CA1200171A - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA1200171A CA1200171A CA000412243A CA412243A CA1200171A CA 1200171 A CA1200171 A CA 1200171A CA 000412243 A CA000412243 A CA 000412243A CA 412243 A CA412243 A CA 412243A CA 1200171 A CA1200171 A CA 1200171A
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- Prior art keywords
- alkyl
- composition
- carbon atoms
- detergent
- nonionic
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
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.
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
L'7~L
DETER~;ENT COMPOSITIONS
Ramon A. Llenado Field of the Invention This invention relates to surfactant combinations which provide good detergency and, optionally, good fluorescer effectiveness and/or suds control and/or corrosion inhibition in a laundry context. Such compositions can be either built or unbuilt, granular or liquid, and can contain the usual auxiliary ingredients common to such compositions.
Description of the Prior Art Alkylpolyglycosides which are surfactants have been disclosed in U.S. Patents 3,598,865; 3,721,633; and 3,772,269. These patents also disclose processes for making alkylpolyglycoside surfactants and built liquid detergent compositions containing these surfactants. U.S. Patent 3,219,656 discloses alkylmonoglucosides and suggests their utility as foam sta~ilizers for other surfactants. Various polyglycoside surfactant structures and processes for making them are disclosed in U.S. Patents 3,640,998; 3,839,318;
3,314,936; 3,346,55~; 4,011,389, ~,223,129.
Summary of the Invention This invention relates to the discovery of certain ~ombinations o surfactants which provide unusually good detergency, especially in cool water, for a variety of fabric typesO Specifically this invention relates to detergent compositions comprising:
(l? from about 1~ to about 90~ of alkylpolysaccharide detergent surfactant having the formula RO (R ) y (Z) x where R is an alkyl, hydroxy alkyl, alkyl phenyl, alkyl benzyl, or mixtures thereof, said alkyl groups containing from akout 8 to about 18 carbon atoms, where each R' contains from 2 to about 4 carbon a~oms, .. ~. .
L7~ -preferably an ethoxy, propoxy, or cJlyceryl ~roup, and y is from O to about 12; and whare each Z ;s a rno;ety derived from a reclucing saccharide containin~3 5 c>r 6 carbon atoms, and x is a number Fro~ about 1-1- to about 10;
~2~ from about 1O to about 90% of a nonionic deterqent surFactant; and (3) from 0~ to about 90g~ of a deterge~lcy builder, th~ ratio of ~1~ to (2~ being from about 1:10 to about 10:1, pre-ferably from abo-~t 3:1 to about 1:3.
A highly preferred variation also comprises frorn 2bout 0 . 01 to about ~.0~ o~ an anionic fluorescer toptical l~rightener~
In another highly preferred variationr ths nonionic cletergent surFactant is selected from the group consistif~g of ~min~ oxid~
cleterg~nt surfactants, amide detergent surfact3nts and mixtures thereof, and the composition additionally comprise~ fro~ about 1~
to about 10~ of an unsaturated soap containin~ frorn ~bout 16 to about 22 carbon atoms, and, preferatlly, frorn ~Ibout 0% ~o 2bout 10-~ of a synthetic anionic detersent surFact2nt ~0 Description of the Preferred Embodiments The Alkyl?olysaccharide Surfactant I t has surprising!y been found that the cosur~actants inter-act ~ith the ~Ikylpolysaccharide surfactant oF this invention -to provicle good laundry detergency for a ~/idz ran~e o f ~abrics .
The alkylpolysaccharicles are those havin~ a hydrophobic ~3roup containing from about 6 to about 30 carbon atoms, preferably ~ro~n about 10 to about 16 carbon atoms and a polysaccharide, e 9., a polyglycoside, hydrophilic group containin~J from about 1~ to about 10, preferably from about 1~ to about 3, most preferably frorn about 1.6 to about 2.7 saccharide units. ~ny reJ-Jcing sacc~arld~
containing 5 or 6 carbon atoms can be useci f e. c~ cos~, ~alactose and galactosyl moieties can substitute for th~ ~1ucosyl rnoieties. ~Optionally the hydrophobic group is attachec3 ~t l:ne 2, 3, 4 etc. positions thus givincJ a glucose or galactose as o~posed to a cJlucoside or Jalac;oside. ) The intersaccharide bonds can be, e.g., between the one po,ition of the additional saccharide units ~2~ '7~
and the 2-, 3-, 4-, and/or 6 positions on thne precedin~
saccharide units.
Optionally, and less desirably, there can ~e a polyalkox;de chain joining the hydrophobic moiety and the polysaecharide moiety. The preferred alkoxide is ethylene oxic~e. Typical hydrophobic groups include alkyl groups, either saturatecl or unsaturated, branched or unbranched containin~3 From a~out S to about 18, preferably from about 10 to about 16 carbon ~tomsA
Preferably, th~ alkyl group is a straight chain satur~tecl alkyl group. The alkyl group can contain up to 3 hydroxy ~3roups andlor the polyalkoxide chain can contain up to about 10, pref~r-ably less than 5, most preferably 0, aikoxide rnoieties. S~Jita~ie alkyl polysaccharides are octyl, nonyldecyl, unclecyldoclecy~
tridecyl, tetradecyl, pentadecyl, he~cadecyl, heptacl~cyl, anc}
octadecyl, di-, tri-, tetra~, penta-, and hexaglucosides, galactosides, lactosides, ~lucoses, fructosides, fructoses, and~or yalactoses. Suitable mi~ctures inciude coconut alkyl, cli-, tr;-, tetra-, and pentaglucosides and tallow alkyl tetra-, pent~ 3nd hexa~ lucosid~s .
DETER~;ENT COMPOSITIONS
Ramon A. Llenado Field of the Invention This invention relates to surfactant combinations which provide good detergency and, optionally, good fluorescer effectiveness and/or suds control and/or corrosion inhibition in a laundry context. Such compositions can be either built or unbuilt, granular or liquid, and can contain the usual auxiliary ingredients common to such compositions.
Description of the Prior Art Alkylpolyglycosides which are surfactants have been disclosed in U.S. Patents 3,598,865; 3,721,633; and 3,772,269. These patents also disclose processes for making alkylpolyglycoside surfactants and built liquid detergent compositions containing these surfactants. U.S. Patent 3,219,656 discloses alkylmonoglucosides and suggests their utility as foam sta~ilizers for other surfactants. Various polyglycoside surfactant structures and processes for making them are disclosed in U.S. Patents 3,640,998; 3,839,318;
3,314,936; 3,346,55~; 4,011,389, ~,223,129.
Summary of the Invention This invention relates to the discovery of certain ~ombinations o surfactants which provide unusually good detergency, especially in cool water, for a variety of fabric typesO Specifically this invention relates to detergent compositions comprising:
(l? from about 1~ to about 90~ of alkylpolysaccharide detergent surfactant having the formula RO (R ) y (Z) x where R is an alkyl, hydroxy alkyl, alkyl phenyl, alkyl benzyl, or mixtures thereof, said alkyl groups containing from akout 8 to about 18 carbon atoms, where each R' contains from 2 to about 4 carbon a~oms, .. ~. .
L7~ -preferably an ethoxy, propoxy, or cJlyceryl ~roup, and y is from O to about 12; and whare each Z ;s a rno;ety derived from a reclucing saccharide containin~3 5 c>r 6 carbon atoms, and x is a number Fro~ about 1-1- to about 10;
~2~ from about 1O to about 90% of a nonionic deterqent surFactant; and (3) from 0~ to about 90g~ of a deterge~lcy builder, th~ ratio of ~1~ to (2~ being from about 1:10 to about 10:1, pre-ferably from abo-~t 3:1 to about 1:3.
A highly preferred variation also comprises frorn 2bout 0 . 01 to about ~.0~ o~ an anionic fluorescer toptical l~rightener~
In another highly preferred variationr ths nonionic cletergent surFactant is selected from the group consistif~g of ~min~ oxid~
cleterg~nt surfactants, amide detergent surfact3nts and mixtures thereof, and the composition additionally comprise~ fro~ about 1~
to about 10~ of an unsaturated soap containin~ frorn ~bout 16 to about 22 carbon atoms, and, preferatlly, frorn ~Ibout 0% ~o 2bout 10-~ of a synthetic anionic detersent surFact2nt ~0 Description of the Preferred Embodiments The Alkyl?olysaccharide Surfactant I t has surprising!y been found that the cosur~actants inter-act ~ith the ~Ikylpolysaccharide surfactant oF this invention -to provicle good laundry detergency for a ~/idz ran~e o f ~abrics .
The alkylpolysaccharicles are those havin~ a hydrophobic ~3roup containing from about 6 to about 30 carbon atoms, preferably ~ro~n about 10 to about 16 carbon atoms and a polysaccharide, e 9., a polyglycoside, hydrophilic group containin~J from about 1~ to about 10, preferably from about 1~ to about 3, most preferably frorn about 1.6 to about 2.7 saccharide units. ~ny reJ-Jcing sacc~arld~
containing 5 or 6 carbon atoms can be useci f e. c~ cos~, ~alactose and galactosyl moieties can substitute for th~ ~1ucosyl rnoieties. ~Optionally the hydrophobic group is attachec3 ~t l:ne 2, 3, 4 etc. positions thus givincJ a glucose or galactose as o~posed to a cJlucoside or Jalac;oside. ) The intersaccharide bonds can be, e.g., between the one po,ition of the additional saccharide units ~2~ '7~
and the 2-, 3-, 4-, and/or 6 positions on thne precedin~
saccharide units.
