AU616438B2 - Antistatic and fabric softening liquid detergent composition - Google Patents

Description

COMMONWEALTH OF AUSTRALIA 6 8 Patents Act 1952 C OMPLETE SPECIFICATION

(ORIGINAL)

Application Number Lodged Complete Specification Lodged Accepted Published Priority 27 October 1987 Related Art at It I

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o e 'tIC #1cC It C 4 IC 4c I CC C C C IP C I C Name of Applicant Address of Applicant Actual Inventor/s Address for Service COLGATE-PALMOLIVE COMPANY 300 Park Avenue, New York New York 10022 United States of America Heidrun E. Maaser F.B. RICE CO.

Patent Attorneys 28A Montague Street, Balmain N.S.W. 2041 6 4 666% S 6o 6 Is Complete Specification for the invention entitled: ANTISTATIC AND FABRIC SOFTENING LIQUID DETERGENT COMPOSITION The following statement is a full description of this invention including the best method of performing it known to us/£i:- This invention relates to liquid detergent coiapositions having antistatic and fabric softening properties.

More particularly, it relates to such compositions which comprise narrow range ethoxylate nonionic detergent (NRE), antistatic and fabric softening cationic compound, and water.

The novel antistatic and fabric softening liquid detergent compositions of this invention, which may hereafter be referred to as softergents, for brevity, are unexpectedly better in detergency against oily soils and/or stains than compositions which are identical except for replacement of the NRE with broad range ethoxylate detergent This unexpectedly beneficial effect is especially pronounced when the invented softergents are used in washing aat¢ 8 a& a variety of fabrics stained with oily soils/stains and when goo the washing is effected at comparatively low temperatures, 20 0

C.

In the prior art it has been disclosed that cationic compounds may be ixcorporated in detergent compositions, such as liquid detergent compositions, to make washed laundry soft and ,antistatic, which is especially important when laundry is being dried in an automatic laundry dryer, in which electro- S*S static charges are often accumul ;ted on the laundry, leading to undesirable clinging together of dried laundered items and to crackling and sparking of such items when the electro- 2 5 static qharges thereon are discharged. It has also been laknown that cationic compounds, when incorporated in detergent compositions, have negative effects on detergency. Such negative effects are expected when anionic detergents are employed, because of chemical reactions between the anionic and cationic materials, but it has also been observed that detergency is diminished when cationic compounds are included in nonionic detergent compositions.

With respect to the compositions of the present invention it has been discovered that such expected detrimental effects of cationic compounds on detergency do not result when NRE's are employed in place of BRE's, and detergency is improved, compared to similar detergent compositions based on BRE's. Such improved detergency of the NRE compositions is not attributable to any better cleaning obtained 0 15 because the NRE is a better detergent than the BRE in liquid i 00 So,0 detergent compositions broadly; rather, it depends on the 0 0 0 j ooo combinations of NRE and cationic compounds in the softergents.

0000 0o. In accordance with the present invention an antistatic oo 0000 o,00 0 and fabric softening liquid detergent composition, or softergent, S 00o comprises a detersive proportion of a narrow range ethoxylate 0 o06 nonionic detergent (NRE), an antistatic and fabric softening 9 00 *000 proportion of an antistatic and fabric softening cationic compound, and water, which liquid detergent composition is of un- 6000 proved detergency vs. oily soils on fabric to be washed with °25 wash water solutions of the detergent composition, compared to Bi "ooo 00 0 0 66 17 similar compositions in which the nonionic detergent component is a broad range ethoxylate nonionic detergent (BRE). Also within the invention are processes for washing laundry in wash water in an automatic washing machine, using the described compositions or components thereof.

A search of the prior art has resulted in the finding of U.S. patent 4,564,463, which relates to liquid laundry detergents based on mixeA nonionic and anionic detergents, including higher fatty alcohol ethoxylates and alkylbenzene sulfonates.

U.S. 4,441,881 describes spray dried particulate detergent compositions containing what are characterized therein as ethoxylated alcohols of narrow ethylene oxide distribution.

It is taught in that patent that improved soil shield properties may be imparted to synthetic fabrics by washing such a I C fabrics with the described detergent composition.

pI a.r In addition to the mentioned patents, it is accepted prior art that commercial fabric softening and antistatic t I liquid detergents have been manufactured based on nonionic and anionic detergents, which include cationic compounds to soften laundry and remove static charges from washed and dried laundry t tCC C c or to prevent development of such charges on such laundry during drying. However, prior to the present invention, so far as is a tknown to applicant, none of the patents or literature references disclosed or suggested the present compositions and none 2 recognized that improved detergency could he obtained from I LI a liquid detergent compositions including NRE and cationic compound, instead of corresponding BRE compositions.

The NRE's that are employed in the invented softergents are nonionic detergents in which the hydrophilic moiety is an ethylene oxide polymer of comparatively narrow distribution, which distinguishes such detergents from those of similar types but wherein the ethylene oxide polymer is of broader distribution (BRE's). Generally, it will be desirable, for improved detergency of the present compositions, for the ethylene oxide chain (including terminal ethanol) to be of such narrower distribution that at least 80% of the nonionic detergent is of a number of ethylene oxide groups bracketing the average number of ethylene oxide groups in the NRE and in the range of to wherein n is the average 0 00 o .o15 number of ethoxies in the NRE detergent. In some instances g 0 Q 000 ooo0 the bracketing may be from to or from to 00oo 0 0 Usually n will be about 6 or 7 but sometimes it can 0o°' be in the range of 4 to 12. Preferably, the percentage of 0 0 t nonionic detergent of ethoxy content in the to (n+3) range or either of the other two ranges previously mentioned I a 0'J will be at least 85%,and more preferably at least Normally, the lower ethoxylated nonionic detergents or S: surfactants, such as those of 1 to 3 ethoxy groups per mole, will be limited to no more than preferably being less S "'25 than 2% and more preferably being less than except when *0 S 0 0 0 n is lower than 7, when such percentages are not applicable to the detergents of ethoxy contents in the n-3 range. Al-o, when n is lower than 7 the "bracketing" will preferably be n±2 or n-1 to n+3. It is difficult to remove the lower ethoxylates entirely, due to the manufacturing method, which produces a range of nonionic detergents of different ethoxy contents, but in the NRE's the distribution curve may be considered as being "squeezed", resulting in a more uniform product. Corresponding BRE's, even those wherein n is 7 or more, will often have more than 5% of lower ethoxy content. Of course, it is also desirable to limit the proportion of unethoxylated lipophile and the NRE's will normally contain less than 1% thereof and often less than 0.5% thereof, t whereas BRE's often contain more than 1% of the lipophile, -,35 higher fatty alcohol.

