CA1200172A

CA1200172A - Detergent compositions

Info

Publication number: CA1200172A
Application number: CA000412232A
Authority: CA
Inventors: Ramon A. Llenado; Denzel A. Nicholson
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1981-09-28
Filing date: 1982-09-27
Publication date: 1986-02-04
Also published as: BR8205654A; EP0075996B1; EP0075996A2; DE3275203D1; IE822335L; GR76287B; IE53900B1; EP0075996A3

Abstract

DETERGENT COMPOSITIONS
Abstract of the Disclosure Detergent surfactant combinations comprising alkylpolygly-coside detergent surfactants and nonionic detergent surfactants provide good detergency and are compatible with anionic optical brighteners, both in built and unbuilt detergent compositions.

Description

DETeCRGENT COr,lPOSlTlONS
Ramon A. Llenado and Denzel A. ~7ic~olson Fielri of the Invention T~lis invention relates to surfactant combinations whic~>
provide good deter~ency and, optionally, ~ood fluoresc~:r ~ffec.-tiveness and/or suds control anri/or corrosion inhi~ n in ~t laundry context. Such compositions can l)e eit~.er huilt c~r un-~
built, granular or liquid, and can contain the usu~l .Jux~liaer~
` ingreciients common to such compositions.
Description of the t'rior Art Alkylpolyglycosides which are surfactants have l-ecn cli~-closedi in U.5. Patents 3,598,865; 3,121,633; ancl ~ 7~r~69~
Thcase patents also c!isclose p!ocesses for makiny alkylpoly~lyco-side surfacta~ts and built liquici detercient co,~?osi~ions containinc, 2û thes~ surfactants. U.S. Patent 3,21~,655 ciiicloses alkyl~oelo~,elu~
cosides and su~ sts their utility as foam stabilizers for c-ther surfactants, Various polyglycosicl~ surfactant strl-ctur~s and processes for making them are disclosecl in U . 5 . Patent~
3,640,99S; 3,~39,318; 3,314,936; 3,346,558; 1~,011,3~ ,2~3,129, Summary of th~ Invention This invention relates to the discovery of ccrtain ~:ornbina~
tions of surfactants which provide unusually ciood ~'etercle:~cy, cs?ecially in cool water, for 2 variety of fabric types. SPDCj fi-call~ th;s invention relates to detergent compositions cornprisin~J:
t 1) frorn ~bout 1~ to about 90~ of an alkylpolysaccharicJe d~tercient surfacsant havinci the fQrmula P~O ( R'O ) y ~ Z ) x ~here R is an alky!, ~ydroxy al!cyi, <-Ikyl ph~n~l, nl~;yl benzyl, or rnixturcs thereof, saicJ al~yl oro~lps containing from about 8 to about 18 car~on ~toms; ~here each R' contains from 2 to aL)out '1 carbon atoms, .~
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'72

- 2 -preferably an ethoxy, propoxy, or cllyceryl ~ro~Jp, ancl y is from O to about 1~; and where each ~ is a mojety clerived from a reclucing sacch~ricle containin~ 5 or 6 carbon atoms, and x is a number From about 1-1- to a~ou~
10;
(2) from about 1~ to about 90% of ~ nonionic deter_~ent surfactant; and

(3) from 0~ to about 90~ oF a detergency builcl~r, th~ r;atio of (I) to (~) being from about 1:10 to about ~1):1, pre~
ferably from about 3:1 to about 1:3.
A highly preferred v ~riation also comprises from 2bout 0.01 ~o about 2,0% oF an anionic fluorescer ~optical brigh-~ener) In another highly preferred variation, the nonionic det~r~ent surfactant i5 selectèd from the group consistin~ of amine nxide cletergent surfactants, amide detergene surfactants ~nd mixtures thereof, and the composition additionally comprises fror~ a~oue 1~
to about 10% of an unsaturated soap containin~ from about 16 to about 22 carbon atoms, and, preferably, from about 0% to ~boot 10O of a synthetic anionic deter~3ent surFact2nt.
Description of tlle Preferred Embodirnents The Alkylpol~saccharide Surfactant It has surprisingly been found that the cosurfactants inter~
act with the alkylpolysaccharide surfactant of this invention to provide good laundry detergency for a ~/icle ran~32 of fabric~
-rh~ alkylpolysaccharicles are those havin~ a l-ydrophobic ~roup containing from abo~lt 6 to about 30 carbon ~toms, ~referably frorn about 10 to about 16 carbon atoms and a polysaccharide, e. 9, a polyglycoside, hydrophilic group containing from about 1~ ~o a~out 10, preferably from about 1~ to about 3, most preferably ~rorn about 1.6 to about 2.7 saccharide units. Any reduc;n~ sacch~rid~
containin~ 5 or 6 carbon atoms can be used, e~q ~lucose, galactose and galactosyl moieties can substitute for the ~31ucosy~
~r)oieties. (Optionally the hydrophobic group is attached at the 2 3, 4 etc. positior~s thus giving a glucose or ga1actos~ a5 opposed to a glucoside or ~alac;oside ) The intersaccharide boncls can be, .9., between the one po,ition of the ac!ditional sacch~fride units ,:i ."~'' L'7Z

and the 2-, 3-, 4-, andlor 6 positions on tne precedin~
saccharide units.
Optionally, and less desirably, there can be a polyalkoxîc1e chain joining the hydrophobic moiety and the ~olysacchar cJe moiety. Th~ preferred all~oxid~ is ethylene oxic!e. Typ;cal llydrophobic groups inclucle alkyl ~roups, eiLher saturated or unsaturated, branched or un~ranched containing from a~out ~: to about 18, preferably from about 10 to about 16 carhon ~ oms.
PreFerably, the alkyl group is a straight chain s~tur~t~d alkyl group. The alkyl group can contain up to 3 hydrc~xy ~rc.wps andlor the po5yalkcxide cha~n can contain up to abo~lt 1~, prefer~
ably less than 5, most preferably 0, alkoxide moieties. Sui-iable alkyl polysaccharides are octyl, nonyldecyl, ~nclecyldod~r.yl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptacl~ yl, anc3 octadecyl, di-, tri-, tetra-, penta-, an(~ he~ca~ cosides, ~alactosides, lactosicles, ~lucoses, fructosides, fruGtoses, :ncllor ~alactoses. Suitable mi~tures include cocon-lt alkyl, cii-, tri-, tetra-, ancl pentaglucosides and tallow all<yl tetra-, pentcl-, anc~
hexa~lucosides.
The preferred alkylpolyglycosides havè the form~lla r~20(CnH;~nO)t(glycosyl)x wherein F~2 jS selected from ~he group consistin~ ~f alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, anci mixtures there~f in which said all;yl ~3roups contain frorn about 10 to a~nut 1~, 25 preferably from about 12 to about ILI carbon atoms; n is ~ or ~
preferably 2; t is from O to abou~ 10, prcferably 0: c:ncl x is ~rom 1-~ to about 10, preferably from about 1~ to about ~, most preFerably from about 1.6 to about 2.7. The glycosyl ;~
preferably derived from ~lucose. To prepare compo~Jnds t~
30 alcohol or alkylpolyethoxy alcohol is formed rirst and then reacted ~/ith glucose, or a source of ~31ucose, to ~orm the ~3lUc:osid~
(attachment at the l-position). The additional ~Iycosyl units are attached between their l-position and the preceding gl3'CbSy~ ~2nits 2-, 3-, 4- andlor 6- position, preferably predomin~te1y t~
35 2-position.