Optionally, and less desirably, there can ~e a polyalkox;de chain joining the hydrophobic moiety and the polysaecharide moiety. The preferred alkoxide is ethylene oxic~e. Typical hydrophobic groups include alkyl groups, either saturatecl or unsaturated, branched or unbranched containin~3 From a~out S to about 18, preferably from about 10 to about 16 carbon ~tomsA
Preferably, th~ alkyl group is a straight chain satur~tecl alkyl group. The alkyl group can contain up to 3 hydroxy ~3roups andlor the polyalkoxide chain can contain up to about 10, pref~r-ably less than 5, most preferably 0, aikoxide rnoieties. S~Jita~ie alkyl polysaccharides are octyl, nonyldecyl, unclecyldoclecy~
tridecyl, tetradecyl, pentadecyl, he~cadecyl, heptacl~cyl, anc}
octadecyl, di-, tri-, tetra~, penta-, and hexaglucosides, galactosides, lactosides, ~lucoses, fructosides, fructoses, and~or yalactoses. Suitable mi~ctures inciude coconut alkyl, cli-, tr;-, tetra-, and pentaglucosides and tallow alkyl tetra-, pent~ 3nd hexa~ lucosid~s .
2~ The preferred alkylpolyglycosides have the formula Fi OtCn~l2nO)~t9lycosyl)x wherein F~ is selected from the group consistin~ of alkyl, 21kyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures therevf in ~hich said alliyl gro~ups contain From about 10 to abc~u~ 18, preferably from about 12 to about 14 carbon atorns; n is ~ or 3, preferably 2; t is from 0 to about t0, preferably 0: and x is from 1-' to about 10, pre~erably from about 1~ -to about 3, mos~
preferably from about 1.6 to about 2.7. The glycosyi is pre~erably derived from glucose. To prepare compounds ~h~
alco'nol or alkylpolyethoxy alsohol is formed first and therl reactecl with glucose, or a source of glucose, to ~nrm the gluco~sde (attachment at the l-position). The addition~l ylycosyl units ~re~
attached between their l-position and the precedin~3 ~Iycosyl ~nits 2-, 3-, 4- andlor 6- position, preferably preclominately the 3s 2-position.
Preferably the content of alkylmonoglycoside is lo~t, prefer-ably less than about 60~, more preferably less than about 50~
Surprisingly, anionic fluorescers which are normally rela-tively ineffective in the presence of conventional ethoxylated S nonionic cietergent surfactants at high levels in the al)sence of substantial levels of anionic detergent surfactants, are very ef~ective when the alkylpolyglycoside surf2ctants ~re present.
For brightener effectiveness, the ratio of ~31kylpolyglycosid2 detergent surfactant to nonionic detergent surfactant should b~
10 greater than about 1:4 preferably greater than about 1:3, most preferably greater than about 1:1. .
THE ~ION!ONIC DETERGENT SURFACT~N T
Nonionic Surfactant Nonionic surFactants, including those having an HLa of from 15 about S to about 17, are well l;nown in the detergency art. They are included in the compositions of the present invention togeth~r ~vith the, e.g., alkylpolyglycoside surfactants defined hereinbe-fore. They may be used singly or in combination ~`Jith one or more of the preferred alcohol ethoxylate nonionic surfactants, 20 described below, to form nonionic surfactant mixtures useful in combination with the alkylpolyglycosicl~.s. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. No. 3,332,8~0, Kcssler et al, issued J~lly 25, 1967, 25 Nonlimiting examples of suitable nonionic surfactants ~vhich may be used in the present invention arè as follo~s:
(1~ The polyethylene oxide condensates of alkyl phenols~
These compounds include the condensation products of alkyi phenols having an alkyl group containing from about 6 to 12 30 carbon atoms in eitller a straight chain or branchecl chair~ con-fi~uration witSl ethylene oxide, said ethylene o xide bein~ present in an amourlt equal to 5 to 25 moles of ethylene oxide per mol~ oF
alkyl phenol. The alkyl substi~uent in such compounc!s can b~
derived, for example, from polymeri~ed propylene, cJi;sobutyleneO
35 and the lil~e. Exam?les of compounds of this type includ~ nony~
,~
i ~`
. . .
phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; doclecylphenol condensed with ~bout 12 moles of ethylene oxide par mole of phenol; dinonyl phenol condensed with about 15 nloles of ethylene oxide per mole of phenol; and diiso-S octyl phenol conder~sed with about 15 moles of ethylene oxide ,oermole of phenol. Comm~,rcially available nonionic surfactants of this type Includ~ Igepat~CO-630, marketed by the GAF Corpora-tion, and Trito X-45, X-114, X-100, and X-102, all r:larketed by the Rohm ~ Haas Company.
(~) The condensation products of aliphatic alcohols with from about I to about 25 moles o~ ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or hranched, pri-mary or secondary, and generally contains from about 8 to about 22 carbon atorns. Examples of such ethoxylated atcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per r:lole of alcohol; and the cond~n-sation product of about 9 moles of ethylene oxide Y~ith coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms). Examples of com~ ercially available nonionic surfactants in this type include Ter~itol~15-S-9, marl;eted by Union Carbide Corporation, t~leodo~45-~, Neo~ol 23-6.5, Neodol 45-7,~nd Neodol 45-'" marketed by ~hell ~hemical Company, and l~yro EOB, marketed by The Procter ~ Gamble Company .
preferably from about 1.6 to about 2.7. The glycosyi is pre~erably derived from glucose. To prepare compounds ~h~
alco'nol or alkylpolyethoxy alsohol is formed first and therl reactecl with glucose, or a source of glucose, to ~nrm the gluco~sde (attachment at the l-position). The addition~l ylycosyl units ~re~
attached between their l-position and the precedin~3 ~Iycosyl ~nits 2-, 3-, 4- andlor 6- position, preferably preclominately the 3s 2-position.
Preferably the content of alkylmonoglycoside is lo~t, prefer-ably less than about 60~, more preferably less than about 50~
Surprisingly, anionic fluorescers which are normally rela-tively ineffective in the presence of conventional ethoxylated S nonionic cietergent surfactants at high levels in the al)sence of substantial levels of anionic detergent surfactants, are very ef~ective when the alkylpolyglycoside surf2ctants ~re present.
For brightener effectiveness, the ratio of ~31kylpolyglycosid2 detergent surfactant to nonionic detergent surfactant should b~
10 greater than about 1:4 preferably greater than about 1:3, most preferably greater than about 1:1. .
THE ~ION!ONIC DETERGENT SURFACT~N T
Nonionic Surfactant Nonionic surFactants, including those having an HLa of from 15 about S to about 17, are well l;nown in the detergency art. They are included in the compositions of the present invention togeth~r ~vith the, e.g., alkylpolyglycoside surfactants defined hereinbe-fore. They may be used singly or in combination ~`Jith one or more of the preferred alcohol ethoxylate nonionic surfactants, 20 described below, to form nonionic surfactant mixtures useful in combination with the alkylpolyglycosicl~.s. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. No. 3,332,8~0, Kcssler et al, issued J~lly 25, 1967, 25 Nonlimiting examples of suitable nonionic surfactants ~vhich may be used in the present invention arè as follo~s:
(1~ The polyethylene oxide condensates of alkyl phenols~
These compounds include the condensation products of alkyi phenols having an alkyl group containing from about 6 to 12 30 carbon atoms in eitller a straight chain or branchecl chair~ con-fi~uration witSl ethylene oxide, said ethylene o xide bein~ present in an amourlt equal to 5 to 25 moles of ethylene oxide per mol~ oF
alkyl phenol. The alkyl substi~uent in such compounc!s can b~
derived, for example, from polymeri~ed propylene, cJi;sobutyleneO
35 and the lil~e. Exam?les of compounds of this type includ~ nony~
,~
i ~`
. . .
phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; doclecylphenol condensed with ~bout 12 moles of ethylene oxide par mole of phenol; dinonyl phenol condensed with about 15 nloles of ethylene oxide per mole of phenol; and diiso-S octyl phenol conder~sed with about 15 moles of ethylene oxide ,oermole of phenol. Comm~,rcially available nonionic surfactants of this type Includ~ Igepat~CO-630, marketed by the GAF Corpora-tion, and Trito X-45, X-114, X-100, and X-102, all r:larketed by the Rohm ~ Haas Company.
(~) The condensation products of aliphatic alcohols with from about I to about 25 moles o~ ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or hranched, pri-mary or secondary, and generally contains from about 8 to about 22 carbon atorns. Examples of such ethoxylated atcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per r:lole of alcohol; and the cond~n-sation product of about 9 moles of ethylene oxide Y~ith coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms). Examples of com~ ercially available nonionic surfactants in this type include Ter~itol~15-S-9, marl;eted by Union Carbide Corporation, t~leodo~45-~, Neo~ol 23-6.5, Neodol 45-7,~nd Neodol 45-'" marketed by ~hell ~hemical Company, and l~yro EOB, marketed by The Procter ~ Gamble Company .
(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylen~ oxide with propylene glycol. The hydrophobic portion of lhese com~
pounds has a molecular weight of from about 1500 to 1800 and cxhibies water insolubility. The addition of polyoxyethylen~
moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where ihe polyox~,~ethyl~n~
content is abou~ 50~ of the total weight of the condensatton product, which corresponds to condensation with up to about ~0 35 moles of e~hylene oxideO Examples of compoun~Js o~ this type !