The nonionic detergents (NRE's) of the invention are manufactured catalytically via reaction of ethylene oxide and 4a C C a suitable lipophile or lipophilic material. Higher alcohols, usually fatty or linear alcohols of 12 to 18 carbon atoms per molecule, which are usually preferably saturated, are the desired reactants with ethylene oxide to make the desired nonionic detergents for the compositions of this invention, t.o a but Oxo-type alcohols and middle phenols, such as nonyl phenols, may also be useful. Preferably the higher fatty o 25 alcohol moiety will be of 12 to 16 carbon atoms and will be S 0 o linear, and more preferably it will be of 12 to 14 or 15 carbon atoms, lauryl alcohol, myristyl alcohol and mixtures thereof. The average ethoxy content of the NRE will be in the range of 4 to 10 EtO's per mole, preferably being 5 to 9 and more preferably, 6 to 8, 6.5 or 7. Other members of the wellknown class of nonionic detergents, such as higher fatty acid esters of polyethoxy ethanol (also of narrow range ethoxylate distribution) may also be useful in some compositions and for particular applications. However, normaly a higher fatty alcohol is employed as the source of the lipophile and the product is a narrow range ethoxylate nonionic detergent that meets the NRE conditions previously recited, with the ethoxy number (n) distribution curve preferably being peaked at n.

NRE's that are presently available are preferably V 1.5 manufactured by catalytic reactions which promote the production oo 000. of a narrow range of polyethoxylates, preferably of peaked a a Z ethoxy number distribution, rather than the more conventional 0011 a broad range of polyethoxylates in the more generally available commercial alkoxylated lipophile detergents, Products produced catalytically are characterized by a normal distribution curve when ethylene oxide content (abscissa) is plodded against weight percent (ordinate) but the peak of the "bell-shape" 1,101 curve is much higher for the NRE than for the BRE nonionic 0 detergents. It has been opined that similar products, of similar distribution curves, may be made by "topping" and "bottoming" BRE's or other NRE's, by removing higher and lower polyethoxylates by solvent extraction, distillations and other suitable physical processes, but it is not thought Ir 7 that such detergents will be as useful as those herein mentioned as preferred because of the probable absence of the same type of "n peaking". The BRE nonionic detergents will include lower percentages of a narrow range of desired polyethoxylates, such as those of 4 to 10 EtO's, often less than 60%,compared to more than 80% for the NRE's. They will also often include at least about 1% of all unit degrees of ethoxylation from 1 to 16 or 1 to 20, even when it is desired to have the average or mean ethylene oxide content at 6 or 7 moles per mole. On the other hand, the NRE which averages 7 moles of EtO per mole will usually contain no higher polymer of ethylene oxide than 14 or 15, and the proportion of polyoxyethylene in the 4 to 10 range is significantly increased. Such increase, the narrower distribution range of the polyethoxy moieties and the "peaked n" thereof apparently change the properties of the NRE for the better S when it is included in a softergent composition of this inven- *u tion. The reason for this difference is not understood at present.

Among the preferred NRE nonionic detergents employable in accordance with the present invention is Tergito Nonionic Surfactant 24-L-60N, which is of the formula S RO(CH 2 CH20) H, wherein R is a mixture of C 12 and C 14 linear "C alcohols and n averages about 7.0. Such product has a cloud point of 60 0 C. for a 1% aqueous solution and is a narrow range ethoxylate. Its properties are described in a product informa- ,25 tion bulletin issued by the manufacturer, Union Carbide tO Corporation, which carries the date of April, 1987. Other «o Li d sd

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-7- Tergitol Nonionic Surfactants which may also be employed, at least in part, with the 24-L-60N, include 24-L-45N, 24-L-75N and 26-L-60N, wherein the 45, 75 and 60 indicate cloud points, in degrees Centigrade. Also, similar products, manufactured by Shell Chemical Company, which have been identified as Shell 23-7P and Shell 23-7Z, may be substituted, although the results are not considered to be as good as for the preferred compositions.

The antistatic and fabric softening cationic compound of the present liquid detergent compositions may be any suitable such compound, such as an imidazolinium salt or a quaternary ammo~iium salt. Both types of fabric softeners are described in U.S. patent 4,000,077. Of the two types of softeners the quaternary ammonium salts are preferred, and of these the 15 quaternary ammonium halides, such as the quaternary ammonium o '0 chlorides, are more preferred.

The quate;:nary ammonium salt fabric softening 0000oooo compound is preferably of the formula go 0

~R

4 20 R R'N-R 'P 00 4 .0.000 wherein R1 and R 2 are lower alkyl of 1 to 3 carbon atoms, prefer- 0 ably 1 to 2, and more preferably 1, R 3 is higher alkyl of 10 to 0090 o 25 20 carbon atoms, preferably 12 to 18, and more preferably 16 to 18, tallowalkyl, R 4 is alkyl of I to 20 carbon atoms 0000 o 0 0 (higher, middle or lower alkyl), and X- is a salt formi:.g anion, 0 0* preferably either chlorine, bromine or methyl sulfate, and more preferably chlorine. In such quaternary salts RI and R are preferably the same lower alkyl, methyl, and

R

3 and R 4 are preferably the same higher alkyl or one is higher alkyl and the other is methyl, with the most preferred fabric softeners being trimethyl tallowalkyl ammonium chloride and dimethyl di-tallowalkyl ammonium chloride. The useful quaternary ammonium halides also include those wherein the higher alkyl(s) is/are hydrogenated tallowalkyl, cocoalkyl, stearyl, cetyl, myristyl and/or lauryl (which sometimes may be ethoxylated), and wherein the lower alkyls are methyl and/or ethyl. Also, other anions than halogen and methyl sulfate may sometimes be substituted.

The fluorescent brightening compound(s) of the present compositions is/are one(s) which is/are substantive to the washed laundry and serve(s) to convert invisible 15 radiation, such as ultraviolet rays, to visible light, thereby appearing to whiten laundry surfaces on which it/they has/have been deposited. Such fluorescent brighteners constitute a t t well-known class of materials in the detergent art and therefore they need not be described at great length herein. Suffice it to say that they will normally be of the stilbene type, and Scc more specifically, they will be of the stilbene sulfonic acid ,or sulfonic salt type. Among such brighteners employed in the compositions of the present invention is that manufactured by Mobay Chemical Corp. and sold under the trade mark Phorwite BBH766 pure, which is 4'4-bis(4-anilino-6-[bis(2-hydroxyethyl) amino]-s-triazin-2-2yl amino-2,2-stilbene disulfonic acid.

