BACKGROUND OF THE I NVENT ION The present invention relates to aqueous liquid detergent compositions and to the use of same in the laundering of fabric materials in general and , in particular, to the laundering under relatively mild washing conditions of fine fabric materials such as nylon, polyester, wool , silk and the like.

Alkyl glycoside materials such as , for example, higher alkyl monoglycosides and higher alkyl polyglycosides are known materials ; are known , at least in certain circumstances , to function as nonionic surfactants; and have been suggested as being suitable for use in certain specially formulated detergent composi¬ tions . See in this regard , for example, Published European Patent Application Numbers 0070074; 0070075; 0070076; and 0070077, all of which published on January 19 , 1983 as well as Published European Patent Applica¬ tion Numbers 0076994; 0076995 ; and 0075996 which published on April 6 , 1983. See also Published European Patent Application Number 0105556 (published April 18 , 1984) which discloses liquid detergent compositions containing anionic surfactants , alkypolyglycoside surfactants , selected nonionic surfactants and optionally also containing various other ingredients such as suds stabilizing amine oxide surfactants , detergent builder materials , and the like; Published European Patent Application Number 0106692 (published April 25 , 1984) which discloses stable heavy-duty liquid detergent compositions containing a mixture of an ethoxylated fatty alcohol nonionic surfactant, an alkylpolyglycoside surfactant and a quaternary ammonium cationic surfactant in conjunction with a polyethylene glycol compound and a wide variety of potential conventional laundry detergent

additives; and U.S. Patent 4 ,493 ,773 (issued January 15 , 1985) which discloses laundry detergent compositions which contain a conventional nonionic detergent surfactant, an alkylpolyglycoside detergent surfactant and a quaternary ammonium cationic fabric softening surfactant and which are said to be capable of including a wide variety of conventional laundry detergent additives such as relatively small amounts of detergent builders, detergency cosurfactants such as trialkyl amine oxides , solvents such as ethanol , and the like.

As is reflected within the prior art references noted above, the various glycoside surfactant-containing laundry detergent compositions suggested to date generally involve the use of said glycoside surfactant in combination with various anionic surfactant materials and/or with various conventional non-glycosidic ethoxylated nonionic surfactant materials and/or in conjunction with one or more of a variety of detergent builder ingredients.

SUM ARY OF THE I NVENTION In accordance with the present invention , it has now been discovered that certain especially beneficial end-use-specific glycoside surfactant-based detergent compositions can be suitably prepared by properly formulating one or more glycoside surfactants with certain antistatic quaternary ammonium surfactants in the absence of (or at least substantially in the absence of) conventionally employed laundry detergent- ingredients such as anionic surfactant ingredients , non-glycosidic ethoxylated nonionic surfactant ingredients and conven¬ tional detergent builder materials.

Thus , the present invention , in one of its aspects , is a substantial ly builder-free fine fabric laundry detergent composition which comprises , on a total composition weight basis: a . from about 10 to about 70 weight percent of a surfactant component which consists essentially of a combination of a glycoside surfactant and an antistatic quaternary ammonium surfactant, the weight ratio of the glycoside surfactant to the quaternary ammonium surfactant being from about 1 :3 to about 10 : 1 ; and b. from about 30 to about 90 weight percent water. Another aspect of the present invention involves the use of the above-described detergent composition in a fabric laundering operation in which said detergent composition is diluted with water to normal laundry usage levels (typically about 1 /4 cup of the above-stated composition in from about 5 to about 15 gallons of wash water) and is then employed to wash or

launder soiled clothing or other soiled fabric materials. More specifically stated, this latter embodiment is essentially a process for laundering soiled fabric materials, said process comprising immersing said fabric material , with at least mild agitation , in a substantially builder-free washing medium comprising , on a total washing medium weight basis , from about 200 part per million to about 1250 part per million of a surfactant component consisting essentially of a combination of a glycoside surfactant and an antistatic quaternary ammonium surfactant in a glycoside surfactant to quaternary ammonium surfactant weight ratio of from about 1 : 3 to about 10 : 1 .