7~
inclucle certain of the commerciatly available Pluronic surfactants, marl;eted by ~Yyandotte Cher~ical Corporation~
t4) The conclensation products of ethylene oxide ~vith the product resultin~ from the reaction of propylene oxicJe an~ ethyl-S cl~ediamine. The hydrophobic moiety of these pro~ucts consists of the reaction product o~ ethylenediamine and excess propylen~
oxide, said moiety havin~3 a molecular ~veight oF from about 2S0û
to about 3000. This hydrophobic moiety is condensed ~/ith ethyl~
ene oxide to the extent that the condensation product c.ontains 1~ from about 40~ to about 8091 by wei~ht of polyoxyethylen~ ~nd has a molerular weight of from about 5,000 to about 11,000. Examples of this type of nonionic ~ rfactant inclucle certain of the commer-cially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.
(S~ Semi-polar nonionic detergent surfactants inclucle water-soluble amine oxides containing on~ alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected ~rom th~ group consisting of alkyl groups and hydroxyalkyl groups 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 consistin~ of alkyl ~rou~s ancJ
hydroxyalkyl groups containin~ from about I to 3 carbon ato~s;
and water-soluble sulfox'des containing one alkyl moiety of from ~bout 10 to 18 carbon atoms and a moiety selected fror~ the group ~5 consisting of alkyl and hydro~yalkyl moieties oF from about I to 3 carbon atoms.
Preferred semi-polar nonionic detergent surfactants are th~
amin~ oxide detergent surfactants having the formula o R ~OF< ) XNR 2 herein R3 is an alkyl, hydroxy alkyl, or alkyl phenyl ~roup or mixtures thereof containing from about a to abou~ ?2 cartjc.n atoms, R is an all;ylene or hydroxy alkylene group containin~3 from 2 to 3 carbon atoms or mixtures thereof, x is ~rc)fn 0 to abou~ 3 and each R is an alkyl or hydroxy alkyl group con~aino ing from I to about 3 carbon ato~s or a polyethylen~ oxide group containing from one to about 3 ethylene ox;de groups and said R5 groups can be a-ttached to each other, e. g ., throu~h an oxygen or nitrogen atom to form a ring structure.
Preferred amine oxide detersent surfactants are C1O 18 alkyl dimethyl amine oxide, C8 18 alkyl dihyciroxy ethyl amine oxide, and C8 12 alkoxy ethyl dihydroxy ethyl amine oxic~e.
. Nonionic detergent surfactants (1)-(4) are conventional ethoxylated nonionic deter~ent surfactants.
Pref~rred alcohol ethoxylate nonionic surfactants for us~ in the compositions of the present invention are biode~raclable and have the formula R8(o~;2H4)noH, wherein R~ is a primary or secondary alkyl chain of ~rom about 8 to about 22, preferably from about 10 to about 20, c~rbon atoms t5 and n is an average of ~rom about 2 to about 12, particularly from at~out 2 to about 9. The nonionics have an HLB (hydrophilic-llpophilic balance) of from about S to about 17, preferably from abou~ 6 to about 15. HLB is defined ~n det~il in ~onionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, page~ 606-613. In preferred nonionic surfactant~, n is from 3 to 7. Primary linear alcohol ethoxylates (e.y., alcohol ethoxylates produced from organic alcohols which contain about 20~ ~-methyl branched isomers~ commercially avail~
able from Shell Chemical Company under the traclename Neodol are preferred from a performance standpoint.
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensat;on product of C1O alcohol ~/ith 3 moles of ethylene oxide; the conden-sation product of tallow alcohol with 9 moles of ethylene oxide;
the condensation product of coconut- alcohol ~ith 5 moles of ~thyl~
ene oxide; the condensation product of coconu t ~Icohol with 6 moles of ethylene oxide; the condensation ,~roduct of C12 alcohoi with 5 moles of ethylene ox;de; the condensation larocluct o~ Cl~ 13 alcohol ~ith 6.5 moles of ethylene oxide, and the same condensa-tion produce which is stripped so as to remove substantially all .~
7~L
lower ethoxylate and noneth~xylated fractions; the condensation product of C12_13 alcohol with 2.3 moles of ethylene oxide~ and the same conclensation produc; which is stripped so as to remove substantially all lower ethoxylate and nonethoxylated fractions;
5 the condensation product of C12_13 aicohol ~ ith 9 moles of ethyl-ene oxide; the condensation product of Cll~ 15 alcohol ~Yith 2.25 moles of ethylene oxide; the condensation product of Cl,l 15 ~Ico-hol with 4 moles o~ ethylene oxide; the cond~nsation product o~
C14 15 alcohol with 7 moles of ethylene oxide; and the condensa~
10 tion product of Cl~ 15 alcohol with 9 moles of ethylene~ oxide.
The compositions of the present invention may contain mix-tures of the preferred alcohol ethoxylate nonionic surfactants together with other types of nonionic sur~actants. On~ of the preFerred nonionic surfactant mixtures contains a~ least one of th~
15 preferrecl alcohol ethoxylate nonionics, and has a ratio of the preferred alcohol ethoxylate surfactant (or surfactants3 to th~
other nonionic surfactant (or surfactants) of from ~bou~ 1:1 to about 5:1. SpeciFic examples of surfactant mix~ures useful in the present invention include a mixture of the condensation product 20 of Cl~ IS alcohol with 3 moles of ethylene oxide ~ Neoclol 1~5-3) and the condensation product of Cll~ 15 alcohol Yith ~ moles o~ etl~yl-ene oxide (Neodol 45-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to abo-lt 3 ~ rnix-ture oF the condensation product of C10 alcohol with 3 moles o~
25 ethylene oxide together with the conclensa, ion product of a secondary C15 alcohol with 9 mol~s of ethylen~ oxide (Tergitoi 15-5-9~, in a ratio of lower ethoxylate nonionic to high~r ethoxylate nonionic of From about 1:1 to about 4:1; a mixture of Neodol 4S-3 and ~rergitol 15~S-g, in a ratio of lower ethoxyla~
3n nonionic to higher ethoxylate nonionic of From about 1:1 tCI ~bout 3 :1; and a mixture o~ Neodol 45-3 with the conàens~etion pro~
of myristyl alcohol with 10 moles of ethylene oxid~, in ~ rat~c of lower ethoxylate to higher ethoxylate of from .lbout 1:1 t~ abo 3 : I .
, Preferred nonionic surfactant mixtures may also contain alkyl glyceryl ether compourlds together with the preferred alcohol e~hoxylate surfactants. Particularly preferred are glyceryl etners having the formula R -O~CH2CH2t)) nCH2CHCH20H
OH
~^/herein R9 is an alkyl or alkenyl group of from aboue 8 to about 18, preferably about 8 to 12, carbon atoms or an alkaryl ~roup having from about 5 to 14 carbons in the alkyl chain, ancl n is from O to about 6, together with the preferred alcohol e~hoxyl-ates, described above, in a ratio of alcohol cthoxylate to glyccryl ether of from about 1:1 to about 4:1, particularly about 7:3.
Glyceryl ethers of the type useful in the present invention ar~
disclosed in U.S. Pat. No. 4,098,713, Jones, issued July l~, 1978;
The ratio of alkylpolyglycoside deter~ent surfactant to nonionic detergent surfactant is from about 10: I to about 1:10, preferably From about 3:1 to about 1:3.
The Detergency Builder ~0 The detergent compositions herein also con~airl from 0% ~o about 90~, pr~ferably From about 5% to about 50~s, ancl more preferably from about 10~ to about 359~ of a deter~ent builder.
Such builders include, by way of example, a crystalline alumino-silicate ion exchange material of the formula NazltAlO2)z (SiO;~)y] xH2O
wherein z and y are at least about 6, the molar ratio of z ~o y is from about 1.0 to about 0.5 and x is ~rom about 10 to about 264.
Amorphous hydra~e~i aluminosilicaee materials useful herein haYe the empirical formula 3~ Alz ( zAlO2 Y~i2 ) wherein ~ is sodium, potassium, ammonium or substitute~ arnrlc~ni-um, ~ is from about 0.5 ~o about 2 and y is 1, said material having a magnesium ion exchange ca,oacity of at least about 50 milligram ecluivalents o~ CaC03 hardness per gram of anhydrous aluminosiiicate.
.... . ~
- l o -The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about Iû9s to about 28~ of ~Jater by ~ eight if crystalline, and potentially even hiyher amounLs of ~ater h amorphous. Highly preFerred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The preferred crystallinQ alur!~inosilicate ion exchange materials are further characterized by a particle size diamQter of from about 0 . I micron to about 10 microns. Amor-phous materials are o~ten smaller, e.g., down to less than about o.01 micron. More preferred ion exchange rn~-t~rials have a parti~
cle size diameter of from about 0.2 micron to about ~ microns.
The term "particie size diameter" herein repres~nts ~ e averaqQ
particle size diameter of a given ion exchan~3~ material as deter-minecl by conv~ntional analytical techniques such as, for example, microscopic determination utili~ing a scanning electron n icroscope.