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r Although the mentioned fluorescent brightener operates very effectively in the present compositions, it is considered that other types of substantive brightening agents may be employed instead, such as those mentioned in Example 1, without loss of the unexpected beneficial improvement in detergency characteristic of the invented compositions.

An anionic detergent is also included in preferred embodiments of the present liquid detergent to improve the substantivity of the fluorescent brightener, and also to add its detersive properties to the composition (anionic detergents being especially effective in removing particulate soils from fabrics). The anionic detergent is preferably of the sulfate or sulfonate type, normally being in the form of a water soluble salt, such as an alkali metal salt, sodium *15 salt. Such detergents are described at length in various

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texts, including Surface Active Agents (Their Chemistry and S Technology) by Schwartz and Perry, and the various annual 8 editions of John W. McCutcheon's Detergents and Emulsifiers.

Although higher fatty alcohol sulfates and various other S '20 sulfates and sulfonates may be employed, it is preferred S^ that the detergent be a higher alkylbenzene sulfonate, such as one wherein the alkyl is of 12 to 18 carbon atoms. More preferably, the alkyl is linear and is of 12 to 16 carbon <C t atoms, dodecyl or lauryl, and the cation is sodium, Disulfonated anionic detergent salts may also be operative in the compositions of this invention.

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To help to solubilize the fluorescent brightener and to buffer the liquid detergent composition to a desirable pH a lower alkanolamine may be present in the liquid detergent composition, and it will contain 1 to 3 carbon atoms in the lower alkanol group(s) thereof. Preferably, the alkanolamine is a trialkanolamine and more preferably it is triethanolamine.

A hydrotropic compound, such as a benzene sulfonate or lower alkyl benzene sulfonate, wherein the lower alkyl is of 1 to 3 carbon atoms, is normally present in the invented compositions to assist in solubilizing some components of the compositions which could otherwise settle out of the aqueous medium. Preferably, such hydrotrope will be present as an alkali metal salt, usually as a sodium salt, and the hydrotrope will be a benzene sulfonate, a xylene sulfonate 15 or a cumene sulfonate.

Also to promote solubility of the various components of the detergent composition, a polar organic co-solvent c will usually be present, which will preferably be a lower alkanol, such as ethanol or isopropanol, with ethanol (normally 20 denatured) being preferred.

t The water employed may be tap water, distilled water S or deionized water, or it may be treated water, such as boiler S feed water taken from the boiler feed system of the manufacturing plant. It is normally desirable that such water be of 25 relatively low hardness, and normally it will be of a hardness f C C a aac a t i S CC af a a a e C

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C C 4 6' a CC a a C Cl a a

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6e6 666 Ca a a I less than 100 as CaCO 3 preferably less than 50 p.p.m., and more preferably it will be of about zero hardness.

Various adjuvants may be included in the invented composition, of which perfume and colorant will be those most commonly employed. The perfume will normally be lipophilic but will be readily solubilized by the surface active and solvent components of the composition. The colorant may be a water dispersible finely divided pigment but it is usually preferable to employ a water soluble dye or mixture of suitable such dyes, although mixtures of dyes and pigments are also feasible. Another component of the invented compositions which might be considered to be an adjuvant is an acidic agent which may be employed to adjust the pH of the liquid detergent downward in those instances where the triethanol- 15 amine and any other alkaline materials present have increased the pH beyond an intended range. Among the useful acidifylift ing agents that may be employed the most preferred is citric acid, which may form a buffer with triethanolamine and other alkaline materials in the formula.

V( c 20 The proportions of the various components of the tZI present liquid detergent compositions will normally be held X within certain ranges to obtain a product of desired charactert istics, which will be of improved detergency against oily stains deposited on a variety of fabrics, and will also be of acceptable appearance and physical characteristics. The major j' IL, component of the invented liquid detergent compositions is I' water and the proportion thereof will normally be a sufficiently solubilizing proportion (in conjunction with any co-solvent and hydrotrope that may be present) for the NRE, the cationic compound and. other components of the composition. The water content will be within the range of 30 to 70%, preferably being 40 to 60%, more preferably being 50 to 60%, and most ly being 53, or about 55%. The proportion of NRE will be a detersive proportion, which usually will be in the irange of to 35%, preferably being 15 to 30%, more preferably being 18 to 25%, and most preferably being about 21%. The proportion of cationic compound will be an antistatic and fabric softening proportion, which will usually be in the range of 2 n preferably 3 to 10%, more preferably 4 to 8% and most preferably about 6%.

a..When fluorescent brightener is present the proportion thereof will be within the range of 0.1 to preferably 0 64 being 0.1 to 1% and more preferably being about The I ranges of proportions for anionic detergent are 2 to 0 4 preferably 3 to 10% and more preferably about Most preferably the molar ratio of cationic softener to anionic detergent is in the range of 0.9:1 to 1:1.1, 1:1. The ranges for alkanolamine solubilizer for the fluorescent brightener are 0.3 to preferably 1 to and more preferably about The proportion of hydrotrope will be in the range of 2 to preferably 3 to and more preferably about When cosolvent is present the proportion thereof will be in the range of 3 to 15%, preferably 4 to 10% and more preferably about Any balance remaining may be of adjuvants, with a normal range for such being 0.1 to Such adjuvants normally include perfume and colorant and the percentages of these will normally be 0.2 to preferably 0.3 to 1% and more preferably about and 0.05 to preferably 0.1 to 0.5% and more preferably about respectively. However such proportions will depend to some extent on the odor level of the product components and their color. Citric acid or other acidifying or neutralizing agent may be considered as another adjuvant but the proportion of such material utilized will normally be only that required to adjust the pH of the liquid detergent composition within a desired range. Such a proportion will usually be in the range of 0.05 to The invented liquid detergent compositions made Swill normally be clear in appearance but can intentionally be made cloudy, opaque or pearlescent. The pH of the product will4 im=aliy be in the range of 7 to 8, ideally being about 7.5, and the viscosity will 4 iermly be in the range of more.

to 125 centipoises at 25 0 C.,4preferably being about 100 cp.