~L~ t~

Preferably the conten~ of alkylmonoglycosicle is lo~v, prefer-ably less than abou~ 60~, more preferably less than about 50~
Surprisingly, anionic fluorescers which are normally rela-tively ineffective in the presence of conventional ethoxylatetl 5 nonionic detergent surfactants at high levels in the absence of substantial levels of anionic detergent surfactants, are Y~ry ef,ective when the alkylpolyglycoside surfactants are present.
For brightener effectiveness, the ratio of alkylpoly~lycosid2 detergent surfactant to nonionic detergent surfactant should b~
10 greater than about 1:4 preferably greater than about 1:3, mc.st preferably greater than about 1:1. .
THE t`lONlONlC DETERGENT SURFACTANT
Nonionic Surfactant Nonionic surFactants, including those having an HLB of frorn 15 about 5 to about 17, are well l;nown in the detergency art. rl~e.y are included in the compositions of the present invention tocJeth~r Yith the, e.~., alkylpolyglycoside surfactants definecl l-~reinbe-fore. They may be used singly or in combination ~Yith one or more of the preferred alcohol ethoxylate nonionic surfactants, 20 described below, to form nonionic surfactant mixtures us~ful in combination with the alkylpolyglycosicles. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issuecl Feb. 20, 1973, and U.S. Pat. No. 3,332,830, l~essler et al, issuecl July 25, 1~67. Nonlimiting e~amples o~ suitable nonionic ~5 surfactants which may be used in the present invention are as follows (I) The polyethylene oxide conclensates of alkyl phenols.
These compounds include the condensation products of alkyl p'nenols having an alkyl group containing from about 6 to 12 3~ carbon atoms in eitl~er a strai~ht chain or branched chain cor~-figuration with ethylen~ oxide, saicl ethylene oxide being pres~nt in an amount equal to S to ~5 moles of ethylene oxide per rn(-l~ o~
alkyl phenol. The alkyl substituent in such compounds can b~
derived, for example, from polymerized propylene, cliisobutylene?, 35 and the like. EXamples of com?ounds of this type includ~ nonyl phenol condensed with about 9.5 moles of ethyl~ne oxicle per mole oF nonyl phenol; doclecylphenol condensecl ~vith about 12 n~oles oF
ethylene oxide per mole of phenol; dinonyl phenol con~iensed ~Jith about 15 n-oies of ethylene oxide per mole of phenol; and cliiso-5 octyl phenol condensed with about 15 moles of ethylene oxide permole of phenol. Commercially available nonionic surfactants of this type include Igepal C0-630, marketed by the G~F Corpora-tion, and Tritor~-45, X-114, X-100, and X-102, all r~arketed by the Rohm ~ Haas Company.
t2) The condensation products of aliphatic alcohols with from about I to about 25 moles of ethylene oxkle. The alkyl chain oF the aliphatic alcohol can either be straight or branched, pri-mary or secondary, and generally contains from about ~ to about 22 carbon atoms, Examples of such ethoxylated alcohols includ~
15 ` the condensation product of myristyl alcohol conclensed with about 10 moles of ethylene oxide per mole of alcohol; and the conclen-' sation prod~;ct of about 9 moles of ethylene oxide ~/ith coconut alcohol ~a mixture of fatty a1cohols with alkyl chains varyin~ in length from 10 to 14 carbon atoms). Examples of cor~rcially available nonionic surfactants in this type include j~r~3it 15-S-g, marl;eted by Union Carbide Corporation, I~leodo~ 5-9, NeocJol 23-6.5, Neodol ~5-7~nd Neodol 45-4, marlceted by Shell Chemical Company, and l~yro~'EOB, marketed by . The Procter Gamble Company .
(3) The condensation products of ethylene oxide ~Yith a hydrophobic base formed by the condensation of l~ropylen~ oxid~
ith propylene ~31ycol. The hydrophobic portion of thes~ com-pounds has a molecular weight of from about 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieeies to this hydrophobic portion tends to increase the ~va~er solubility of the molecule as a ~vhole, and the liquid character of the product is retained up to the point ~Yhere the polyoxyethylene content is about 50~6 of the total ~vei~3ht of the conclensation product, which corresponds to condensation with up to abou~ 40 moles of ethylene oxide. Examples of compounds of this typ~

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.~
inclucle certain of the commercially available Pluronic sum'actants, mari;eted by ~'lyanclotte Chemical Corporation~

(4) The condensation products of ethylene oxicle with the procluct resulting from the reaction of propylene oxide and ethyl-cnecliamine. The hydrophobic moiety of these proc~ucts consists of the reaction procluct of ethylenediamine and ~xcess propylene oxicle, said moiety having a molecular ~vekJht o~ from about 2500 to about 3000. This hydrophobic moiety is condensed with ethyl-ene oxide to the extent that the condensation product contains lû from about 40~ to about 80~ by weight of polyoxyethylene and has a molecular veight of from about 5,000 to about 11,~00. Examples of this type of nonionic surfactant include certa;n of the comrner-cially available Tetronic~)compounds~ marketed by Wyandotte Chemical Corporation.

(5) Semi-polar nonionic detergent surfactants inclucte water-soluble amine oxides containing one alkyt moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the ~roup consisting of alkyl gro~lps and hydroxyalkyl ~roups containin~
from I to about 3 carbon atoms; ~Yater-soluble phosphine oxides containing one alkyl moiety oF about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl grou,~s ancl hydroxyalkyl groups containing from about I to 3 carbon atoms;
and ~Yater-soluble sulfoxides containing on, e alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group con,isting of alkyl and hydroxyalkyl moieties of from about I to 3 carbon atoms.
Preferred semi-polar nonionic detergent surfactants are the amine oxide detergent surfactants having the formula R3 (OR )XNR 2 ~herein R3 is an alkyl, hyclroxy alkyl, or alkyl phenyl ~roup or mixtures thereof containing from about ~ to about 22 carhon atoms, R4 is an alkylene or hydroxy alkylene group containin~
from 2 to 3 carbon atoms or mixtures thereof, x is from 0 ~o about 3 and each R is an alkyl or hydroxy alkyl group contain-ing from I to about 3 carbon atoms or a polyethylene oxide group containing from one to about 3 ethylene oxide groups ~nd saicl R5 groups can be attached to each other, e.~., throu~h an oxygen or nitrogen atom to form a ring structure.
Preferred amine oxide detergent surfactants are ClO 18 alkyl S dimethyl amine oxide, C8 18 alkyl dihydroxy ethyl amine oxicJe, and C8 12 alkoxy ethyl dihydroxy ethyl amine oxicie.
Nonionic ~eter9ent surfactants (1)-(4) are conventional ethoxylated nonionic detergent surfac~ants.
Preferred alcohol ethoxylate nonionic surfactants for IJSe ~n 10 the compositions of the present invention are biode~r~c~able ancl have the formula R (C2~4}nff' wherein R8 jS a primary or secondary alkyl chain o~ from about- 8 to about 22, preferably from about lO to about ~0, carbon ~atoms 15 ~ and n is an average of from about 2 to about 12, particul~rly from a~out 2 to about 9. The nonionics have an HLB thY~rophilic-lipophilic balance) of from about 5 to about 17, pr~fe~ably fror~
about 6 to about 15. HLe is definecl in cletall ;n ~onionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, pages 606-613. In preferred nonionic surfactants, n is from 3 to 7. Primary linear alc:ohol ~thoxylates (e.g., alcohol ethoxylates produced from organic alcohols which contain about 20~ 2-methyl branched isomers, commercially avail-able from Shell Chemical Company under the traclenarn~ Neoclol ) are preferred from a performance stanclpoint.
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of Clo alcohol with 3 moles of ethylene oxide; the conden-sation product of tallow alcohol ~,vith 9 moles of cthyi~n~ oxide;
the condensation product of coconut alcohol with '. moles nf ~thyl-ene oxide; the condensation product of coconu~ ~lcohol ~Yith 6 moles of ethylene oxide; the condensatior~ procluct of (`~12 ?,lcohol with 5 moles of ethylene oxide; the condensation ,oroduct nf Ci2 13 alcohol ~,vith 6.5 moles of ethylene oxide, an~ tne same condensa-tion product which is stripped so as to remove subslantially al3 f`. ~1 ~2~