The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchang~
capacity, which is at least about 200 mg. equivalent of CaCO3 water hardnesslg. of aluminosilicate, calculatecl on an anhydrous basis, and ~Yhich generally is in the ran~e oF from about 30û mg~.
ecl . /g . to about 352 mg . eq . l~. The aluminosilicat~? ion exchan~2 materials herein are still Further characterized by their calcium ion exchange rate which is at least about 2 grains C~ /gallon/-minute/gram/gallon of aluminosilicate [anllydrous basis), and generally lies within the range of from about 2 grainslgalionl-minute/gram/gallon to about 6 grains/gallonfminute/~ram/~3allon~
based on calcium ion hardness. Optimum ~luminosilicates for builder purposes exhibit a calcium ion exchange rat~ of at least about 4 grains/sallon/minute/gram/gallon.
The amorphous aluminosilicate ion exchan3e materials usually have a hlg exchange capacity of at least ahQ~3t 50 mg~ eq.
CaCO3/g. (12 mg. I~tg 19. ) and a Mg exchang~ rate of at leas~
about I grain/gallonlminute/gram/gallon. Amorphous materlals do not exhibit an observable diffraction pattern ~Y~en examined by Cu radiation 11. 54 Angstrom Units) .
Aluminosilicate 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 str~-c-ture and can be naturally-occurring aluminosilicates or syntheti-cally derived. A method for producing aluminosilicate ion ex-change material~ is discussed in U.S. Patent 3,985,669, Krummel, et al. issued October 12, 1976~ Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available lmder the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange mater ial has the formula Nal 2~ (A102)1~tSiO2)12l XH2 wherein x is from about 20 to about 30, especially about ~7.
Other examples of deter~3ency builders includ~ ~vater-soluble - neutral or alkaline salts.
Other useful ~vater-soluble salts include the compouncls commonly known as deter~ent huilder materials. Builders are generally selected from the various ~vater-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, I)orates, polyhydroxysulfonates, polyacetates, carboxylates, ancl polyc~r-boxylates. Preferred are the alkali metal, especially soclium, sal ts of the above.
Specific examples of inorganic phosphate builders are soc3ium and potassium tripolyphosphate, pyrophosphate, polyrneric meta-phate having a degree of polymerization of frorn about ~, to ~1, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene~ diphosphonic acic3, ~he sodium and potassium salts of ethan~ l-hyc roxy~ diph(Js~
phonic acid and the sodium and potassium salts ~f ethan~
triphosphonic acid. Other phosphorus builder compounds arc disclosed in U.S. P~tents 3,1S~,581 3,213,030, 3,4~021;
3,422,137; 3,400,176 and 3,400,148, ,, .
i:
7~
Examples of nonphosphorus, inorganic builders are sodium and potassiu;n carbonate, bicarbonate, sesquicarbonate, tetra-borate decahydrate, and sili'c2~e having a ~i;olar ratio of SiO2 to alkali metal oxide oF from about 0.5 to about l~.0, pr~ferably from about 1.0 to about 2.4, ~later-soluble, nonphosphorus organic builclers useful herein inclucle the various alkali metal, ammonium ancl substituted ammonium polyacetates, carboxylates, polycarboxylates and poly hydroxysulfonates. Examples of polyacetate and polycarboxyla-te builders are the sodium, potassium, lithium, ammoni-lm and sub~
stituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, ben~ene polycarboxylic acids, and citric acid.
Highly preferred polycarboxylate builders herein are set forth in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967. 5uch materials include the water-solubla salts of homo- and copolymers of aliphatic carboxyl;c acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acicl, aconitic acid, citraconic acid and methylenemalonic acid.
Other builders include the carboxylated carboh~c~rates of U.S. Patent 3,723,322, Diehl.
Other useful builders herein are sodium ancl potassiutrt carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexanehexacarboxylat~, cis-cyclopentanetetracarboxylate phloro-glucinol trisulfonate, water-soluble polyacrylates ~having molecular weights of from about 2,000 to about 200,000 for exampi~, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarboxylat~?s for use herein are the po5y--acetal carboxyla~es described in U.S. Pat. 4,144,226, issue~
A1arch 13, 1979 to CrutchField et al, and U . S. Pa~. 4,246 ,4g5, issued March 27, 1979 to Crutchf ie1d et al . These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an 7~
ester of glyoxylic acid and a polymerization initiator. The re-sulting polyacetal carboxylate ester i5 then attach2d to chemical Iy stable end groups to stabili~e th~ polyacetal carboxylate a~3ainst rapid depol~/~erization in alkaline solu.ion, conver.ed to tne 5 correspondin~ salt, and aclded to a surfactant.
Other detergency builder materials useful herein are the "seeded builder" compositions disclosed in Belgian Pa~ent No. 798,~56, issued Oct. 29, 1973. Specific examples of such seeded builder mixtures are: 3:1 wt.
tO mixtures of sodium carbonate and calcium carbonate having 5 micron particle diameter; ~.7:1 wt. mixture~ of sodi~m sestllJicar-bonate and catcium carbonate having a particle cliameter of 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonat~ and calcium hydroxide havin~l a particle diameter of 0.01 micron; and a 3:3: i 15 wt. mixture of sodium c~rbonate, sodium alu~inate ancJ calcium oxide having a particle diameter of 5 microns.
Oth~r Ingredients In addition to the essential detergent ~;urfactants clescribed hereinbefore, the detergent compositions herein can cont~in from 20 about 1~ to about IS~, preferably from about 2~ to ~Ibout ~, of an or~3anic surf~ctant sel~cted from the ~roup consi~itin~ o~ ~nionic, ~witterionic, ampholytic, and cationic surfactants, anc~ mixtures thereof. Surfactants useful herein are listed in U. S. Pat.
3,664,961, Norris, issued ~;lay ~3, 1972, and U.S. Pat. 3,919,678, 25 Laughlin et al, issued Dec. 30, 1975. Useful cationic surfactants also include those described in U,S. Patent
pounds has a molecular weight of from about 1500 to 1800 and cxhibies water insolubility. The addition of polyoxyethylen~
moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where ihe polyox~,~ethyl~n~
content is abou~ 50~ of the total weight of the condensatton product, which corresponds to condensation with up to about ~0 35 moles of e~hylene oxideO Examples of compoun~Js o~ this type !
7~
inclucle certain of the commerciatly available Pluronic surfactants, marl;eted by ~Yyandotte Cher~ical Corporation~
t4) The conclensation products of ethylene oxide ~vith the product resultin~ from the reaction of propylene oxicJe an~ ethyl-S cl~ediamine. The hydrophobic moiety of these pro~ucts consists of the reaction product o~ ethylenediamine and excess propylen~
oxide, said moiety havin~3 a molecular ~veight oF from about 2S0û
to about 3000. This hydrophobic moiety is condensed ~/ith ethyl~
ene oxide to the extent that the condensation product c.ontains 1~ from about 40~ to about 8091 by wei~ht of polyoxyethylen~ ~nd has a molerular weight of from about 5,000 to about 11,000. Examples of this type of nonionic ~ rfactant inclucle certain of the commer-cially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.
(S~ Semi-polar nonionic detergent surfactants inclucle water-soluble amine oxides containing on~ alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected ~rom th~ group consisting of alkyl groups and hydroxyalkyl groups 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 consistin~ of alkyl ~rou~s ancJ
hydroxyalkyl groups containin~ from about I to 3 carbon ato~s;
and water-soluble sulfox'des containing one alkyl moiety of from ~bout 10 to 18 carbon atoms and a moiety selected fror~ the group ~5 consisting of alkyl and hydro~yalkyl moieties oF from about I to 3 carbon atoms.
Preferred semi-polar nonionic detergent surfactants are th~
amin~ oxide detergent surfactants having the formula o R ~OF< ) XNR 2 herein R3 is an alkyl, hydroxy alkyl, or alkyl phenyl ~roup or mixtures thereof containing from about a to abou~ ?2 cartjc.n atoms, R is an all;ylene or hydroxy alkylene group containin~3 from 2 to 3 carbon atoms or mixtures thereof, x is ~rc)fn 0 to abou~ 3 and each R is an alkyl or hydroxy alkyl group con~aino ing from I to about 3 carbon ato~s or a polyethylen~ oxide group containing from one to about 3 ethylene ox;de groups and said R5 groups can be a-ttached to each other, e. g ., throu~h an oxygen or nitrogen atom to form a ring structure.
Preferred amine oxide detersent surfactants are C1O 18 alkyl dimethyl amine oxide, C8 18 alkyl dihyciroxy ethyl amine oxide, and C8 12 alkoxy ethyl dihydroxy ethyl amine oxic~e.
. Nonionic detergent surfactants (1)-(4) are conventional ethoxylated nonionic deter~ent surfactants.
Pref~rred alcohol ethoxylate nonionic surfactants for us~ in the compositions of the present invention are biode~raclable and have the formula R8(o~;2H4)noH, wherein R~ is a primary or secondary alkyl chain of ~rom about 8 to about 22, preferably from about 10 to about 20, c~rbon atoms t5 and n is an average of ~rom about 2 to about 12, particularly from at~out 2 to about 9. The nonionics have an HLB (hydrophilic-llpophilic balance) of from about S to about 17, preferably from abou~ 6 to about 15. HLB is defined ~n det~il in ~onionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, page~ 606-613. In preferred nonionic surfactant~, n is from 3 to 7. Primary linear alcohol ethoxylates (e.y., alcohol ethoxylates produced from organic alcohols which contain about 20~ ~-methyl branched isomers~ commercially avail~
able from Shell Chemical Company under the traclename Neodol are preferred from a performance standpoint.