The! composition and process of the present invention are especially wel l suited to and beneficial for the laundering under relatively mild washing conditions (e. g . , mild or gentle machine agitation or handwashing and at low or cold wash water temperature) of fine fabric materials such as silk , nylon , polyester and wool . It is a particularly noteworthy feature or benefit of the present invention that the aforementioned antistatic quaternary ammonium surfactant materials provide , at a given usage level of same, substantially more pronounced or enhanced antistatic control within the subject glycoside surfactant-based formulations than they do in comparable compositions wherein conventional ethoxylated alcohol nonionic surfactants are employed in place of said glycoside surfactant component.

DETAI LED DESCRI PTION OF THE I NVENTION

Glycoside surfactants suitable for use in the practice of the present invention include those of the formula: RO(R'O) _y (Z) _χ A wherein R is a monovalent organic radical (e.g . , a monovalent saturated aliphatic , unsaturated aliphatic or aromatic radical such as alkyl , hydroxyalkyl , alkenyl , hydroxyalkenyl , aryl , alkylaryl , hydroxyalkylaryl , arylalkyl , alkenylaryl , arylalkenyl , etc. ) containing from about 6 to about 30 (preferably from about 8 to about 18 and more preferably from about 9 to about 13) carbon atoms; R' is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R'O) represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof) ; y is a number having an average value of from 0 to about 12; Z represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit) ; and x is a number having an average value of from 1 to about 10 ( preferably from 1 .5 to about 10 and more preferably from about 1 .5 to about 5 ) . Glycoside surfactants of the sort mentioned above, and various preferred subgenera thereof, are described in U . S. Patent 4, 483 ,779 to Llenado et al (issued November 20, 1984) the discussion and descrip¬ tion of which is hereby incorporated by reference. Glycoside surfactants suitable for use herein also include those of the Formula A above in which one or more of the normally free (i . e. , unreacted hydroxyl groups of the saccharide moiety , Z , have been

alkoxylated (preferably , ethoxylated or propoxylated) so as to attach one or more pendant alkoxy or poly (alkoxy) groups in place thereof. in such event, the amount of alkylene oxide (e.g . , ethylene oxide, propylene oxide, etc. ) employed will typically range from abut 1 to about 20 ( preferably from about 3 to about 10) moles thereof per mole of saccharide moiety within the Formula A glycoside material .

In glycosides of the Formula A above, the RO( R O) group is general ly bonded or attached to the number 1 carbon atom of the saccharide moiety , Z . Accordingly , the free hydroxyls available for alkoxylation are typically those in the number 2 , 3 , 4 and 6 positions in 6-carbon atom saccharides and those in the number 2 , 3 and 4 positions in 5-carbon atom saccharide species . Typical ly , the number 2 position hydroxyls in 5-carbon saccharides , and the number 2 and 6 position hydroxyls in 6-carbon saccharides , are substantial ly more reactive or susceptible to alkoxylation than those in the number 3 and 4 positions. Accordingly , alkoxylation wil l usual ly occur in the former locations in preference to the latter. Examples of the indicated alkoxylated glycoside materials , and of method¬ ology suitable for the preparation of same , are described in United States Patent Application Serial No. 06/704, 828 filed February 22 , 1985 by Roth et al .

Glycoside surfactants especial ly preferred for use herein include those of the Formula A above wherein R is an alkyl group containing from about 8 to 18 (especially from about 9 to about 13) carbon atoms; y is zero; Z is glucose or a moiety derived therefrom; and x has an average value of from 1 .5 to about 5 (especially from about 1 .5 to about 3) .

-8-

Glycoside surfactants of particular interest for use in the practice of the present invention preferably have a hydrophilic-lipophilic balance (H B) in the range of from about 10 to about 18 and most preferably in the range of from about 12 to about 14.

Quaternary ammonium surfactants suitable for use herein include any of the known members of that particular family of surfactants that effectively control the build-up of static electricity on fabric materials washed or otherwise treated therewith and thus generally include those of the formula:

^R 4 +

R-, - N - R ₅ Y B R ₆ wherein R. is a higher alkyl radical having at least about 8 carbon atoms and preferably having between about 12 and about 22 carbon atoms; R ₅ is the same as Ry or is a lower alkyl radical having from 1 to 4 carbon atoms; and R _fi and R ₇ are independently selected from the group consisting of lower alkyl radicals having 1 to 4 carbon atoms; benzyl radicals; phenyl radicals; hydroxyalkyl radicals (especially hydroxy lower alkyl radicals such as hydroxy ethyl and hydroxy propyl ) ; and hydroxyalkoxyalkyl radicals which include, for example , the hydroxy polyethers formed by the condensation of ethylene oxide and/or propylene oxide; and Y is a neutralizing anion .