Manufacturing the invented compositions is relatively simple, with no critical operations being required, except for making sure that the fluorescent brightener is dissolved, S usually in alcoholic co-solvent. Usually, the tormula r_

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proportion of water or about 80% or more of such proportion is pumped to a mixing vessel or tank and the various components of the detergent compositions are serially admixed in the aqueous medium, followed by addition of the balance of water.

Sometimes the co-solvent may be added first and at other times it may be retained for subsequent addition with the balance of water, at or near the end of the mixing process. In other instances particular components, such as the brightener, may first be dissolved in the co-solvent or sometimes in a part of the aqueous medium containing the hydrotrope. Although such techniques may facilitate more rapid manufacture of the liquid detergent, in desired form and of desired appearance, usually the intended product is obtainable without practicing such process variations (except for dissolving the brightener).

After admixings of all the components are completed, the balance of water, if any, may be added, also with stirring, and the t i i: pH may be adjusted. After pH adjustment and checking of the 'tic viscosity to make sure it is within specifications, the product V may be bottled directly or may be filtered and bottled.

Using the invented compositions is simple and satisfactory, from the user's standpoint, there being little for the consumer to do except to measure out the desired amount of the liquid detergent composition and add it to the wash water 0 C in an automatic washing machine,. Such machines will hold C 25 to 70 liters of water, with about 67 liters being common, and

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1/2 cup of liquid detergent, which corresponds to about 120 grams thereof, will be employed per wash. However the composition formula can be changed so that 1/4 cup or 60 grams charged to the washing machine would wash effectively. The laundry (usually about 6.5 lbs. or 3 kg.) is added to the wash water and the machine is turned on. The wash water will normally be of a hardness no greater than 300 as CaCO 3 and the water temperature will normally be in the range of 10 to 90 0

C.

It is recognized that rarely, if ever, following American practice, will the temperature of the wash water approach boiling, but the washing processes of this invention are operable at such higher temperatures. Preferably the water hardness will be no higher than 200 with the range of i 100 to 200 p.p.m. being, considered normal. Of course, lower hardness wash waters may also be used. Within the broad o 09 0 0 temperature range previously mentioned a preferred range is 10 to 50 0 C. and for most significantly improved detergency, o compared to detergencies obtained when similar BRE composia 0 0 tions are employed, such range will be 10 to 25 0 e.g., 20 about 20 or 21 0

C.

.0 Normally the washing cycle will be 5 to 30 minutes, Swith a rinse cycle of 1 to 5 minutes, and sometimes a plurality, usually 2 or 3, of ririe cycles may be used. Drying times will usually be between 10 and 60 minutes, with most drying times in the 20 to 40 minutes rangeand. drying will usually be so 0 9 at "normal" drying temperatures for automatic laundry dryers, rather than at "high" settings. Of course, both washing and drying conditions will be determined by the nature of the laundry, the soil and/or stains on it, and the characteristics of the washing and drying apparatuses being used. Top loading automatic washing machines will usually be employed, but sideloading machines are also acceptable. The laundry charged will normally be from 2 to 4 kilograms, about 3 kg.

In, the washing process it will be highly preferred to add the described liquid detergent composition to the washing machine but it is also feasible to add its various components, alone or in mixtures, to the washing machine, to produce essentially the same wash water composition. The wash water resulting will contain a detersive proportion of NRE and a "15 fabric softening and antistatic proportion of cationic 1 compound. Such proportions will be in the range of 0.01 to i c 0.2% and 0.001 to respectively, preferably being 0.02 a to 0.1% and 0.002 to 0.05%, respectively, and more preferably C t C being 0.03 to 0.06% and 0.005 to 0.02%, respectively, e.g., about 0.04% and about 0.01%, respectively. The concentration C C of fluorescent brightener will be within the range of 0.0001 t to 0.01%, preferably 0.0002 to 0.005%, 0.001%. The Sconcentration of anionic detergent will be in the range of C t I t 0.001% to preferably 0.005% to about C C Q5 0.01%. Concentrations of other components of the liquid t t 1 I detergent composition (except water) in the wash water and ranges thereof, in percentages of wash water, may be obtained by multiplying such exemplified concentrations for the liquid detergent composition by 0.0018 for the ideal charge to the wash water, or lower and upper ranges of such concentrations may be calculated by multiblying the composition concentrations by 0.0010 (for the lower limit) and 0.0030 s *1 (for the upper limit). Thus, it is more preferred to employ the liquid detergent composition at a concentration in the wash water of about 0.18% but, depending on the nature of the laundry, such concentration may be within the range of 0.10 to 0.30% or within a narrower preferred range of 0.15 to 0.25%.

15 0 gooQ o0 O 000 4 0044 a d o oe o a o o The following examples illustrate but do not limit the invention. Unless otherwise indicated, in such examples and in this specification and the appended claims, all parts are by weight and all temperatures are in OC.

a o o04 b 0.

4404 4 004 0B 0 EXAMPLE 1 Component NRE Tergitol Nonionic Surfactant 24-L-60N 21.0 Monotallowalkyl trimethylammonium chloride Sodium linear dodecylbenzene sulfonate Sodium xylene sulfonate Ethanol Triethanolamine Fluorescent brightener (Phorwite BBH766, pure) 0.4 Perfume 0.4 Colorant 0.2 Citric acid (for pH adjustment) q.s.

Water (deionized) 53.5 100.0 A narrow range ethoxylate nonionic detergent which is a condensation product of higher fatty alcohol of 12-14 carbon atoms and s an average of 7 moles of ethylene oxide per mole, with over thereof of 4-10 ethoxylate groups per mole Stilbene-type fluorescent brightener (any of such brighteners 20 may be employed, preferably of the stilbene sulfonate or stilbene sulfonic acid types, such as other Phorwites, and Tinopals, e.g., Phorwite HRS, Phorwite BHC or Tinopal 5BM, or mixtures thereof) The percentage given is for compositions in which no citric acid was included. If citric acid is employed the percentage C tt t t 25 of water is decreased accordingly.