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensat;on product of C1O alcohol ~/ith 3 moles of ethylene oxide; the conden-sation product of tallow alcohol with 9 moles of ethylene oxide;
the condensation product of coconut- alcohol ~ith 5 moles of ~thyl~
ene oxide; the condensation product of coconu t ~Icohol with 6 moles of ethylene oxide; the condensation ,~roduct of C12 alcohoi with 5 moles of ethylene ox;de; the condensation larocluct o~ Cl~ 13 alcohol ~ith 6.5 moles of ethylene oxide, and the same condensa-tion produce which is stripped so as to remove substantially all .~
7~L
lower ethoxylate and noneth~xylated fractions; the condensation product of C12_13 alcohol with 2.3 moles of ethylene oxide~ and the same conclensation produc; which is stripped so as to remove substantially all lower ethoxylate and nonethoxylated fractions;
5 the condensation product of C12_13 aicohol ~ ith 9 moles of ethyl-ene oxide; the condensation product of Cll~ 15 alcohol ~Yith 2.25 moles of ethylene oxide; the condensation product of Cl,l 15 ~Ico-hol with 4 moles o~ ethylene oxide; the cond~nsation product o~
C14 15 alcohol with 7 moles of ethylene oxide; and the condensa~
10 tion product of Cl~ 15 alcohol with 9 moles of ethylene~ oxide.
The compositions of the present invention may contain mix-tures of the preferred alcohol ethoxylate nonionic surfactants together with other types of nonionic sur~actants. On~ of the preFerred nonionic surfactant mixtures contains a~ least one of th~
15 preferrecl alcohol ethoxylate nonionics, and has a ratio of the preferred alcohol ethoxylate surfactant (or surfactants3 to th~
other nonionic surfactant (or surfactants) of from ~bou~ 1:1 to about 5:1. SpeciFic examples of surfactant mix~ures useful in the present invention include a mixture of the condensation product 20 of Cl~ IS alcohol with 3 moles of ethylene oxide ~ Neoclol 1~5-3) and the condensation product of Cll~ 15 alcohol Yith ~ moles o~ etl~yl-ene oxide (Neodol 45-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to abo-lt 3 ~ rnix-ture oF the condensation product of C10 alcohol with 3 moles o~
25 ethylene oxide together with the conclensa, ion product of a secondary C15 alcohol with 9 mol~s of ethylen~ oxide (Tergitoi 15-5-9~, in a ratio of lower ethoxylate nonionic to high~r ethoxylate nonionic of From about 1:1 to about 4:1; a mixture of Neodol 4S-3 and ~rergitol 15~S-g, in a ratio of lower ethoxyla~
3n nonionic to higher ethoxylate nonionic of From about 1:1 tCI ~bout 3 :1; and a mixture o~ Neodol 45-3 with the conàens~etion pro~
of myristyl alcohol with 10 moles of ethylene oxid~, in ~ rat~c of lower ethoxylate to higher ethoxylate of from .lbout 1:1 t~ abo 3 : I .
, Preferred nonionic surfactant mixtures may also contain alkyl glyceryl ether compourlds together with the preferred alcohol e~hoxylate surfactants. Particularly preferred are glyceryl etners having the formula R -O~CH2CH2t)) nCH2CHCH20H
OH
~^/herein R9 is an alkyl or alkenyl group of from aboue 8 to about 18, preferably about 8 to 12, carbon atoms or an alkaryl ~roup having from about 5 to 14 carbons in the alkyl chain, ancl n is from O to about 6, together with the preferred alcohol e~hoxyl-ates, described above, in a ratio of alcohol cthoxylate to glyccryl ether of from about 1:1 to about 4:1, particularly about 7:3.
Glyceryl ethers of the type useful in the present invention ar~
disclosed in U.S. Pat. No. 4,098,713, Jones, issued July l~, 1978;
The ratio of alkylpolyglycoside deter~ent surfactant to nonionic detergent surfactant is from about 10: I to about 1:10, preferably From about 3:1 to about 1:3.
The Detergency Builder ~0 The detergent compositions herein also con~airl from 0% ~o about 90~, pr~ferably From about 5% to about 50~s, ancl more preferably from about 10~ to about 359~ of a deter~ent builder.
Such builders include, by way of example, a crystalline alumino-silicate ion exchange material of the formula NazltAlO2)z (SiO;~)y] xH2O
wherein z and y are at least about 6, the molar ratio of z ~o y is from about 1.0 to about 0.5 and x is ~rom about 10 to about 264.
Amorphous hydra~e~i aluminosilicaee materials useful herein haYe the empirical formula 3~ Alz ( zAlO2 Y~i2 ) wherein ~ is sodium, potassium, ammonium or substitute~ arnrlc~ni-um, ~ is from about 0.5 ~o about 2 and y is 1, said material having a magnesium ion exchange ca,oacity of at least about 50 milligram ecluivalents o~ CaC03 hardness per gram of anhydrous aluminosiiicate.
.... . ~
- l o -The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about Iû9s to about 28~ of ~Jater by ~ eight if crystalline, and potentially even hiyher amounLs of ~ater h amorphous. Highly preFerred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The preferred crystallinQ alur!~inosilicate ion exchange materials are further characterized by a particle size diamQter of from about 0 . I micron to about 10 microns. Amor-phous materials are o~ten smaller, e.g., down to less than about o.01 micron. More preferred ion exchange rn~-t~rials have a parti~
cle size diameter of from about 0.2 micron to about ~ microns.
The term "particie size diameter" herein repres~nts ~ e averaqQ
particle size diameter of a given ion exchan~3~ material as deter-minecl by conv~ntional analytical techniques such as, for example, microscopic determination utili~ing a scanning electron n icroscope.
The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchang~
capacity, which is at least about 200 mg. equivalent of CaCO3 water hardnesslg. of aluminosilicate, calculatecl on an anhydrous basis, and ~Yhich generally is in the ran~e oF from about 30û mg~.
ecl . /g . to about 352 mg . eq . l~. The aluminosilicat~? ion exchan~2 materials herein are still Further characterized by their calcium ion exchange rate which is at least about 2 grains C~ /gallon/-minute/gram/gallon of aluminosilicate [anllydrous basis), and generally lies within the range of from about 2 grainslgalionl-minute/gram/gallon to about 6 grains/gallonfminute/~ram/~3allon~
based on calcium ion hardness. Optimum ~luminosilicates for builder purposes exhibit a calcium ion exchange rat~ of at least about 4 grains/sallon/minute/gram/gallon.
The amorphous aluminosilicate ion exchan3e materials usually have a hlg exchange capacity of at least ahQ~3t 50 mg~ eq.
CaCO3/g. (12 mg. I~tg 19. ) and a Mg exchang~ rate of at leas~
about I grain/gallonlminute/gram/gallon. Amorphous materlals do not exhibit an observable diffraction pattern ~Y~en examined by Cu radiation 11. 54 Angstrom Units) .
Aluminosilicate 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 str~-c-ture and can be naturally-occurring aluminosilicates or syntheti-cally derived. A method for producing aluminosilicate ion ex-change material~ is discussed in U.S. Patent 3,985,669, Krummel, et al. issued October 12, 1976~ Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available lmder the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange mater ial has the formula Nal 2~ (A102)1~tSiO2)12l XH2 wherein x is from about 20 to about 30, especially about ~7.
Other examples of deter~3ency builders includ~ ~vater-soluble - neutral or alkaline salts.
Other useful ~vater-soluble salts include the compouncls commonly known as deter~ent huilder materials. Builders are generally selected from the various ~vater-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, I)orates, polyhydroxysulfonates, polyacetates, carboxylates, ancl polyc~r-boxylates. Preferred are the alkali metal, especially soclium, sal ts of the above.
Specific examples of inorganic phosphate builders are soc3ium and potassium tripolyphosphate, pyrophosphate, polyrneric meta-phate having a degree of polymerization of frorn about ~, to ~1, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene~ diphosphonic acic3, ~he sodium and potassium salts of ethan~ l-hyc roxy~ diph(Js~
phonic acid and the sodium and potassium salts ~f ethan~
triphosphonic acid. Other phosphorus builder compounds arc disclosed in U.S. P~tents 3,1S~,581 3,213,030, 3,4~021;
3,422,137; 3,400,176 and 3,400,148, ,, .
i:
7~
Examples of nonphosphorus, inorganic builders are sodium and potassiu;n carbonate, bicarbonate, sesquicarbonate, tetra-borate decahydrate, and sili'c2~e having a ~i;olar ratio of SiO2 to alkali metal oxide oF from about 0.5 to about l~.0, pr~ferably from about 1.0 to about 2.4, ~later-soluble, nonphosphorus organic builclers useful herein inclucle the various alkali metal, ammonium ancl substituted ammonium polyacetates, carboxylates, polycarboxylates and poly hydroxysulfonates. Examples of polyacetate and polycarboxyla-te builders are the sodium, potassium, lithium, ammoni-lm and sub~
stituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, ben~ene polycarboxylic acids, and citric acid.
Highly preferred polycarboxylate builders herein are set forth in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967. 5uch materials include the water-solubla salts of homo- and copolymers of aliphatic carboxyl;c acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acicl, aconitic acid, citraconic acid and methylenemalonic acid.
Other builders include the carboxylated carboh~c~rates of U.S. Patent 3,723,322, Diehl.