~ 8 --lower ethoxylate ancl nonethoxylated fractions; the condensation product oF C12 13 alcohol with ~.3 moles of ethylen~ oxide, and the same conclensation product which is stripp~cl so as to remove substantially all lower ethoxylate and nonethoxylated fractions;
the condensation product of C12 13 alcohol with 9 moles o~ ethyl-ene oxide; the cond~nsation product of Cl~l 15 alcohol ~Yith 2.25 nloles of ethylene oxide, .he condensation prod~lct of Cll~ 15 alco-hol with 4 moles of ethylene oxide; the condensation product of C14 IS alcohol with 7 moles of ethylene oxid~; and the cond~nsa~
tion product of C14 15 alcohol with ~ moles of ~?thyl~ne oxide, The compositions of the present invention may contain mix--tures of the preferred al~ohol ethoxylate nonionic surfactants together with oth~r types of nonionic sur~act~nts. One of the preferred nonionic surfactant mixtures contains a~ least one of the preFerred alcohol ethoxylate nonionics, and has a ratio of -the preferred alcohol ethoxylate surFactan,t (or surFactants) to the other nonionic surfactant (or surfactants) of from about 1:1 to about 5 :1. Speci Fic examples of surfactant mixtures usef~ll in the present invention include a mixture of the condensation product of C14_l5 alcohol with 3 rloles of ethylene oxide ( Neodol 1~5-3) anc~
the condensation product of C14 15 alcohol with 9 moles of ethyl-ene oxide [Neodol 45-9), in a ratio of lower ethoxylat~ nonionic to higher ethoxylate nonionic of from abo~lt 1:1 to about 3~ mix-ture o~ the conclensation product of C10 ~Icohol with 3 moles of ethylene oxide together with the conclensation product of a secondary C15 alcohol w;th 9 moles of ethylerle oxicle (Ter~itol 15-5-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to a~out 4 :1; a mixture of Neodol 45-3 and Tergitol 15-S-9, in a ratio of lo~Y~r ~thoxylat~
nonionic to higher ethoxylate nonionic of"from about 1:1 to about 3 :1; and a mixture of l~eodol 45-3 with the condens~ation product:
of myristyl alcohol with 10 moles of ethylene oxid~, in a ratio of lower ethoxylate to higher ethoxylate of from about 1:1 to about 3:1 ~.' ~ ,. . ,- .
. : I .
1, ,~

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Preferred nonionic surfactant mixtures may also contain alkyl glyceryl ether compounds together ~Yith the preFerred alcohol ethoxylate surfactants. Particularly preferrec3 are ~Iyceryl ethers having the formula R t CH2C~2O ) nC~2 CHC~I~OH
0~1 herein R9 is an alkyl or aikenyl group of from about 8 ~o about 18, preferably about 8 to 12, carbon atoms or an alkaryl group having from about S to 14 carbons in th~ alkyi chain, and n i5 from O to about 6, together with the preferred alcohol ethoxyl-ates, described above, in a ratio of alcohol ethoxylate to glyceryl ether of from about 1:1 to about 4:1, particularly about 7:3~
Glyceryl ethers of the type useful in the present invention are ~ disclosed in U.S. Pat. No. 4,098,713, Jones, issued July ~, 197~, The ratio of alkylpolyglycoside ~3eter~ent s~lrfactant to nonionic detergent surFactant is from about 10:1 to about 1:10, preferably From about 3:1 to about 1:3.
The Detergency Builder The detergent compositions here;n also contain from 0~ to 20 about 90%, preferably from about 5~ to about 50~, and more preferably from about 10% to about 35% of a cleter~ent builder.
Such builders include, by way of exampl~, a crystalline alumino-silicate ion exchange material oF the formula Nazl ~AIO2)z' tSiO2)yl xH2O
25 wherein z and y are at least about 6, the molar ratic~ c,f z to y is from about 1.0 to about 0.5 and x is from about 10 to about 264.
Amorphous hydrated aluminosilicate material~ useful herein ha~e the empirical formula l~lz kAlO2 ySiO ~ ) 30 ~vhereln ~1 is sodium, potassiurl, ammonium or st~bstituted ammoni-um, z is from about ~.5 to about 2 anc~ y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents oF CaCO3 hardness per gram of anhydrous aluminosilicate.

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~ 10 -- .
The aluminosilicate ion exchanye builcler materials herein are in hycJratecl form and contain from about Ingi to about 2~6 o~ ~vater ~
by weight if crystalline, and potentially even higher amounts o-f ~i ~/ater if a~-lorphous. ~lighly preferred crystalline aluminosilicate ion exchange materials contain from about 1~ -to about ~2% water in their crystal ma-lrix. The preferred crystalline aluminosilicate ion exchanse materials are further characterized by a particl~ size diamQter of from about 0.1 micron to about 10 microns. Amor-phous materials are often smaller, e.g., down to less t~an about 5`
0.01 micron. More preferred ion exchange materials hav~ a parti-cle size diameter of from about 0.~ micron to about ~ microns.
The term "particle size diameter" herein reprcsents th~ avera~Q
particle size diameter of a given ion exchan~e mctteri~l as cleter-mined by conventional analytical techniques such as, for exampl~
microscopic cletermination utili~in~ a scanning electron mi~roscope~
The crystalline aluminosilicate ion exchan~e materials herein are usually further characterized by their calcium ion exchange ~-capacity, which is at least about ~00 mc. equivalent o~ CaCO3 ~later hardness/g. of aluminosilicate, calculatec; on an ar hydrous basis, and which generally is in the :-ange of from about 30û mg.
eq./g. to about 352 mg. eq./y. The aluminosilicate ion ~xchang2 materials herein are still f~lrther characterized by their calcium ion exchange rate which is at least about, ~ ~rains Ca Igallon/~
minutetgram/gallon of aluminosil;cate ~anhydro-Js basi~), and ~ -25 generally lies within the range of from about ~ ~rciinslgallon/-minute/gram/gallon to about 6 grains/gallonJmlnute/c3rat~/~allon, r;.
based on calcium ion hardness. Optimum aluminosilicate~ for ~.
builder put poses exhibit a calcium ion exchan~e rate of at least about 4 grainslgallon/minute/gram/gallon. !~'`''~
The amorphous aluminosilicate ion exchange materials usually have a hl9 exchange capacity of at least a~out 50 mg. eq.
CaC031g. (1~ mg. Mg /g.) and a Mg exchange ra~e r~f at least about 1 grain/gallon/minuee/gramJgallon. ~morpho-~s rnaler;als do not exhibit an o~servable diffraction pattern s~lhen examined by -;
Cu radiation ~1.54 An~3strom Units3.