A liquid detergent of the above composition is made by C 4* admixing all the components with the water, in the following order: triethanola-mine, brightener, ethanol, hydrotrope (SXS), NRE, sodium dodecylbenzene sulfonate, quaternary ammonium chloride, citric acid (if needed to adjust the pH! to 7.5) and Optionally, the fluorescent brightener may be dissolved in aqueous ethanol and the other mentioned components may be admixed with half of the formula amount of water, with the balance of water being added last. The product resulting is a clear liquid. Optionally, a colorant may also be incorporated, such as about 0.5% of C.I. Acid Blue 80 (with the percentage of water being decreased accordingly). The viscosity of the liquid detergent is about 100 cp. at 25 0 C. The liquid detergent composition made is stable at room temperature for at least six months, without any stratification or settling out of components and the ,15. product remains clear and effective as a fabric softening and antistatic detergent composition of improved detergency (compared to similar BRE compositions) for at least that length of time.

The invented liquid detergent is tested against a *:control composition, identical therewith except for replacement of the Tergitol Nonionic Surfactant 24-L-60N by Neodol 25-7.

Ail The following is a description of the test procedure.

StA Maytag automatic washing machine is thoroughly rinsed before beginning the washing test. The mAchine is then filled with 64.3 liters of ta~p water and the hardness of the 25 water is adjusted by addition of calcium chloride and t 11 magnesium sulfate or other suitable water solt~ble calcium

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4and/or magnesium hardness salts, until it is of a hardness of 150 as CaCO 3 Agitation is begun and 1/2 cup (120 grams) of the test liquid detergent composition is added to the wash water, followed by thirteen sets (three in each set) of soiled test swatches, which were initially white before soilings. Such swatches include a variety of fabrics employed in the manufacture of clothing and other items to be laundered, among which are single knit polyester, double knit polyester, polyester/cotton blend, acetate and nylon. The swatches each measure about 7.6 x 8.9 cm. Different oily stains, such as French dressing, liquid makeup, soot in oil, etc., had been applied to the swatches, using a Benz Soiler for such applications, so that thirteen stain/fabric combinations resulted, each in triplicate. The washing machine cycle is set for ten ,15 minutes and the rinse cycle is two minutes. After completion S of the washing and rinsing the swatches are removed and are dried for thirty minutes (or until dry) in a Maytag automatic C C laundry dryer at "normal" drying setting. The stained swatches are then measured for reflectances, using a small area reflectometer (Gardner Average reflectometer readings (Rd) are calculated for each of the thirteen sets of stained swatches, and such S averages are added to arrive at a total Rd which is indicative t t of the extents of removals of the oily soils/stains by the detergent composition being tested. The h-her the Rd total

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Ccc t C I

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C C 7; ttCr It :E C

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C I (hereafter referred to as Rd) the whiter the swatch after washing.

The Rd for the liquid detergent of the formula given above is found to be 781 whereas that for the control composition based on Neodol 25-7 is 704. Such a difference, 77 units, is very significant, and the differences in stain removals are apparent to the naked eye. When the test is repeated, with the only difference being that the wash waters are at 38 0 C. instead of 21°C. (100°F. instead of the Rd total for the invented composition is 841 and that for the control composition is 789, which is also significant and represents an observable difference in stain removal. In a repeat of this experiment, using a new set of stained swatches, the Rd totals at 21 0 C. washing were 800 for the invented composition and 738 for the control, 0 a

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a which figures are consistent with those previously given.

o 'Also tested in such "repeat experiment" was a detergent composition in which instead of Tergitol Nonionic Surfactant 24-L-60N there was employed a topped 23-6.5 nonionic detergent.

20 Such nonionic detergent is a condensation product of a mole o.f higher fatty alcohol of 12-13 carbon atoms with 6.5 moles of ethylene oxide, from which higher fatty alcohol and lower alkoxylates (of 1-3 ethoxies) have been removed by distillation. The Rd total for the detergent composition incorporating such nonionic detergent instead of the 24-L-60N or 0 21 the 25-7 was 753, which is higher than that for the control but considerably lower than that for the invented composition.

Such result indicates that while removing any free higher fatty alcohol and lower ethoxylate of 1-3 ethoxy groups from the nonionic detergent is useful to improve the detergency of the present compositions, it is more desirable to "squeeze" the ethoxylate distribution curve or cause it to peak, by "removing" higher and lower ethoxylates, outside the 4-10 ethoxy range (for nonionic detergents averaging 6 to 8 ethoxy groups per mole), and such "removal" is preferably a result of the catalytic manufacturing process.

In a further repetition of the test comparisons of the invented composition to the control BRE nonionic detergentbased composition, at 21 0 C. the Rd totals were 750 and 725, t .15 and at 38°C. they were 795 and 747, for the experimental and S control detergent compositions, respectively. In such wash- Sings commercial products sold as liquid BOLD and liquid TIDE, were also tested and the invented composition was better in detergency than both commercial products at both 21 0 C. and 38 0 although the liquid TIDE was almost as good at 21°C.

St-C I I t t 1 EXAMPLE 2 For comparison with the first reported test in Example 1, in which Tergitol Nonionic Surfactant 24-L-60N was tested against Neodol 25-7, in a test of a liquid detergent composition with NRE vs. one with BRE as the nonionic detergent component thereof, other Tergitol Nonionic Surfactants were also tested in the same detergent composition. Such other surfactants were identified as 24-L-35N, 24-L-45N and 24-L-50N.

The Rd's for 21 0 C. and 38 0 C. washingswere 706 and 688, 743 and 745, and 746 and 743, respectively, compared to 781 and 841 and 704 and 789, for 24-L-60N and 25-7 formulas, respectively. Other tests run at the same time on liquid BOLD yielded Rd's of 654 and 747, respectively. Thus, all the 21°C. washes with NRE compositions yielded higher Rd's than the BRE composition and the commercial product.

However, results with the 35N, 45N and 50N NRE's were not as good as those for the 60N NRE and are not considered to be t as good as those for a 75N NRE. It appears that such differences S, in detergency are due to differences in ethoxylate distribution and/or differences in cloud points of the NRE's.

fEthoxylate distributions of the various NRE's are S reported in aTergitol Surfactants Technical Service Bulletin entitled Ethoxylate Distribution of Tergitol 24-L Nonionic Surfactants by Gas Chromatography, issued by the Ethylene Oxide Derivatives Division of Union Carbide Corporation.

rThe following table, Table 1, summarizes the ethoxylate Ic distribution (by gas chromatography) of the two preferred NRE's mentioned above, and of comparable BRE's.