Other useful builders herein are sodium ancl potassiutrt carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexanehexacarboxylat~, cis-cyclopentanetetracarboxylate phloro-glucinol trisulfonate, water-soluble polyacrylates ~having molecular weights of from about 2,000 to about 200,000 for exampi~, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarboxylat~?s for use herein are the po5y--acetal carboxyla~es described in U.S. Pat. 4,144,226, issue~
A1arch 13, 1979 to CrutchField et al, and U . S. Pa~. 4,246 ,4g5, issued March 27, 1979 to Crutchf ie1d et al . These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an 7~
ester of glyoxylic acid and a polymerization initiator. The re-sulting polyacetal carboxylate ester i5 then attach2d to chemical Iy stable end groups to stabili~e th~ polyacetal carboxylate a~3ainst rapid depol~/~erization in alkaline solu.ion, conver.ed to tne 5 correspondin~ salt, and aclded to a surfactant.
Other detergency builder materials useful herein are the "seeded builder" compositions disclosed in Belgian Pa~ent No. 798,~56, issued Oct. 29, 1973. Specific examples of such seeded builder mixtures are: 3:1 wt.
tO mixtures of sodium carbonate and calcium carbonate having 5 micron particle diameter; ~.7:1 wt. mixture~ of sodi~m sestllJicar-bonate and catcium carbonate having a particle cliameter of 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonat~ and calcium hydroxide havin~l a particle diameter of 0.01 micron; and a 3:3: i 15 wt. mixture of sodium c~rbonate, sodium alu~inate ancJ calcium oxide having a particle diameter of 5 microns.
Oth~r Ingredients In addition to the essential detergent ~;urfactants clescribed hereinbefore, the detergent compositions herein can cont~in from 20 about 1~ to about IS~, preferably from about 2~ to ~Ibout ~, of an or~3anic surf~ctant sel~cted from the ~roup consi~itin~ o~ ~nionic, ~witterionic, ampholytic, and cationic surfactants, anc~ mixtures thereof. Surfactants useful herein are listed in U. S. Pat.
3,664,961, Norris, issued ~;lay ~3, 1972, and U.S. Pat. 3,919,678, 25 Laughlin et al, issued Dec. 30, 1975. Useful cationic surfactants also 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 followin~ are representative examples of surfactants 30 useful in the present compositions.
Water-soluble salts of the higher fatty acids t i .e ~, "soaps" are useful anionic surfactants in ~he compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alky1olammonium salts of higher fatty acids containing from about 8 to about ~4 carbon atoms, and pre~erably from about . .
~2~J~
12 to about 18 carbon atoms~ Soaps can be made by direct saponification of fa~s and oils or by the neutraiizatior3 of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures o-f fatty acids derived from coconut oil and taliow, i . e , sodium or potassium tallow and coconut soap~ The pre-ferred soap, as discussed hereinbefore and hereinafter, especially in combination with semipolar or amide nonionic detergent sur-factants, is at least partially lJnsaturated.
The Unsaturated Soap t 0 The unsaturated fatty acid soap of this invention contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration. Preferably the nurnber of carbon atoms in the unsaturated fatty acid soap is from abollt 16 to abou~ 18.
The unsaturated soap, in common with other anionic deter~
~;ent and other anionic materials in the detergent comp~sitions of this invention, has a cation which renders the soap water-soluble and/or dispersible. Suitable cations include socli--m, potassium, ammonium, monoethanotar~monium, die~hanolamonium, triethanol~
amrnonium, tetramethylammonium, etc. cations. Sodium ions are preferred although in liquid formula;ions ammoniu~, and triethanolammonium cations are useful.
A level of at least about 120 of the ~nsa~uratec~ f~tty acid soap is desirable to provide a noticeable recluction in suclsing and corrosion. Prererred levels of unsaturatecl fatty acid soap are from about 1% to about 15~6, preferably from about 1~ tc~ a~out lû~, most preferably frorl about ~ to about 5O. The unsaturated fatty acid soap is preferably present at a level tha~ tilt provide a level of from about 15 ppm to about 200 ppm, prefera~ly from about 25 ppm to about 125 ppm in the ~vash solution at r~om~
mended U.S. usage levels and from about 30 ppm to a~out loOn ppm, preferably from about 50 ppm to about 50~ pp~n for European usage levels.
~lono-, di-, and triunsaturated fatty acids are all ess~nti~lly equivalent so it is pre'erred to use mostly mon~unsaturat~d soaps to minimize the risk of rancidity. Suitable sources of l.nsaturated , , IL7~
fatty acids are well known. For example, see Bailey's Industrial Oil and Fat Products, Third Edition, Swern, publishecJ by inter-science Publisher ( 1964), Preferably, the levei of saturated soaps is kept as low as s pos~ible, preferably less than about 60~, pre,erably less than about 50~ of the total soap is saturated soap I lowever, lo:Y
levels of saturated soaps can be used. Tallow and palrn otl soaps can be used.
Useful synthetic anionic surfactants also inclucJe the ~vater-10 soluble salts, preferably the alkali metal, ammonium ancJ alkylol-ammonium salts, of or~3anic sulfuric reaction products having în their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulf-/ric acid ester group.
1 S Such synthetic anionic detergent surfactants are ctesirable additives at a level of from about l~ to about l~ to increas~ th~
overall deter~ency effect and, if clesired, increase the level oF
suds. ( Included in the term "alkyl" is the alkyl portion of acyl groups. ) Exam,~les of this group of synthetic surfactants are the ~0 sodium and potassiu~ alkyl sul`fates, especially those obtainecl by sulfatin~ the higher alcohols (C8-CI8 carbon atoms) such as thos~
produced by reducing the glycerides of tallow or cocon-lt oil; and the soclium and potassium alkylbenzene sul fonates in ~hich the alkyl ~3roup contains from about 9 to about IS caroon atoms, in straigh~ chain or branched chain configuration, e.g., those of the type described in U.S. Pats. 2,220,099 and 2,477,383. ~spec;ally valuable are linear straight chain alkylbenzene sul~onates in l,vhic~
the avera~e number of carbon atoms in the alkyl 3roup is from about ll to 13, abbrevlaeed as Cll 13LAS.
Preferred anionic detergent surfactants are th~ alky1 poiy--ethoxylate sulfates, particularly those in which th~ alkyl contains ~rom abou~ 10 to about 22 carbon atoms, prefel ably from about l~
to about 18 and ~herein the polyethoxylate chain contains frorn about I to about IS ethoxylate rnoieties preferably from about I to about 3 ethoxylate moieties These anionic detergent surfact2nts ,~, are particularly desirable for formulating heavy-duty liquid laundry deter~ent composi tions.
Oth~r anionic surfactants herein are the sodium alkyl cly-ceryl ether sulfonates, especially those ethers oF higher alcoho)s
Patent 4,239,659, Murphy, issued Dec. 16, 1980. The followin~ are representative examples of surfactants 30 useful in the present compositions.
Water-soluble salts of the higher fatty acids t i .e ~, "soaps" are useful anionic surfactants in ~he compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alky1olammonium salts of higher fatty acids containing from about 8 to about ~4 carbon atoms, and pre~erably from about . .
~2~J~
12 to about 18 carbon atoms~ Soaps can be made by direct saponification of fa~s and oils or by the neutraiizatior3 of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures o-f fatty acids derived from coconut oil and taliow, i . e , sodium or potassium tallow and coconut soap~ The pre-ferred soap, as discussed hereinbefore and hereinafter, especially in combination with semipolar or amide nonionic detergent sur-factants, is at least partially lJnsaturated.
The Unsaturated Soap t 0 The unsaturated fatty acid soap of this invention contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration. Preferably the nurnber of carbon atoms in the unsaturated fatty acid soap is from abollt 16 to abou~ 18.
The unsaturated soap, in common with other anionic deter~
~;ent and other anionic materials in the detergent comp~sitions of this invention, has a cation which renders the soap water-soluble and/or dispersible. Suitable cations include socli--m, potassium, ammonium, monoethanotar~monium, die~hanolamonium, triethanol~
amrnonium, tetramethylammonium, etc. cations. Sodium ions are preferred although in liquid formula;ions ammoniu~, and triethanolammonium cations are useful.
A level of at least about 120 of the ~nsa~uratec~ f~tty acid soap is desirable to provide a noticeable recluction in suclsing and corrosion. Prererred levels of unsaturatecl fatty acid soap are from about 1% to about 15~6, preferably from about 1~ tc~ a~out lû~, most preferably frorl about ~ to about 5O. The unsaturated fatty acid soap is preferably present at a level tha~ tilt provide a level of from about 15 ppm to about 200 ppm, prefera~ly from about 25 ppm to about 125 ppm in the ~vash solution at r~om~
mended U.S. usage levels and from about 30 ppm to a~out loOn ppm, preferably from about 50 ppm to about 50~ pp~n for European usage levels.
~lono-, di-, and triunsaturated fatty acids are all ess~nti~lly equivalent so it is pre'erred to use mostly mon~unsaturat~d soaps to minimize the risk of rancidity. Suitable sources of l.nsaturated , , IL7~
fatty acids are well known. For example, see Bailey's Industrial Oil and Fat Products, Third Edition, Swern, publishecJ by inter-science Publisher ( 1964), Preferably, the levei of saturated soaps is kept as low as s pos~ible, preferably less than about 60~, pre,erably less than about 50~ of the total soap is saturated soap I lowever, lo:Y
levels of saturated soaps can be used. Tallow and palrn otl soaps can be used.
