lauric acid.
16. The composition of claim 12 wherein the bleaching agent is sodium perborate monohydrate and the bleach activator is tetraacetylethylenediamine.
17. The composition of claim 12 wherein the fatty acid chain contain at least 10 carbon atoms.
18. The composition of claim 17 wherein the fatty acid chain contain 12 to 22 carbon atoms.
CA000588765A 1988-01-21 1989-01-20 Sugar esters as detergency boosters Expired - Fee Related CA1317849C (en)

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US4889651A (en) * 1988-01-21 1989-12-26 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
US5047168A (en) * 1988-01-21 1991-09-10 Colgate-Palmolive Co. Sugar ethers as bleach stable detergency boosters
US4800038A (en) * 1988-01-21 1989-01-24 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators detergency boosters and fabric softeners
DK27789D0 (en) * 1989-01-23 1989-01-23 Novo Industri As DETERGENT - COMPOSITION
GB8922593D0 (en) * 1989-10-06 1989-11-22 Unilever Plc Detergent composition
US5688757A (en) * 1990-01-22 1997-11-18 Novo Nordisk A/S The Procter & Gamble Co. Sugar derivatives containing both long and short chain acyl groups as bleach activators
DE19507668C2 (en) * 1995-03-04 2000-01-27 Suedzucker Ag Detergent formulations containing an acylated disaccharide carboxylic acid
GB9606913D0 (en) 1996-04-02 1996-06-05 Unilever Plc Surfactant blends processes for preparing them and particulate detergent compositions containing them
JP6468738B2 (en) * 2014-06-26 2019-02-13 ライオン株式会社 Liquid cleaning agent

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GB1548379A (en) * 1975-05-19 1979-07-11 Jeyes Group Ltd Bleach compositions
ZA841402B (en) * 1983-03-15 1985-10-30 Colgate Palmolive Co Bleaching and laundering composition free of water-soluble silicates
US4483778A (en) * 1983-12-22 1984-11-20 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
IN165978B (en) * 1985-08-20 1990-02-17 Colgate Palmolive Co
US4889651A (en) * 1988-01-21 1989-12-26 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
US5047168A (en) * 1988-01-21 1991-09-10 Colgate-Palmolive Co. Sugar ethers as bleach stable detergency boosters
US4800038A (en) * 1988-01-21 1989-01-24 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators detergency boosters and fabric softeners

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DK17789D0 (en) 1989-01-17
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