2 i C mw .4 4, 4 4- .4 .44~.4 4, TABLE 1 Weight Percent of RO(cH 2

CH

2 0) nH n 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Total Tergitol 24-L-60N Tergitol 24-L-60 -0.6 1.3 0.2 0.9 0.4 1.8 1. 1 2.7 6.6 13.1 19.5 21.5 16.3 9.5 4.1 1.3 0.4 97.3 3.1 5.4 7.0 9.0 10.3 11. 1 11.2 10. 0 8.0 6.3 4.3 1.8 Tergitol 24-L-75N 0.3 0.0 0.2 0.4 1.2 3.1 7.6 14.3 20.3 20.6 15.5 8.8 3.9 0.9 97.1 Tergitol 24-L-75 0.9 0.6 1.2 3.6 5.3 6.8 8.6 10.6 10.9 10.5 9.4 7.6 2.2 85.6 91.5 25 100% recovery of the sample is not achieved due to holdup of higher ethoxylates in the GC column EXAMPLE 3 Component NRE (Tergitol Nonionic Surfactant 24-L-60N) 21.0 Sodium linear dodecylbenzene sulfonate 3.7 Sodium xylene sulfonate Quaternary ammonium chloride Mixture No. 87064 Ethanol Triethanolamine Fluorescent brightener 0.4 Perfume 0.4 Colorant 0.2 Citric Acid (for pH adjustment) q.s.

Water (zero hardness) 56.8 100.0 Akzo Chemie proprietary mixture No. 87064, of two di-higher alkyl dimethyl quaternary ammonium chlorides and one ethoxylated higher alkyl trimethyl ammonium chloride 20** Stilbene-type fluorescent brightener, like that of Example 1 This detergent composition-is made according to the method of Example 1 and is tested in the same manner. For ease of identification and comparisons it will be referred herein as Example 3(a).

I

I

o 0o tp00 *Y 0 44 4 'It' Ut., It 0( *4 Formula 3(b) is the same as Formula 3(a) except that 6% of sodium linear dodecylbenzene sulfonate is employed, together with 6% of the quaternary ammonium halide mixture so that the percentage of water is decreased by 3.3%.

Formula 3(c) is the same as Formula 3(a) except that 3.8% of sodium linear dodecylbenzene sulfonate is present, the quaternary ammonium chloride is monotallowalkyl monooctyl.

dimethyl ammonium chloride, and 6% of such quaternary salt is present, so that the percentage of water is decreased by Control experiments in which Neodol 25-7 is employed in replacement of Tergitol Nonionic Surfactant 24-L-60N are designated as such in the following table.

The following is a summary of the Rd's obtained for the invented composition (experimental) runs and for the controls after washings at 21 0 C. and 38 0

C.

TABLE 2 F'

I

ft <I2 Formula No.

3(a) 3(b) 3(c) Rd (21°C.) 24-L-60N 785 750 765 25-7 (control) 737 725 704 Rd (38 0

C.)

f4

[I

3(a) 3 (b) 3(c) 831 794 805 771 748 710 46'-- 4

I.

It is seen that the Rd's for the invented or experimental compositions are significantly higher than those for the controls. Additionally, liquid BOLD and liquid TIDE were tested. The Rd's for liquid BOLD were 674 and 712 for 21 0 C. and 38 0 respectively and the corresponding Rd's for liquid TIDE were 746 and 758.

It is seen from these data that the invented compositions are superior in detergency to the controls (NRE's are better than BRE's.). The invented compositions are also better, on the average, than the commercial liquid detergents tested.

i EXAMPLE 4 In another set of experiments, some of which parallel those already described, the composition of the following base formula, identified as Formula was made, together with variations of such formula, and control formulations including BRE instead of NRE.

"t 15 4 5i si 44,.

If S I S I 4 J 1n n A

CI"CC

1

O

w Component NRE (Tergitol Nonionic Surfactant 24-L-60N) Sodium linear dodecylbenzene sulfonate Sodium xylene sulfonate Trimethyl monotallowalkyl ammonium chloride Ethanol Triethanolamine Fluorescent brightener Perfume Colorant Citric acid (for pH adjustment) Watep (zero hardness) 21.0 0.4 0.4 0.2 q.s.

53.5 100.0 t I 1 t t t

I

Stilbene-type brightener like that of Example 1 '15 This detergent composition is made according to the method of Example 1 and is tested in the same manner.

Formula 4(b) is the same as Formula 4(a) except that the percentage of sodium linear dodecylbenzene sulfonate is reduced to 4.4 and the quaternary ammonium chloride is changed to Akzo Chemie WA104 (proprietary mixture of two higher alkyl lower alkyl ammonium chlorides). Formula 4(c) is the same as Formula 4(a) except that the percentage of sodium linear dodecylbenzene sulfonate is reduced to 3.6% and the quaternary ammonium chloride is dimethyl ditallowalkyl ammonium chlorii Formula 4(d) is the same as Formula 4(a) except that the concentration of sodium linear dodecylbenzene sulfonate is reduced to 3.9% and the quaternary ammonium chloride is dimethyl monotallowalkyl monooctyl ammonium chloride. Formula 4(e) is the same as Formula (a) except for the omission of the quaternary ammonium chloride.

Thus, Formula 4(e) is, in effect, a secondary control, which, as will be seen from the data, shows that any improvement in detergency of the invented compositions is not due merely to the NRE being a better detergent than the BRE in liquid detergent compositions, and establishes that the presence of the fabric softening and antistatic cationic compound is required in such compositions to obtain the improved comparative detergency reported herein.

Following is a summary of the Rd's obtained for ,15 the compositions of Formulas 4(a) -4 t TABLE 3 Formula No. Rd (21 0

C.)

24-L-60N 25-7 (controls) 4(a) 780 725 4(b) 790 707 4(c) 776 709 4(d) 736 671 4(e) 787 792 Rd (38°C.) 4(a) 850 815 4(b) 855 802 4(c) 845 787 4(d) 803 763 4(e) 841 831 From the above data it is evident that although changes in the quaternary ammonium halide in the formulas of the invented compositions have been made, improvement in detergency of the products of this invention is still shown, compared to control compositions in which the NRE of the present formulation was replaced by a BRE of comparable fatty alcohol and average polyethoxylate components. Additionally, when the quaternary ammonium halide is omitted from the formulas there is essentially no difference in detergency between the NRE and BRE compositions. It should 23 be noted that it is considered that best detergency improvement is obtainable when the percentages of cationic compound and anionic detergent are equal or about equal, and the proportions thereof should not be outside the 1:2 to 2:1 range.

Preferably the molar ratio of cationic compound to anionic detergent will be about 1:1.