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,'\tuminosilicate ion exchange materials useful in the practice of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in struc-ture ancl can be naturally-occurring aluminosilicates or syntheti-5 cally derived. A method for producing aluminosilicate ion eY~-change materials is discussecl in U.S. Patent 3,~85,669, ~rummet, et al, issued October 12, 1976, Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are avallable under the desl~nations Zeolite 10 A, Zeolite P (~), and Zeolite X. In an especially r~referred embodiment, the crystalline~ aluminosilicate ion exchan~e material has the formula Na121 tAlo2)t2~sio2)t2l XH2 ~ wherein x is from about 20 to about 30, especially about 27.
lS Other examples of detergency bui!ders include ~vater-solubl~
neutral or alkaline salts.
Other useful ~vater-soluble salts include the compounds commonly known as deter~ent builder materials~ Builders are g~nerally selected from the various ~Yater-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates, and polycar-boxylates. Preferred are the alkali metal,'especially soclium, salts of the above.
Specific examples of inor~anic phosphate builders are sodium and potassium tripolyphosphate, pyrophospha~e, polymeric meta-phate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene~ diphosphonic acicl, the sodium and pota~sium salts of ethane l-hydroY~y-l,l-diphos-phonic acid and the sodiùm and potassium salts of ethane, i,l~2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,422,137; 3,400,176 and 3,400,148, ~z~ z Examples of nonphosphor-ls, inorganic builclers are so~lium and potassium carbonate, bicarbonate, ses~uicarbonate, tetra-borate decahydrate, and silicate having a l~:olar ratio of SiO2 to alkali metal oxicle of from about ~.5 to about 4.0, preferably fror about 1.0 to about 2.4.
~'/ater-soluble, nonphosphorus organic build~rs useful herein inclucle the various alkali m~tal, ammonium ancl substitutec~
ammonium polyacetates, carboxylates, polycarboxylates and poly-hydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodiu~, potassium, lithium, ammonium and sub-stituted ammonium salts of ethylenediamine tetraacetic acicl, nitrilotriacetic acid, oxydisucctnic acid, mellit;c ~?cid, benzene polycarboxylic acids, and ci~ric acid.
Highly pre~erred polycarboxylate ~uilders herein are set forth in U.S. Patent No. ~,308,067, Diehl, issued March 7, 1967~ Such materials include the ~/ater~soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acicl, rnesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic ac~d.
Other builders include the carboxylated carbohyclrates of U.S. Patent 3,723,322, Diehl Other useful builders herein are sodium anc~ potass;um carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexanehexacarboxylate, cis-cyclopentanetetracarboxylate phloro-glucinol trisulfonate, ~Yater-soluble polyacrylates ~having molecular weights of from about ~,000 to about 200~noo for exampl~), and the copolymers of maleic anhydride ~i th vinyl methyl cther or ethylene .
Other suitable polycarboxylates for use herein are the poly-acetal carboxylates described in U.S. ~ Pat. 4,144,226, issued ~larch 13, 1979 to Crutchfield et al, and U.S. Pat. ~ 46,L~gS, issued March 27, 1979 tCt Crutchfield et al. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an '~
,.. ~- , ~2~

~ 13 --ester of glyoxylic acid and a polymerization initiator. The re-sultin~ polyacetal carboxylate ester is th~n attached to chernically stable end groups to stabilize the polyacetal carbox~late against rapid depoly~erization in alkaline solu;ion, convertecl to tiae correspondin9 salt, and added to a surfactant.
Other detergency builder materials usefu1 herein are the "seeded builder" compositions disclosed in Belgian Patent No. 798,856, issued October 29, 1973 Specific examples of such seeded builder mixtures are: 3:1 wt, mixtures of soclium carbonate and calcium carbonate having 5 micron particl~ diameter; ~.7:1 wt; mixtures of sodium sesquicar-bonate and calcium carbonate having a particl~ clia~netcr of 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonat~ at)d calcium hydroxide havin~ a particle diameter of 0.01 mic.ron; and a 3:3: 1 ~vt. mixture of sodium carbonate, sodium aluminate antl calcium o~id~ having a particle diameter of 5 ~icrons.
Oth~r In~3redients ln addition to the essentia1 deterg~nt surfactants clescribed hereinbefore, the detersent compositions herein can contain from about 1~, to about 15~,, preferably from about 2P~ to about 8~, of ~n organic surfactant sel~cted from the group consisting of i~nionic, zwitterionic, ampholytic, and cationic surfac~ants, ancl mix;ures thereof. Surfactants useful herein are listecl in U. S. Pat.
3,66l~,9~1, Norris, issued N,ay 23, 197~, and U.S. Pat. 3,919,678, 25 Laughlin et al, issued Dec.. 30, 1975. Use~u1 cationic surfactants a1so include those described in U.S. Patent 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S.
Patent 4,239,659, Murphy, issued Dec. 16, 1980. The following are representative examples of surfactants use~ul in the present composition ~ Jater-solubl~ salts oF the higher fatty acids, i.e, "soaps'l, are useful anionic surfact~3nts in ~he compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammon-ium, and alkylolammonium salts oF higher fatty acids containing from about 8 to about ~4 carbon atoms, and preferably from abou~

~2"~ 7Z

12 to about 18 carbon atoms. Soaps can be ma~le ~y direct sapnni~ication of fats and oils or by the neutr~liz~tion of free fatty acids. Particularly use,ul are the sodium ancl potassium salts of the mbctures oF fatty acids derived from coconut oil ~nd tallow, 5 i . e., sodium or potassium tallo~v ancl coconut soap. The pre ferred soa?, as discussed hereinbefore and llereinafter, especiall~
in combination with semipolar or amide nonionic detergent sur~
factants, is at least partially unsaturated.
The Unsaturated Soap The unsaturated fatty acid soap of this inventior) contain~
from about 16 -to about 22 carbon atoms, pref~rably in a straigh~
chain confi~uration. Preferably the numbe~ of car~on atoms in the unsaturated fatty acid soap is from about: 16 to about 1~.
The unsaturated soap, in common with other anionic d~ter-li gent and other anionic materials in the detel~ent cor:~positions o~
this invention, has a cation which renders the soap ~vat~r~sol~bl~
ancllor dispersible. Suitable cations includ~ soc~iun-, pntassium, amrnonium, monoethanolammonium, diethanolamoni~lm ;triethanol-ammonium, tetramethylammonium, etc. cations. Sodium ;ons are preferred although in liquid formul~tions aMmons~m~ and triethanolarnmon;um cations are useful.
A level of at least about 1~ of the onsaturatec~ ~atty acicl soap is desirable to provide a noticeable reduction ;n sudsing and corrosion. Pre;erred levels of unsaturatéd fatty ~cid ~oap are from about 1~ to about 15~, preferably from ~bout 1~ tc> about 10~, most preferably fror:~ about 2~ to about tj~ rh~ unsaturated fatty acid soap is preferably present at a level that ~ill provicle a level of from about 15 ppm to about 200 pp~, preferably from about 25 ppm to about 125 p?m in the ~-~ash sollltion at: recom~
3~ mended U. S. usa~e levels and from abou"t 30 ppn to ~bout 100 ppm, preferably from about 50 ppm to about 500 pprn for European usage levels.
I~lono-, di-, and triunsaturated fatty aci(ts are c~il cssen-tiall~
equivalent 50 it is preferred to use mostly monctunsaturated so~ps 35 to minimize the ri'sk oF rancidity. Suitabl~ sources of unsat-Jr~ted 2~7~