While the choice of the anion , Y , in the Formula B above is not particularly critical , the chloride, methyl sulfate and ethyl sulfate anions are generally the most conveniently and commonly employed.

Other anions suitable for use include nitrite , other halides , sulfate, other alkyl sufates , oleate , palmitate, stearate, benzoate, organic phosphates , and the like.

An especially preferred group of antistatic quaternary ammonium surfactants for use herein include those of the formula:

H0-CH-CH ₂ -(-0-CH-CH ₂ ) _n -N-(CH ₂ -CH-0-}--CH ₂ -CH-0H X C

^R 3 wherein R. is hydrogen or methyl (preferably hydrogen) ; R ₂ is methyl or ethyl ; R, is a monovalent organic radical of from about 8 to about 18 carbon atoms (preferably normal or branched , saturated or. unsaturated aliphatic radical of from about 8 to about 18 carbon atoms) ; n is a number having an average value of from 0 to about 50 ( preferably from 0 to about 15) ; and X is a neutralizing anion (especial ly chloride, methylsulfate or ethyl sulfate) . An especial ly preferred quaternary antistatic surfactant for use herein is ethyl bis (polyethoxy ethanol ) higher al kyl ( e. g . , C _R - C. _ al kyl ) ammonium ethyl sulfate.

The total amount of surfactant ingredient employed in the compositions hereof is typical ly in the range of from about 10 to about 70 (preferably from about 15 to about 40 and most preferably from about 15 to about 30) weight percent on a total composition weight basis. Further (and has been noted above) , said surfactant ingredient consists essential ly of a combination of a glycoside surfactant and an antistatic quaternary ammonium surfactant in a glycoside to quaternary ammonium surfactant weight ratio of from about 1 : 3 to

about 10 : 1 . Said ratio is preferably from about 1 : 1 to about 10: 1 and is more preferably from about 1 .6: 1 to about 6: 1 .

The water content of the subject detergent compositions is typically from about 30 to about 90 weight percent and is preferably from about 60 to about 85 (and most preferably from about 70 to about 85) weight percent, said ranges all being stated on a total composition weight basis. As has also been mentioned above, the compositions hereof are typically employed in actual laundering operations by diluting approximately a quarter cup of same with from 5 to 15 gallons of wash water and using same in such diluted form to launder clothing or other textile fabric articles in the usual fashion . As such , the surfactant ingredient concen¬ tration, within the diluted wash water is typically from about 200 to about 1250 ppm on a total wash water weight basis . The manner in which the detergent composi¬ tions hereof are prepared or formulated is not particu¬ larly critical and such can be readily accomplished in any convenient fashion as may be desired in a given instance. Oftentimes , however , the aforementioned glycoside and quaternary ammonium surfactant ingredients are conveniently prepared , purchased or otherwise obtained in the form of relatively concentrated (e.g. , 40 to 80 weight percent active) aqueous solutions of same and it is therefore generally convenient to admix them together (in the desired active ingredient ratios or proportion) in that form and to thereafter dilute the resulting mixture (if and when necessary or desired)

with water to the desired total active surfactant , ingredient content.

In addition to the above specified surfactant ingredients and water , the compositions can optionally (and frequently wil l desirably) contain relatively minor amounts , typically less than about 5 (more typically less than about 2 and most typically less than about 1 ) weight percent (total composition weight basis) of the usual types of non-builder , non-surfactant auxiliary ingredients as are commonly or customarily employed in conventional laundry detergent compositions such as , for example, perfumes; optical brighteners; pearlescing agents; colorants; viscosifying agents; and the like. Further , it should also be noted that while the composi- tions hereof are desirably "substantially free" of detergency builder ing redients , it is nonetheless comtemplated that relatively minor amounts (e. g . , less than about 10, preferably less than about 5 and most preferably less than about 2 , weight percent on a total composition weight basis) of builder ingredients such as alkal i metal salts of citrates , phosphates , carbonates and the like can nonetheless be included therein without deviating or departing from the spirit or scope of the instantly claimed invention . The present invention is further illustrated and understood by reference to the following working examples in which all parts and percentages are on a weight basis unless otherwise indicated .