EXAMPLE In a set of experiments utilizing NRE's of different cloud points (which may correspond to ethoxylate distribution curve heights) and measuring detergencies of fabric softening/ antistatic liquid detergent compositions containing them as the nonionic detergent components, compared to a BRE formula, a composition of Formula 5(a) was made together with variations of such formula and a control formula. Formula 5(a) is the same as Formula 4(a) of Example 4 and the control is the same 15 as in such example, also with Neodol 25-7 replacing Tergitol Nonionic Surfactant 24-L-60N. Formula 5(b) is the same as Formula 5(a) except for the replacement of the 24-L-60N detergent with 24-L-75N and Formula 5(c) is the same as except that the replacing detergent is Tergitol Nonionic Surfactant 24-L-50N. The test results are tabulated in J Table 4.

A l *i

K

TABLE 4 Formula No.

Rd (21WC.) (a) 5 (b) (c)

NRE

735 717 700

BRE

669 Rd (380C.) (a) (b) 5 (c) 777 809 718 The tests reported in Table 4 are repeated, with the following results, as given in Table TABLE t *0 o 0 0 o 00 o 00 0 0 0 0 15 0006 0000 000* 00 0 0 00 0 00 0 o~ 0 0 0 0 04 0 0 0 000% ,t4 itt Formula No.

Rd (210C.) 5 (a) 5 (b) (c)

NRE

739 745 697

BRE

6 '77 Rd (380C.) (a) 5 (b) 5 (c) 771 806 691 745 From the above data it is evident that the inclusion of a NRE detergent improves detergency of the described NRE liquid detergent compositions compared to comparable BRE compositions when test swatches stained with oily soils are, S 5 washed in cold water (21 0 Both the 24-L-60N and 24-L-75N NRE's increase detergency more in the softergent conmositions than does the BRE when test swatches are washed at a higher temperature (38 0 EXAMPLE 6 In the previous examples variations in the NRE and quaternary ammonium halide were made in the various formulas reported. In addition to those modifications, the anionic detergent may be replaced by other sulfonates and/or sulfates, Ssuch as sodium lauryl sulfate and sodium tallowalkyl sulfate S 15 or sodium hydrogenated tallowalkyl sulfate, and the hydrotrope I may be replaced by sodium benzene sulfonate or sodium cumene sulfonate. Instead of ethanol, mixtures of ethanol and lower polyols, such as glycerol and ethylene glycol, may be used. Other stilbene fluorescent brighteners may be substituted and instead of triethanolamine, mixtures of triethanolamine and other alkanolamines, such as isopropanolamine and diethanolamine, may be used. Instead of citric acid, other weak acids, including gluconic acid, may be employed. Of course, different dyes and perfumes may also be substituted without adversely affecting the desired results. In addition to changing the various components of the compositions the proportions thereof may be altered, such as by l10% and without going outside the ranges specified herein. The changed compositions described will have the desirable properties of the invented softergents and will be of improved detergency, compared to identical compositions in which a BRE nonionic detergent is employed instead of the desired NRE nonionic detergent. Furthermore, similar results are obtainable, corresponding to those of these working examples, when the components of the detergent compositions are individually added to the wash water.

The invention has been described with respect to various working examples and illustrations thereof but is 4 *41(5 not to be limited to these because it is evident that one of skill in the art, with the present specification before him, will be able to utilize substitutes and equivalents without r departing from the invention.

4

Claims (6)

1. An antistatic liquid detergent composition which comprises a detersive proportion of a narrow range ethoxylate nonionic detergent (NRE), an antistatic and fabric softening proportion of a cationic compound, and water, which liquid detergent composition is of improved detergency vs. oily soils on fabric to be washed with aqueous wash water solutions of the detergent composition, compared to similar compositions in which the nonionic detergent component is a broad range ethoxylate nonionic detergent (BRE).

2. A liquid detergent composition according to claim 1 wherein the NRE is a higher fatty alcohol ethoxylate condensation product of a higher fatty alcohol and ethylene oxide, with the higher fatty alcohol being of 12 to 16 carbon atoms and the ethylene oxide being in polyethoxy ethanol groups averaging 4 to 10 ethoxy groups per mole, with at least 80% of the NRE being higher fatty alcohol ethoxylates of ethoxy contents in the range of 4 to 10 ethoxy groups per mole, the antistatic cationic compound is a quaternary ammonium salt, and the proportions of such NRE, quaternary ammonium salt and water are in the ranges of 10 to 35%, 2 Sto 15%, and 30 to 70%, respectively. 37

3. A liquid detergent composition according to claim 2 which comprises 15 to 30% of a NRE which is a condensation product of a saturated higher fatty alcohol of 12 to carbon atoms and an average of 5 to 9 moles of ethylene oxide per mole of such higher fatty alcohol, in polyethoxy ethanol groups, with at least 85% of the NRE being higher fatty alcohol ethoxylates in the range of 4 to 10 ethylene oxide groups per mole, 3 to 10% of fabric softening and antistatic quaternary ammonium salt of the formula o ao 1 0 2 I2 1 3 SR N R X 4 S 15 wherein R 1 and R are lower alkyl of 1 to 3 carbon atoms, R is higher alkyl of 10 to 20 carbon atoms and e* R is alkyl of 1 to 20 carbon atoms, and X is chlorine, bromine or methyl sulfate, a brightening proportion, within the range of 0.1 to of a fluorescent 20 brightening compound, a fluorescent brightener substantivity increasing proportion of an anionic sulfate and/or sulfonate detergent, within the range of 2 to a fluorescent brightener solubilizing and liquid detergent composition buffering proportion, within the range of 25 0.3 to of lower alkanolamine, a hydrotropic proportion, within the range of 2 sto 10%, of a hydrotropic compound, 3 to 15% of a polar organic co-solvent for the non-aqueous components of the liquid detergent composition, which promotes solubility of such components in the composition and promotes transparency of the composition, 40 to 60% of water, and any balance of adjuvant(s).