fatty acids are ~vell known. For example, see Ea~ley's Induserial Oil and Fat Products, Third Edition, S~Yern, published by intef-science Publisher (1964~, Preferably, the level of saturated soaps is kept ~s low as 5 possible, preferably less than about 60~, prc,erably less than about 50% of the total soap is saturatecl soap. HoweYer, lo~^f levels of saturatetl soaps can be used. Tallow and palm oll soa,os can be used.
Useful synthetic anionic surfactants also inclucle the ~vater-10 soluble salts, preferably the alkali metal, ammonium and alkylol-ammonium salts, of or~3anic sulfuric reaction products havin~ in their molecular structure an~ alkyl group containin~ from about lO
to about 20 carbon atoms and a sulfonic acid or sulfur;c acid ester groupO
l 5 Such s~nthetic anionic detergent surfactants ar^e desirable additives at a level of from about 1~ to about 10~ to increase the overall detergency effect and, if desired, increase the level of suds. ( Included in the term "alkyl" is the alkyl portion of acyl ~lroups. ~ Examples of this ~roup of synthetic surfactants ~?re the sodium and potassiur:l alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-CI8 carbon atoms) such ~s thos~
produced by reducin~ the g1ycerides of tallow or coconut oil; and the soc~ium and potassium alkylbenzene sLIl fonates in which the alkyl group contains fro~ about 9 to about IS caroon atoms, in straight chain or branched chain configuration, e.~., those of the type described in U.S. Pats. 2,220,0~ and 2,~7,383. Especially valuable are linear strai~ht chain alkylbenzene sulFonate5 in ~hich the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cll 13L~S.
Preferred anionic detergent surfactants are the alkyl poly~
ethoxylate sulfates, particularly those in which the alkyl contains from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 and wherein the polyethoxylate chain contains from about I to about IS ethoxylate moieties preferably from about I to 35 about 3 ethoxylate moieties. These anionic detergent surfactants ,?~,'7 are particularly desirable for formulatin~ heavy~ Jty licl~iid laundry detergent composition~
Other anionic surfactants herein are ~he sodiur~ at~iyl gly- x ceryl ether sulfonates, especially those ethers of higher alcohols clerived from tallow ancl coconut oil; sodium coconut oil ~atty acid 7~C
mono~lyceride sulronates and sulrates; soclium or potassium sal~s of all~yl phenol ethylene oxide ether sulfates containing from about I to about 10 units o~ ethylene ox;de per molecule and ~vherein the alkyl grou,~s contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulFates contain;ng about I to abnut 10 units of ethylen~ oxide p~r molecule and wherein the alkyl group contains from abou~ i0 to about 20 carbon atoms.
O~her useful anionic surfactants herein in~:lude th~ Yàter-soluble salts of esters of alpha-sulfona~ed fatty acids conta;nin~3 from about 6 to 20 carbon atoms in the fatty acid ~roup and frorn ~`
about I to 10 carbon atoms in the ester group; llvater-solubl~ salts of ~-acyloxy-alkane-l-sulfonic acids containin~ from about ~ to -carbon atoms in the acyl ~3roup and from about 9 to about 23 ~0 carbon atQrns in the alkane moiety; alkyt elher sulfates containin~
frorn about 10 to 20 carhon atoms in the alkyl ~roup and fron~
about I to 30 moles of ethylene oxide; water-soluble salts of olefin i`
sulfonates containin~ from about 12 to 2~1 carbon atnms; and beta-alkyloxy alkane sulfonates containir,~ from ~bo--t I to 3 2S carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives o~ heterocyclic secondary and tert;ary am;n~s ~-in which the aliphatic moiety can be straight chain or branched and wherein one of the ~liphat;c substituents contains frorn abo~t 8 to 18 carbon atoms and at least one aliphatic subtituent con^
tains an anionic water-solubilizing cyroup.
Zwitterionic surfaotants include derivative of aliphatis:
quaternary ammon;um, phosphon;um, and sulfoniurn compounds In ~--`.

- ~L2~

, ~ ~
wllich one of the aliphatic substituents contains from about ~ to 18 carbon atoms. !~
Particularly preferred auxiliary surfactants herein inclwcJc ~' linear alkylbenzene sul,ronates containing from about 11 to 1'~
5 carbon atoms in the al ~yl group; tallo~,Yalkyl sul~ates; coconutal'~yl glycer~l ether sulfonates; alkyl ether sulF~tes wherein -tl-e alkyl moiety con-tains from about 14 to 18 carbon atoms and wh~rein the ~' average degree of ethoxylation is from abou~ I to ~ lefin or paraffin sulfonates containin~ from about 11~ to 1~ carbon a~oms;
10 and alkyldimethylammoniurn propane sulfonates and alkyldimethyl-ammonim hydroxy propane sulfonates wherein the alkyl ~roup contains from about 14 to 18 ~arbon atoms. ~ ' Specific preferred surfactants ~or use herein inckJde:
sodium, potassium, mono-, di-, and triethanolammoniu-n C~ 5 15 all<yl polyethoxylatel 3 sulfates; sodium linear Cll 13 alkylbenzerle sulfonate; triethanolamine Cll 13 alkyl~en~ene sulfonat~; sodi~Jm tallow alkyl sulfate; sodium coconut all<yl ~Iyceryl ether ~ulfonate; "`
the sodium satt of a sulfated condensation product of a tallo~ `
alcohol ~vith about 1~ moles of ethylene oxic!e; 3-~N,N-climethyl-N-20 coconutallcylammonio)-2hydroxypropane-1-sulfonate;
3-~N,N-dimethyl-N-coconutalkylammoniopropane-l-sulfon~ste; ~'-

6- t N-dodecylbenzyl-N, N -dimethylammonio} -hexanoate; an cJ cocon u t alkyldimethyl amine oxide.
Other adjunct components l,vhich may be included in the 25 compositions of the present invention, in their conventional art-established'levels for use ~i.e., from O to about 90~), inclucle solvents, bleachin~ agents, bleach activators, soil-susp~n~Jiny ~' agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting a~ents ~monoethanolamin~. sodiur 30 carbonate, sodium hydroxide, etc. ), enzymes, enzym~sta~ilizln~
agents, perfum~s, fabric soften;ng components, static c:ontrol agents, and the like.
Fatty acid amide detergent surfactants useful herein inciucle those havin~ the formula~
p~6 -C-N~7 2 ?,~

- - 7 ~

- ~- I

~g`J~

~vhorein R6 is an all;yt group containing from abo~lt 7 to about 21 (preferably from about 9 to about 17) carbon atoms ancl each R
is selected from the group consisting of hyclrogen, Cl 1~ alkyl, Cl ~ hyclroxy alkyl, and -tc2H4o)xH ~Yhere x varies from about I to c~l~out 3.
Preferred amides are C8 2d ammonia amicles, monoethanolammon-iurm, diethanolamides, and isopropanol amidPs.
A special advantage of the combinat,on of cletergent surfac-tants here;n is their superior compatibility ~vith an;onic Fluores-10 cent or nptical brighteners. Nonionic surfactants, especiallyethoxylatecl nonionic detergent surFactants, normally cJiminish the ~ffectiveness of such brighteners. Ylith the acklition of the all;ylpolyglycoside surfactant, the brightener ~ff~ctiveness is clramatically improved, especialty on cottor-. From abo~tt 0.01 to 15 about 2~, preferably from about 0.1 to about 1~ optical Ltri~htener car) be useà.
Suitable brighteners include the following:
bis anilino lR) triazinyl amino stilbene sulfonat~ ha~in~ the formula:

X ~ ~ N

N ~ N l~J~ C ~
R SO~I _ 2 ~r/herein ~ is preferably Na, but can be any compattibie cation such as potassium, ammonium, substit~lted ammoni~lm, e.g, mono-, di-, and triethanolammonium, etc.; ~ can b~
3 0 R2- O ~ ' H -~vhere R is selected from H, phenyl, Cl ~1 alkyl, or Cl hydroxyalk~l; morpholino-, hydroxy; 5 NaO3S O -NH-;

~ (C~'2CH2'3CH2NH- C~ -N~3-;
NaO3S O -NH- O -NH-;

or mixtures thereof; and R can be H or S03M.
In repres0nted structures, R ar,d X are:
R X ~
,~N 1~1 . . .
4 H ) 2 ~¦

O `''' -NHCH2C~13 " ``
~0 -NHCH2CHOHCH3 .`
N ~ O II
7e -NHC2Hl~OH
-N ~C~l3) CH2CH2OH

-NHC2HSOCH3 ,;,~, -OH

N~IC2~ o~ aO35- O --N~-S ~
-N ~ O C~13O- <}N~l-10~1(OCH2CH2)3CH2NH- H(~)CH2CH2)3 2 {~ -NH-( I IOCH2CH2 )2N_ ~Na35 ~ O
tetraso~ium 4 ,4'-bis[ (4 '-bis(2"'-hydroxyethyl}amino~"-(3""-sulphenyl)al~ino-1",3",5"-triazin-2"-yl~amino]-2,2' stilbeneclisulfo-nate;
15~ disodium-4-~6'-sulfonaphtho[1',2',d]triazol-~-yl)-2-stilbene-sulfonate;
disodium t~,4'-bis~t4"-(2"'-hydroxyethylamino)-6"-anilino~
3" ,5''-triazîn-2"-yl)amino]-2 ,2'-stilbenedisulfonate;
disodium 4,1~'-bis[ ~1"-(2"'-hydro~<yethoxy)-6"-anilinsr~l" ,3" ,-5"-triazin-2"-yl)amino]-2,2'-stilbenecJisulfonate;
disodium 'I,4'-bist4-phenyl-1,2,3-tr;azol-2-yl~-2,2'-stElb~nedi-su I fona te;
sodium 4-~2H-naphtho[1,2-d]tria~ol-2-yl)stil~ene-2-su~fonate;
disodium 4,4'-bis-t2-sulfostyryl~biphenyl;
disodium 4-(2H-6-sulfonaphthotl,2-d]triazol-2--yl)stilbene-2-su I fona te; and disodium 3,7-bis(2,11-dimethoxybenzarnido}-2,~-clib~Qzothio-phenedisul fonate-5 ,5-dioxide.
Other suitabte brighteners are disclosed in U.S. Paten~s 3,537,993 Coward et al; issued November 3, 19-70 ancl 3,95~,~8 Sunclby, issued April 27, 1976, The compositions of the present in-~ention can be manu-factured and used in a variety of forms such as solids, powders, granules, pastes, and liquids. The compositions can be used in 35 the current U.S. Iaundering processes ~y forming ac~ueous ~U~'7~ `

solution containin~ from about 0.01-Qo -to about 1%, preferably frorn about û.05~ to about 0.5%, and most preferably -from about û.05S6 `'~
to about 0.25Qo of the composition in water and a~i-tating -the soiled '-~
fabrics in that aqueous solution. The fabrics are then rinsed and 5 clried. ~Yhen used in this manner the preferred compositions of the present invention yield exceptionally good deteryency on a variety of fabrics. ~
In a preferred embo~iment a laundry deter~ent, preferably, an aqueous heavy-duty liquid, contains ~a~ from a~out 1'-~ to about -~
20P~ (preferably From about 4~ to about 10~ of the alkylpo3y-glycoside detergent surfactant; (b) from about 1~ to about 10 (preferably from al~out 2~ tio about 6~) of an amin~ oxîd~ cleter- i~
gent surfactant tc) from 1~6 to about IQ~ ~preferably from abouc 1 to about 6~6) of a water-soluble soap of an unsaturated fatty ~2cid containing from about 16 to about 22 carbon atoms; ~d) from 0~ to about ~0~ (prefera~ly from about 10~ to about 30%~ of a water-soluble cletergency builder, preferably selected from the ~roup consisting of pyrophosphates, nitrilotriacetates, and mixtures thereof; (e) frorn about 0~ to about lO~d lpreferably from about 0%
to about 5~) of water-solu~le synthetic anionic cletergent sur-fac.ant; and, preferably, and 1 f) the l~alance water.
Such detergent compo~;itions provide excellent deter~ency, clo not clamage washing machines unacceptably, and can be forrnulated to provide different sudsing patterns by varying the amount and 2S types of synthetic anionic detergent surfactant and the amount of unsatura.ed soap. Preferably such formulas clo not contain more than about 5% conventional ethoxylated nonionic surfactants.
Sodium, potassium, ammonium, and alkanolammonium cations are preferred . ~`~
All percentages, parts, and ratios herein are by weigh-~
unless otherwise sp~cified.
The following example~ illustrate the composition anc~ method ~, of the present invention.
.: .

~ r ~v~

EX~lPLE I
Unbuilt Combina~ion of Cl2_1s alkyl Cl2 13 all;yl ~lun~er ~`lhiten2ss Uni .s ( H'~`JU) I~t poly~31yco- pol~ethoxy-Clay R2moval sic!es2_3 lat~6 5Polyester ~
ppm in ~`J'a,hCotton ~i.e. Poiycotton) Polyester 500 - 9.~ 15.l~ 2.~ ~~
~00 lO0 6.4 15.5 l~.6 300 200 6.3 17.1 7.1 -lO200 300 4.4 17.6 7.1 1~)0 1~0~ 2 .7 1 6 . 3 7 . 1 - 500 -~.3 I5.6 6.8 Test Condition: 95F water havin~ 6 ~rain~ of mixecl hard-ness and a mini~asher.
~s can be seen from the above results, th~ alkylpnly~l~tco sid~ surfactant has an unexpected problem ~ith cleanin~ poly- ~`
~ster. In ~eneral, the alkylpoly~lycosides are consiclerecl non-ionic sur~Cactant replacements, but, surprisin~ly, they achieve their best la-lndry results in combination ~/ith nonionic surFac-tants, esp~cially those that are optimized for cleanin~ relati~Jely hyclrophobic surfaces. The all;yl polyglycosides in these exarnple~
~vere derived from glucose. Similar results 2re obtained ~ith the ot'ner alkyl ~Iycosid~s describcad herein. , ,,-E X AI~il PL~