EXAMPLES 1 - 4 In these examples , a series of fine fabric detergent compositions are prepared by dissolving a C. - , ₃ alkyl polyglucoside surfactant having a degree of polymerization of about 2.5 (APG 23-3) and an antistatic quaternary ammonium ("Antistatic Quat") surfactant, specifically an ethyl bis (polyethoxy ethanol) higher alkyl ammonium ethyl sulfate, in water and the resulting compositions are then evaluated at various representative diluted usage levels for cleaning and/or static control effectiveness in the laundering of wool , polyester and nylon fabric materials.

In these examples , the total surfactant ingredient content of the compositions prepared and tested is about 20 weight percent on a total composition weight basis and the APG : Antistatic Quat ratio employed therein is as shown in Table A below.

For comparative purposes , experimental formulations are also prepared and evaluated in which there is employed as the surfactant ingredient: the APG alone; a linear al kyl ethoxylate ( LAE) alone (i .e. , ethoxylated C. __ ₁ -. fatty alcohol , 7 moles ethylene oxide per mole fatty alcohol ) ; and the LAE in combination with the Antistatic Quat. The results of the cleaning and static control evaluations for these various formulations are summarized in Table A below.

In obtaining these evaluation results , the cleaning effectiveness is determined with a Tergotometer apparatus using a 10 minute wash cycle at a water temperature of 85°F ( 29.4°C) a water hardness of 120 ppm and an agitator speed of 75 rpm. The static electricity build-up is quantitatively determined using a

Simco Electrostatic Locator , Model SS2 and is qualita¬ tively evaluated by observing the degree of "static cling" exhibited by the laundered fabric upon removal from the dryer.

TABLE A

Usage. Cliεaning Performance Static Charge

Example Surfactant, , Level Build up (Volts) Degree of Number Ingredient ^l - ^ά - ^Δ - (ppm) Wool Nylon Polyester Nylon Polyester Static Clin

1 3:1 weight ratio of 700 Good Good Fair 500 100 None APG 23-3:Antistatic Quat

2 3:1 weight ratio of 525 Good Good Fair 3,500 500 Slight

APG 23-3:Antistatic Quat

3 3:1 weight ratio of 350 N.D. ⁶ N.D. N.D. 2,400 3,500 Slight APG 23-3:Antistatic Quat

4 6:1 weight ratio of 700 Good Good Fair 3,000 400 None

APG 23-3:Antistatic Quat

Control 1 APG 23-3 Alone 700 Good Good Fair 14,000 10,000 Moderate - H

Control 2 LAE Alone 700 Good Good Fai 10,000 15,000 High

Control 3 3:1 weight ratio of 700 Good Good Fair 5,000 3,000 Moderate LAE:Antistatic Quat

1. APG 23-3 = C,„ ,- alkyl polyglucoside having an avera<ge degree of polymerization (D.P.]1 of about 2.5.

2. Antistat1c Qάat ¹ * Ethyl bis (polyet:hoxy ethartol) fatty alkyl ammonium ethyl sulfate.

3. LAE = ethoxylated C, _{2 15} fatty alcohol, 7 moles ethylene oxide per mole fatty alcohol

4. Parts by weight of active surfactant per million parts by weight of wash water.

5. Mixed Polyester and Nylon dryer load.

6. N.D. = Not determined.

As can be seen from the results in Table A (i .e. , comparing Example 1 with Control 3 ) , the anti¬ static quaternary ammonium surfactant provides notably better static control when used in conjunction with the glucoside surfactant than it does when used with the conventional ethoxylated alcohol nonionic surfactant material .

While the present invention has been described and illustrated by reference to certain representative examples and embodiments thereof , such is not to be interpreted as in any way limiting the scope of the instantly claimed invention .