Useful synthetic anionic surfactants also inclucJe the ~vater-10 soluble salts, preferably the alkali metal, ammonium ancJ alkylol-ammonium salts, of or~3anic sulfuric reaction products having în their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulf-/ric acid ester group.
1 S Such synthetic anionic detergent surfactants are ctesirable additives at a level of from about l~ to about l~ to increas~ th~
overall deter~ency effect and, if clesired, increase the level oF
suds. ( Included in the term "alkyl" is the alkyl portion of acyl groups. ) Exam,~les of this group of synthetic surfactants are the ~0 sodium and potassiu~ alkyl sul`fates, especially those obtainecl by sulfatin~ the higher alcohols (C8-CI8 carbon atoms) such as thos~
produced by reducing the glycerides of tallow or cocon-lt oil; and the soclium and potassium alkylbenzene sul fonates in ~hich the alkyl ~3roup contains from about 9 to about IS caroon atoms, in straigh~ chain or branched chain configuration, e.g., those of the type described in U.S. Pats. 2,220,099 and 2,477,383. ~spec;ally valuable are linear straight chain alkylbenzene sul~onates in l,vhic~
the avera~e number of carbon atoms in the alkyl 3roup is from about ll to 13, abbrevlaeed as Cll 13LAS.
Preferred anionic detergent surfactants are th~ alky1 poiy--ethoxylate sulfates, particularly those in which th~ alkyl contains ~rom abou~ 10 to about 22 carbon atoms, prefel ably from about l~
to about 18 and ~herein the polyethoxylate chain contains frorn about I to about IS ethoxylate rnoieties preferably from about I to about 3 ethoxylate moieties These anionic detergent surfact2nts ,~, are particularly desirable for formulating heavy-duty liquid laundry deter~ent composi tions.
Oth~r anionic surfactants herein are the sodium alkyl cly-ceryl ether sulfonates, especially those ethers oF higher alcoho)s
5 clerived from tallow ancl coconut oil; sodium coconut oil fatty acid nlonoglyceride sulfona~es and sulrates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfa-tes containing from about I to about lO units oF ethylene oxide per molecule and ~,herein the alkyl groups contain from abou~ ~; to abo~Jt l?. c~rbon 10 atoms; and sodiun7 or potassium salts of alkyl ethylene oxid~ ether sulfates containing about I to about lO units of e-thylene oxide p~?r molecule and wherein the alkyl group contains from ~ou~ lû to about 20 carbon atoms.
Other useful anionic surfactants herein incluc1e th~ ~v~ter~
15 solubls salts of esters of alpha sulfonated fatty acids containin~
from about 6 to ~0 carbon atoms in the fatty acid ~roup and from about I to lO carbon atoms in the ester group; ~vater-sol~ble salts of 2-acyloxy-al~;ane-l-sulTonic acids containin~ ~rom al~out ~ to ~
carbon atoms in the acyl group and from about 9 to about 23 20 carbon atorns in the alkane moiety; al~yl ether sulfates conta;nin~
from about lO to 20 carbon atoms in the alkyl ~roup and from about I to 30 moles of ethylene oxide; water-solubl2 salts of olefi~?
sul fonates containing from about 12 to 2l~ carbon atnms; ancl beea-alkyloxy alkane sulfonates containin~ from about I to ~
2S carbon atorns in the alkyl group and from about 8 to ~0 car~on atoms in the alkane moiety.
Ampholytic surfactants include derivatives of aliph~tic or aliphatic derivatives of heterocyclic secondary and tertiary amtnes in ~vhich the aliphatic moiety can be straight chain or hr~nch~d 30 and ~vherein one of the ~liphatic substituents contains from a~out 8 to 18 carbon atoms and at ieast one aliphat~c substit~nt cQn~
tains an anionic water-:,olubili~ing group.
Z~vitterionic surfactants include derivati~es of a.lip~ati~
quaternary ammoniurn, phosphonium, and sulfonil3m compo~in~s in .. . _ _ .
"
~2~
which one of the aliphatic substi euents contains from about 8 to 1 ca r bo n a toms .
Particularly preferred auxiliar~ surFactants 'nerein includ~
lirlear alkylbenzene sulfonates containing from about 11 to 14 carbon atoms in the al' yt group; tallo~tYalkyl suhCates; coconutalkyl ~Iyceryl ether sulfonates; alkyi ether sulFates wherein the alkyl moiety contains from about 14 to i8 carbon atoms and l,vherein the average degree of ethoxylation is from about I to 4; olefin or paraffin sulfonates containinS from abou~ to 16 c~l-bon atoms;
and alkyldimethylammonium propane sulfonates and allcyldimethyl-ammonim hydroxy propane sulfonates wh~r~in th~ ~Ikyl ~rcup contains from about 14 to 18 carbon atoms.
Specific preferred surfactants for use ller~in includ~:
sodiurr, potassium, mono-, di-, and trtethanolammoniur~ C14 î5 alkyl polyethoxyiatel 3 sulfates; sodium linear Cll ~3 alkylbenzene sulfonate; triethanolamine Cll 13 alkylbenzene sulfonate; sodiu~
tallow alkyl sulfate; sodiun~ coconut alkyl glyceryl ether sulfonate;
the sodium salt of a sulfated condensation product oF a tallow alcohol ~vith about 4 moles oF ethylene oxide; 3-(N,N-dimeth~l-N-coconutal~ylammonio)-2hydroxypropane-1-sulfonate;
3- ( N, N-dimethyl-N-coconutalkylammoniopropane-l-sLIl fona te;
Other useful anionic surfactants herein incluc1e th~ ~v~ter~
15 solubls salts of esters of alpha sulfonated fatty acids containin~
from about 6 to ~0 carbon atoms in the fatty acid ~roup and from about I to lO carbon atoms in the ester group; ~vater-sol~ble salts of 2-acyloxy-al~;ane-l-sulTonic acids containin~ ~rom al~out ~ to ~
carbon atoms in the acyl group and from about 9 to about 23 20 carbon atorns in the alkane moiety; al~yl ether sulfates conta;nin~
from about lO to 20 carbon atoms in the alkyl ~roup and from about I to 30 moles of ethylene oxide; water-solubl2 salts of olefi~?
sul fonates containing from about 12 to 2l~ carbon atnms; ancl beea-alkyloxy alkane sulfonates containin~ from about I to ~
2S carbon atorns in the alkyl group and from about 8 to ~0 car~on atoms in the alkane moiety.
Ampholytic surfactants include derivatives of aliph~tic or aliphatic derivatives of heterocyclic secondary and tertiary amtnes in ~vhich the aliphatic moiety can be straight chain or hr~nch~d 30 and ~vherein one of the ~liphatic substituents contains from a~out 8 to 18 carbon atoms and at ieast one aliphat~c substit~nt cQn~
tains an anionic water-:,olubili~ing group.
Z~vitterionic surfactants include derivati~es of a.lip~ati~
quaternary ammoniurn, phosphonium, and sulfonil3m compo~in~s in .. . _ _ .
"
~2~
which one of the aliphatic substi euents contains from about 8 to 1 ca r bo n a toms .
Particularly preferred auxiliar~ surFactants 'nerein includ~
lirlear alkylbenzene sulfonates containing from about 11 to 14 carbon atoms in the al' yt group; tallo~tYalkyl suhCates; coconutalkyl ~Iyceryl ether sulfonates; alkyi ether sulFates wherein the alkyl moiety contains from about 14 to i8 carbon atoms and l,vherein the average degree of ethoxylation is from about I to 4; olefin or paraffin sulfonates containinS from abou~ to 16 c~l-bon atoms;
and alkyldimethylammonium propane sulfonates and allcyldimethyl-ammonim hydroxy propane sulfonates wh~r~in th~ ~Ikyl ~rcup contains from about 14 to 18 carbon atoms.
Specific preferred surfactants for use ller~in includ~:
sodiurr, potassium, mono-, di-, and trtethanolammoniur~ C14 î5 alkyl polyethoxyiatel 3 sulfates; sodium linear Cll ~3 alkylbenzene sulfonate; triethanolamine Cll 13 alkylbenzene sulfonate; sodiu~
tallow alkyl sulfate; sodiun~ coconut alkyl glyceryl ether sulfonate;
the sodium salt of a sulfated condensation product oF a tallow alcohol ~vith about 4 moles oF ethylene oxide; 3-(N,N-dimeth~l-N-coconutal~ylammonio)-2hydroxypropane-1-sulfonate;
3- ( N, N-dimethyl-N-coconutalkylammoniopropane-l-sLIl fona te;
6- ( N-dodecylben~yl-N, N-dimethylammonio) -he~anoate; ancl coconut alkyldirlethyl amine oxide.
Other adjunct components ~vhich may be inclucled in the compositions of the present invention, in their conventional art-established levels for use ~i.e., from 0 to a~o~3t 90%), include solvents, bleaching agents, bleach activators, soil-suspending a~ents, corrosion inhibit~rs, dyes, fillers, opticat brighteners, ~err~icides, pH adjusting agents ~ monoethanolamil-~, sodiu~3 carbonate, sodium hydroxid~, etc. ), enzy~es, ~nzyme-stabilizin~
agents, perfumes, fabric softening cornponents, stat;c control ag~nts, and the like.