(Unbuilt ~lixtures) C12-l5 allcyl Cl2_13 alkyl "
polyslyco- polyethoxy-~ Dirty ~loto~ Oil P~emova~
sides2 3 late3from Polye~ter Fa~rics 300 ppm 0 ppm lO
30~l~0 ppm 60 ppm ~ . ~, IZ0 ppm 120 ppm 27 O ppr~ 300 ppm l~ ~r;
Same condi~ions as in Exarlple 1.
As can be seen ~ror~ the above data, despi~e the ~en~rally 35 inferior r~sults obtained in cleanins r~latively hydrophobic sL r--.
~L'Z`~ 2 ~aces with an alkylpoly~lycoside surfactant, the m;xtures o, an ~, alkylpolyg!ycoside and a nonionic surfactan t provicles syner~ist;c ~.
results. ~., ~`Jhiteness ~laintenance 1 Redeposition Test) C12 13 alkyl ~unter Whiteness Units ( H~'~U) C12_15 alkyl polyethoxy- White polyglyco- late3 Cotton l,'lhite '~Yhit~
side2 3Neodol 23-3 ~-shirt Polycotton Polyester 300ppm 0 73 68 36 240ppm 60 74 ~0 39 180ppm 120 79 13 1~0 60ppm 240 73 ~ 73 ~t9 0 300 71 73 3~) ~
The solutions ~vere unbuilt and used the same conditions as ``
Exam?les I and 11, t'ne grades bein~ the averacle for the two types of soils.
As can be seen from the above data, there is a syn~r~is;ic improvement in redeposition on cotton for the mixtures c~f surfac-tants.
E X ~ 1 P L E I V
C12_15 alkyl C12-13 all~yl polyglyco- polethoxy- ~ I`.1enstrual Stain Removal~-side2 31~te3 from polycotton ' 300 ppm () 50 . .
240 ppr~ oO 60 180 ppm 120 63 ppm 240 70 ~-O ppi~ 3~0 63 ~ ;~
Same test conditions as in previous exampl~s with unbuilt solu~ions. `~:
, ~ .
.~:

, , ~2`~?~1~2 -- 21~ --As can be seen from the above, the unexp~ctedly poor showing of the alkylpoly~lycoside with respect to this stain can -, be improved andlor synergistic improvement obtainecl by addi-tion of the nonionic surfactant, depending upon the ratio used.
5EXA~l PLE V
Built Per,rormance on Clay Soil Hunter ~`~hiteness Units (~IWU) Cotton Polycotton Polyester Commercial built anionic deter~ent composition ' 11.0 19.9 22.5 C12_15 alkYIPIY91YCside2_3 ~
lS C~2 13 all~YIPIYethoxylate6,5 12.7 21.2 ~ 3 ~uilt with 25% sodium tripolyphosphate ~5TP) and 10~ socli-um carbonate, the totai composition being used at a lev21 of 1200 ppm .
20Test Conaition: 60F water having 9 grains of mixed hard-ness and miniwasher.
As can be seen from the above the mixed surfactant system of this invention provides equivalent or superior clay removal across a variety of fabric types as compared to more conventlonal 25anionic surfactants.
.~

~2~ 72 EX~IPLE Vl Cl2_l5 alkyl C12 13 alkyl polyglyco- polye~hoxy-sides ~ 3 late 6 . S
~ coconut alkyl Coconut alkyl dimethylamine dime-thylamine oxide (1:1) oxide Clay Removal, H~'JU
Cotton 14.6 li.2 ;, Polycotton ~8 . 5 22 ~1 Polyester ~ 59 . a 55 . 2 Removal, %
Dirty motor oil 30 ~7 :
Chocolate syrup ~3 93 Grass 67 73 ~`
Bacon grease 57 53 I\,lenstrual stain 83 73 .:
Spaghetti sauce 50 67 Body Soil Removal, PSU~ s.
Commercial Unbuilt Heavy- ;
Duty Liquid t(~ontrol) ~1.5 ~`lhiteness, Soler 2A
T-shirt 78 , f7 Polycotton 86 85 ~t,~`
Polyester 46 39 The surfactant mixture was 139~ oF the formula ~nd the build-er was sodiurn nitrilotriacetate at 18~. The test concJi tiO115 ~re ~100 ppm of the composition, 95F, 6 grains o~ mixed harclne~s~
*PSU equals Panel Score Units wherein exp~rt graders 3ssign ':
30 values based on 0 = no difference; I = difference; and 2 = clear difference.

~. -, ,~ . .

:

-~;~`U(:~L7;~

EX~lilPLE Vl I
Unbuilt HC)L Perforrnance c~
The invention vs. unl:)uilt commercial heavy-duty l;ctuid `;;
detergent composition tHDL).
Panel Score Units vs. Commercial Product Cotton Polyester Di rty motor oi l ~0 . 3 *0 . 4 Bacon ~3rease ~1. 0 -~0 .8 Gravy +1.4 *0.2 10 Spaghetti sauce `~0.3 ~.9 Grass +1.7 +1.5 - Chocolate syrup 1 _0.11 ~0.6 TEST CONDITION: 450 ppm actives, ~5F water havin~ 6 grai-ls mixed hardness and a mini washer.
15 Composition of the invention: C12 13 all<ytpoly~thoxyl~t~31 C12-15 all~ylpoly91ycosid~2_3 at a ratio o~ 1:1. ;
EXA~IPLE Vl 11 Formu la Pa rts C12 15 alkylpoly~llycoside2-3 13-3 2G C12_13 alkYIPIYethoxylate6 5 13.3 Sodium tripolyphosphate 12. 0 Na2 CO3 13 . 3 Polyacetaldehyde deter~ency builder 28.8 ~nionic brightener* 1.0 25 *bis(anilino-hydroxyethylmethylamino-triazinylamlno)stilbene disulfonate (sodium saltl.
Fluorescer Effectiveness Filtered Vnfiltered HWU H`.`/UDelta F Soler 2A ~.
3~C12_15 alkylpoly~llyC- ~~
side2 31Neodol 23-6.5 79 111 22 87 Commercial built anionic ~-detergent ~controll 80 106 1~ 80 `;

7~

Significant technical differences: H~'~U=2; Soler 2A-2; and F=t . i`~
EXAl\lPLE I X
;~edeposition ancl ~`~hi tenessl Bri~htness Test Cot~on T-Shirt The following results using unbuilt mixtures oF surfactants clearly demonstrate the effect of the allcylpoly~lycosic1e in im- --proving anionic brightener effectiveness in the presenc~ of non-ionic surfactants. The ~ata show clearly th~t at least about 40 10 of the surfactant system should be alkylpoly~lycosicle. Five to six HWUs are a substantial ~mprovement. ~-C12_l3 alkyl- C12-t3 alkyl- Unfiltered~
polyglycosid~2 3 polyethoxylate3 Hunter ~Yhiteness Units eefore ~fter t)elta '``
~Vashin~ Washin~ ~ oss) 100 0 120 110 10 "~
122 113 !3 -11~ 109 9 2~ 20 80 119 92 27 0 100 11~ 91 27 `, *To measure brightener effect Conditions: ~liniwasher, 6 ~rains mixed hardness, 100F, one cycle 300 ppm total surfactant, 15 ppm of the brightener of 2S E~ampl2 Vl 11.
EXAI`~tPLE X
The allcylpolyglycosides improve the perfortnancc o~ very water soluble ~high HLB) nonionics.
F~atio Clay Cleanin~ Per~ormance 30C12_l3 alkyl-C12 13 alkyl- Hunter Whiteness Uni~s poly91ycosi~e2-3poiyeehoxylatel2 Polyester Polycotton Cotton ~, IOo 0 25.9 2.~ 1.2 ~-27. ~ 3.3 2.5 i`~
35 60 40 28.8 ~.2 3.~ -~0 29 O i 5 . 0 ~.2 -0 loO 28 . i 2 . 2 2 .1 ;
~;z~a~7~