4. A liquid detergent composition according to claim 3 which comprises 18 to 25% of a NRE which is a condensa- tion product of a saturated higher fatty alcohol of 12 to 14 carbon atoms and an average of 6 to 8 moles of ethylene oxide per mole of such higher fatty alcohol, in polyethoxy ethanol groups, with at least 90% of the NRE being higher fatty alcohol ethoxylates in the range of 4 to 10 ethylene oxide groups per mole, 4 to 8% of antistatic quaternary ammonium chloride of the formula R 2 R 1 N R 3 Cl R 4 wherein R and R are lower alkyl(s) of 1 to 2 carbon atoms each, R 3 is higher alkyl of 12 to 18 carbon atoms and R 4 is either lower alkyl of 1 to 2 carbon atoms or higher alkyl of 12 to 18 carbon atoms, 0.1 to 1% of a fluorescent brightening compound, which is a stilbene brightener, 3 to 10% of a higher alkylbenzene sulfonate detergent, 1 to 2% of triethanol- amine, 3 to 7% of a hydrotrope selected from the group consisting of alkali metal benzene sulfonate, alkali metal xylene sulfonate and alkali metal cumene sulfonate, 4 to of ethanol, 50 to 60% of water, and the balance, 0.1 to of adjuvant(s). A liquid detergent composition according to claim 4 wherein the antistatic quaternary ammonium chloride is monotallowalkyl trimethylammonium chloride, the fluorescent brightener is a stilbene disulfonic acid, a stilbene di- sulfonate, or a mixture thereof, the higher alkylbenzene sulfonate detergent is alkali metal dodecylbenzene sulfonate, the hydrotrope is sodium xylene sulfonate and the adjuvants include perfume and colorant.

6. A liquid detergent composition according to claim 5 which consists essentially of about 21% of NRE, about 6% of monotallowalkyl trimethylammonium chloride, about 6% of sodium linear dodecylbenzene sulfonate, about 6% of ethanol, about 5% of sodium xylene sulfonate, about of triethanolamine, about 0.4% of fluorescent brightener(s), Sabout 0.4% of perfume, about 0.2% of colorant(s) and about

53.5% of water, which liquid detergent composition is clear in appearance, stable on storage, of a pH in the range of 7 10 to 8, and of a viscosity in the range of 75 to 125 centipoises H at S7. A liquid detergent composition according to claim 6 which consists of 21% of NRE, 6% of monotallowalkyl trimethylammonium chloride, 6% of sodium linear dodecylbenzene sulfonate, 6% of ethanol, 5% of sodium xylene sulfonate, 1.5% of triethanolamine, 0.4% of fluorescent brightener(s), 0.4% of perfume, 0.2% of colorant(s) and 53.5% of water, which liquid detergent composition is of a pH of about and of a viscosity of about 100 centipoises at 25 0 C. 8, A process for washing laundry, fabrics of which are soiled with an oily soil, which comprises washing such laundry in wash water in an automatic washing machine, which wash water contains a detersive proportion of NRE and a fabric softening and antistatic proportion of cationic compound, which washing makes the laundry soft and antistatic and removes the oily soils from the laundry significantly better than such soil is removed when such laundry is washed with wash water that i i.detntical except for replacement of the NRE with BRE. 9. A washing process according to claim 8 wherein the NRE is a higher fatty alcohol ethoxylate condensation product of a higher fatty alcohol and ethylene oxide, with the higher fatty alcohol being o. 12 to 16 carbon atoms and 5 the ethylene oxide being in polyethoxy ethanol groups averag- S ing 4 to 10 ethoxy groups per mole, with at least 80% of the I O NRE being higher fatty alcohol ethoxylates of ethoxy contents i| in the range of 4 to 10 ethoxy groups per mole, the antistatic compound is a quaternary ammonium salt, and the concentrations of such NRE and quaternary ammonium salt in the wash water are in the ranges of 0.01 to 0.2% and 0.001 to respect- o 4 ively, the wash water is of a hardness no more than 300 p.p.m,, a4,. S as CaCO 3 and the water temperature is in the range of 10 to *o 4 o* o i s. ACI t; ^0L L*q-C-- p A washing process according to claim 9 wherein the NRE is a condensation product of a saturated higher fatty alcohol of 12 to 15 carbon atoms and an average of 6 to 8 moles of ethylene oxide per mole of such higher fatty alcohol, in polyethoxy ethanol groups, with at least 85% of the NRE being higher fatty alcohol ethoxylates of ethoxy contents in the range of 4 to 10 ethylene oxide groups per mole, the antistatic quaternary ammonium salt is of the formula R 2 1 3 R 1 -N -R X R 4 wherein R 1 and R are lower alkyl(s), R 3 is higher alkyl and R 4 is higher, lower or middle alkyl, and X is chlorine, bromine or methyl sulfate, the wash water includes 0.02 to 0.1% of the NRE, 0.002 to 0.05% of the antistatic quaternary ammonium salt, a brightening proportion, within the range of 0.0001 to 0.01%, of a fluorescent brightening compound, and a fluorescent brightener substantivity increasing proportion, within the range of 0.001 to 0.1% of an anionic sulfate and/or sulfonate detergent, and the wash water is at a temperature in the range of 10 to 50 0 C. 11. A washing process according to claim wherein the NRE is a condensation product of a saturated higher fatty alcohol of 12 to 14 carbon atoms and an average of 6 to 8 moles of ethylene oxide per mole of such higher fatty alcohol, in polyethoxy ethanol groups, with at least of the NRE being higher fatty alcohol ethoxylates in the range of 4 to 10 ethylene oxide groups per mole, the antistatic quaternary ammonium salt is of the formula S+ R 2 R N R Cl R 4 i 1 2 wherein R 1 and R are lower alkyl(s) of 1 to 2 carbon atoms Seach, R 3 is higher alkyl of 12 to 18 carbon atoms and R is either lower alkyl of 1 to 2 carbon atoms or higher alkyl of 12 to 18 carbon atoms, the wash water includes 0.03 to 0.06% of the NRE, 0.005 to 0.02% of the antistatic quaternary ammonium chloride, 0.0002 to 0.005% of fluorescent brighten- ing compound, which is a stilbene brightener, and 0.005 to 0.02% of higher alkylbenzene sulfonate detergent, the wash water is of a hardness of 100 to 200 as CaCO 3 and the S 20 wash water is at a temperature in the range of 10 to 25 0 C. 4-2- 12. A washing process according to claim 11 wherein the quaternary ammonium chloride is monotallowalkyl trimethyl ammonium chloride and the wash water contains about 0.04% of NRE, about 0.01% of monotallowalkyl trimethyl ammonium chloride, about 0.01% of sodium linear dodecyl- benzene sulfonate and about 0.001% of fluorescent brightener. Dated this 20th day of October 1988 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant F.B. RICE CO. J1 t cIt V