ConcJitions: ~liniwasl-er, unbuilt, 6 ~3rains ~t mj~;ed hard-ness, 100F, 300 ppm total active. ~^~
~ \s can l~e seen from the above data, the mixtures are clear-Iy sLlperior. From I to 2 ~I~',U are a substantial difference in this 5 t~st.
EXAI~;PLE X I
Alkyl Polyglucosides Improve the Performance of Oil Soluble (Low HLB) Nonionic Deter~3ent Surfactants (HWU) fP.S.tJ,) 10Ratio Clay Remo~al Li pid Facial from Soil F~emoval C12 1 alkyl- C 2 alkyl- Poly- from ~`
polygl~coside2_3 pol~ox~late3 esterCottonPolycotton r 100 0 23 . 9 ~ 0 . 2 24. 9 -~. I 0 ~ 5 1560 40 24.6 -11.9 û.6

8.8 -~1.0 -~).ll 0 100 -0 . 8 -27. ~--1) . 9 Conditions: ~liniwasher, Unbuilt, 6 ~r~îns mixecl hardness, 100F, 300 ppm. (LSD95 = 1.2 Hl,YU for clay cand ~ 5C) 20 P. S . U. for facial scil. ) Clearly, the above results show the improvement from mixin~
conventional (ethoxylated) nonionic de-ter~ent surfact~nts with alkylpolyglycosides. The mixtures provide a substantîal i~prove-ment in deter~ency.
EXAI~lPLE X 11 Combina,ions of alkyl pDlyglucosides and ser~ polar nonionîc ,~i and/or amide deterg~nt surfactan~s are compatible with unsatur ated soap, but not with saturated soap~

Formula C12_13 al~YIPIY91YCside2~3 7.3^/.3 7.3 7.3 7.3 C~2 15 alkyldimethylamine oxide3.3 3.3 3.3 ~.3 3.3 Sodium oleate 2.2 ~ 4.~1 12`0(~3 ~2 Soclium ta I lowa te - 2 . 2 Sodium stearate - - 11.4 - - '`
Soclium CILI 15 alkyl polyethoxylate 1,45 1.~5 - 2.9 ~ r, 2 25 sulfate Cocor-ut diethanolamide 0.13 0.13 0.25 ~.13 0.25 Sodium nitrilotriacetate 18.2 18~2 18.2 18.2 1~.2 -Sodium carbonate 2.$ 2.8 2.8 2.~ 2.8 Sodium toluene sulfonate 2 2 2 2 2 ~, E~hyl alcohol 3 3 3 3 3 ~Vater ---Balance Compositions 1-3 and ~ were lower sudsing than f~rmula and were ~ore compatible with washing machine surfaces (less corrosive) Cornposition 3 formed an unsightly soap scum in the ~;, rinse water despite the presence of materials tcnown to inhibit ,~,-formation of such scums. Composition, 3 also formed' a thick gel ;c, rather than a free flowing, clear liquid. It is clear that there must not be a substantial excess of saturated soap over ~nsatura~
ted.' The soap must be at least about 40~ unsaturated soap.
It has additionally been discovered that the performance of ", these compositions is improved if the total free fatty alcohol ', containing from about 8 to about 20 carbon atoms is less than , about 5~, preferably less than about 2%, most preferahly less ;' than about 1%.
~, ~VHAT IS CLAI~ D IS:
r ,~,, o:

.
r, .

~ ~ ~
~. ' r S
~, . .

Claims

WHAT IS CLAIMED IS:

1. A detergent composition comprising:
(A) from about 1% to about 90% of an alkylpolysaccharide detergent surfactant of the formula RO(R'O) y(Z)x where R is an alkyl hydroxy alkyl, alkyl phenyl, hydroxy alkyl phenyl, alkyl benzyl or mixtures thereof said alkyl groups containing from about 8 to about 18 carbon atoms; where each R' contains from 2 to about 4 carbon atoms and y is from 0 to about 12; and where each Z is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms, and x is a number from about ?to about 10:
( B) from about 1% to about 90% of a nonionic detergent surfactant;
(C) from 0% to about 90% of a detergency builder, the ratio of (A) to (B) being from about 1:10 to about 10:1; and;
(D) from about 0.01% to about 2% of an anionic optical brightener .

2 . The composition of Claim I wherein Component (I) has the formula R2(CnH2nO),(glucosyl)x wherein R is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof n is 2 or 3, t is from 0 to about 10, the glycosyl moiety is derived from glucose, and x is from about 1 1/2 to about 3.

3. The composition of Claim 2 wherein the nonionic surfactant has an HLB of from about 5 to about 17 and the anionic optical brightener is present in an amount from about 0.1 to about 1%.

4. The composition of Claim 1 wherein the anionic optical brightener is selected from the group consisting of:
bis anilino (R) triazinyl amino stilbene sulfonate having the formula:

wherein M is potassium, ammonium, substituted ammonium, or mixtures thereof; and R and X are:
R X
-N(C2H4OH)2 " ;
" ;

" ;

" ;
-NHC2H4OH " ;
-N(CH3)CH2CH2OH " ;
-NHC3H6OCH3 " ;
-NHC2H4OH " ;
-NHC2H4OCH3 " ;
-OH " ;

-NHC2H4OH ;

;

H(OCH2CH2)3CH2NH- ;

HOCH2CH2)2N- ;
tetrasodium 4,4'-bis[ [4"-bisl2"'-hydroxyethyl)anilino-6 -(3""-sulphenyl)amino-1",3",5"-triazin-2"-yl)amino]-2,2''-stilbenedisulfo-nate;
disodium-4-(6'-sulfonaphtho[1',2',d] triazol-2-yl)-2-stilbene-sulfonate;
disodium4,4'-bis[(4"-(2"'-hydroxyethylamino)-6"-anilino-1"",-3",5"-triazin-2"-yl)amino] -2,2'-stilbenedisulfonate;
disodium 4,4'-bis[ (4"-(2"'-hydroxyethoxy)-6"-anilino-1",3",-5"-triazin-2"-yl)amino]-2,2'-stilbenedisulfonate;
disodium 4,4'-bis(4-phenyl-1,2,3-triazol-2-yl)-2,2'-stilbenedi-sultonate;
disodium 4,4'-bis-(2-sulfostyryl)biphenyl;
sodium 4-(2H-naphtho[1,2-d] triazol-2-yl)stilbene-2-sulfonate;
disodium 4-(2H-6-sulfonaphtho[1,2-dltriazol-2-yl)stillbene-2-sulfonate; and disodium 3,7-bis(2,4-dimethoxybenzamido)-2,8-dibenzothio-phenedisulfonate-5,5-dioxide and mixtures thereof.

5. The composition of Claim 4 wherein the ratio of (A) to (B) is from about 1:3 to about 3:1.

6. The composition of Claim I wherein the detergency builder is, present at a level of from about 20% to about 50% and is selected from the group consisting of hydrated Zeolites A, X, and P, having a particle size of from about .01 to about 10 microns, alkali metal ammonium or substituted ammonium tripolyphosphates, pyrophosphates, carbonates, silicates, borates, polymeric meta-phosphates, nitrilotriacetates, citrates, and polyacetal carboxyl-ates and mixtures thereof.

7. The process of cleaning cotton fabrics in an aqueous deter-gent solution containing from about 0.01% to about 1% of the detergent composition of Claim 1.