Fatty acid amide detergent surfactants use~ul herein include those havin~ the formula:
O
p~6 -C-NP< 2 wherein R6 is an all;yl group containing from about 7 to about 21 (preferably From about 9 to about 17) carbon atoms and each P~
is selected from the group consisting of hydrogen, Cl ~ alkyl, Cl ~ hydroxy alkyl, and -(C2H~O)xH where x varies from about I to about 3.
Preferred amides are C8 20 ammonia amides, monoethanolammon-ium, diethanolamides, and isopropanol amides.
A special advanta~e of the combinat;~n of deter~ent surfac-tants herein is their superior compatibility ~vith anionic fluores-10 cent or optical bri~hteners. Nonionic ~urfactants, ~speciallyethoxylated nonionic detergent surfactants, normally climinish the effectiveness of such brighteners. K~ith th~ aclclition of the alkylpolyglycoside surfactant, the brightener t ffectiveness is drarilatically improved, especially on cotton. From ca~out 0~01 to l S about 2~, preferably from about 0 .1 to about 1~ optical bri~htener can be used.
Suitable brighteners include the following:
bis anilino ~ R) triazinyl amino stilbene sulfonate havin~ the formula:
H
X\ N~ N~
N ~ N 1~
l l C-R 50~ 2 ~herein hl is preferably Na, but can be any compatible cation such as potassium, amnlonium, s~bstituted ammonium, e.g, mono-, di-, and triethanolammoni--m, c~c.; X c~n be R2~ NH-where R is selected from H, phenyl, Cl ~ alkyl, or C~
hydroxyalkyl; morpholino-, hydroxy; 5 !
lZt~
Na 3 O NH-;
C 3 O N H ;
H~OCH2CH2)3CH2NH- O -NH-;
O35- O -NH-C~ -NH-;
or mixtures thereo~; and R can be H or SO3 In represented structures, R and X are:
R X
15 -N~C2H4H)2 ~J
-NH-O "
-N ~ O l' -N (CH3)CH CH20~ 1 -NHC2H~OC1 13 "
,, , . , . _ _ .. . . _ _ _ .
-~2~t~
-OH "
C2H40H Na35 0 -NH-N ~ O CH30- ~NII-H(ocH2cH2)3cH~NH- H(OCH2C~2)3C 2 {> -N~t-tO
(HOCH2CH2)2N- O--Na35 ~ -Nl~- O -I~H-tetrasodium 4,4'-bisl (4"-bis(2"'-hydroxyethyl)amino-6"-~3""-sulphenyl)amino-l" ,3" ,S"-tria2in-2"-yl)amino~-2 ,2'-stilbenedisulfo~
nate;
disodium-4-(6'-sulfonaphthol 1' ,2' ,dl tria201-2~yl)-2-stilbene-sul fonate;
disodium 4,4'-bisl (4"-(2"'-hydroxyethylamino)-6"-anilino-1'1 ,-3",5"-triazin-2"-yl)amino]-2,2'-stilbenedis(Jlfonate;
disodium 4,4'-bis[ (4"-(2"'-hydroxyeehoxy)-6"-anilino-1",3",-20 S''-tria2in-2''-yl)amino]-2,2'-stilbenedisulfonate;
disodium 4,4'-bis(4-phenyl-1,2,3-tria~ol-2-yi)-1,2'-stilbenecli-sulfonate;
sodium 4-(2H-naphtho[1,2-d]tria~ol-2-yl)stilbene-2-~ulfonate;
disocJium 4,4'-bis-(2-sulfostyryl)biph~nyl:
disodium 4-~2H-6-sulfonaphtho~1,2-dltria~ol-2-yl)stilben~2-sulfonate; and disodium 3,7-bis(2,4-dimethoxybenzamido)-?,~-dibenzothio^
phenedisulfonate-S ,5-dio)cide.
Other suitable bri~3hteners are disclosed in U . S. Pztents 30 3,537,993 Coward et al; issued Novemb~r 3, 1970 and 3,9$3,~80 Sundby, issued April 27, 1976, The compositions of the present inventior\ can be manu~
factured and used in a variety of forms such as solids, po~^/detos~
granules, pastes, and liquids. The compositions can be used ir~
35 the current U.S. Iaunderin~ processes by forming aqu~us ~.
IL7~
solution containincg from about 0.01% to about I~, pre-Ferably from about 0.05~ to about 0.5%, and most preferably frorn about 0.05 to about û.25% of the composition in ~vater and a~itating -the soil~d fabrics in that aqueous solution. The fabrics are then rinsed and 5 dried. ~Yhen used in this manner the preFerred compositions of the present invention yield exceptionally good detergency on a variety of fabrics.
I n a preferred embodiment a laundry detercJent, preferably, an aqueous heavy-duty liquid, contains ~a) from about l~i to about 20~ (preferably from about 4~s to about 10~3 of the alkylpoly-glycoside detergent surfactant; (b) from about l~ to abollt lO~i lpreferably from about 2% to about 6~) of an amine oxi~e deter-gent surfactant tc) from 1% to about lO~ (preferably from a~out l~
to about 6~) of a water-soluble soap of an unsaturated fatty acid containincJ from about 16 to about 22 carbon atoms; (d~ from 0~ to about 40~ (preferably from about lO~ to about 30~s~ o~ a water-soluble deter~ency builder, preferably selected from the ~;ro~p consisting of pyrophosphates, nitrilotriacetatesr and mixtures thereof; le) from about 0~ to about lO~ (preF~rably from about 0 to about 5~) of water-solu'~le synthetic anionic cletergent sur factant; and, preferably, and (f) the l~alance ~vater.
Such deter~ent compositions provide excellent detergency, clo not clamage washing machines unacceptably, ~nd can be ~ormulatec3 to provide different sudsing patterns by varyin~ the arnount and 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 surfact~nts.
Sodium, potassium, ammonium, and alkanolammonium cations are preferred .
All percentages, parts, and ratios herein are ~y weiyht unless otherwise specified.
The following examples illustrate the compositions and me~hc,d of the present invention.
EXAI~IPLE I
Unbuilt Co~bina ion oF
Cl2-l5 alkyi C12 13 al~ yl ilunter ~`Jni;en2ss Uni~s ~HWU) 55i~c~spolye hox~- Polyester ~
2-3 6.5 Colton Blend ppm in ~la,hCotton (i.e. Poiycotton) Polyester 500 - 9.4 15.4 2.g ~~
400 lO0 6.'1 15.5 4.
300 200 6.3 17.1 7.1 lO200 300 4.4 17.6 7.1 lO0 400 2 .7 1 6 . 3 7 . 1 - 500 -0.3 15.~ 6.8 Test Condi-tion: 95F ~,vater havin~ 6 ~rains c~f mixed 12ar ~-ness and a mini~ ~asher.
As can be seen from th~ ~bove results~ th~ ~llcylpolyglycc--side surFactant has an unexpected problem ~Jith cleanin~ poly-~ster. In general, the alkylpoly~lycosides are consiclere~ non-ionic surfactant replacements, but, surprisin~ly, they ach;eve their best laundry results in combination ~ith nonionic sur~ac-20 tants, especially those that are optimi~ed for cleanin~7 relativ~ly hyclrophobic surfaces. The alkyl polyglycosicles in these examplos were clerived from glucose. S;milar resul ts are obtainecl wit~ the other all;yl ~Iycosides describod herein.
EXAI'ilPLE I I
(Unbuilt ~tix;ures) C12 15 alkyl Cl2_13 Y
polyglyco- polyetho~cy-~ Dirty l~lotor Oil P~erno~a) sides2 3 late3from Polyester Fabri :s 30û ppm 0 ppm 1~) 302L'0 ppm 60 ppm 20 l~0 ppm 120 ppm 27 0 pp~ 300 ppm 17 Same conditions as in Example 1.
As can be seen from the above data, despite ~h~ gener~lly 35 inferior results obtain~d in cleanin9 relatively ~ydrophobic sur-'7~
faces with an aikylpoly~lycoside surfactant, the mixtures o- an alkylpoly~3lycoside and a nonionic surfactant provicles syner~3istic results.
Whiteness .~laintenance ( Redeposition ~est) C12 13 alkyl Hunter ~,'lhit~ness Units (H~'~IU}
C12_15 alkylpolyethoxy- White polyglyco- lat~3 Cot~on l,'Jhite SVhite side2 3Neodol 23-3 T-shirt Polycotton Polyester 300ppm 0 73 G8 3fi 240ppm 60 74 70 ~9 15 180ppm 120 7~ 73 ~}0 60ppm 240 73 73 0 300 71 ~3 ~9 The solutions ~Yere unbuilt and used the same conditions as Examples 1 and 11, the grades bein~ the avera~3e for the two 20 types of soils.
As can be seen from the above data, there is ~ syner~istic improvement in redeposition on cotton For the mixtures of surfac-EXAI`ilPLE IV
25 C12 15 alkyl Ci2-13 alkyl polyglyco- polethoxy% I`ilenstrual Stain Remov~l side2 3 late3 frorn polycotton 300ppm o 50 240ppr~ O0 G0 30 180ppr;) 120 ~3 60ppm 240 7n Oppm 300 63 Same test conditions as in previous examples ~ h unh~
solutions .
,, ~2~
-- 21~ --As can be seen from the above, the un~xpectedly poor showin~3 of the alkylpolyglycQside ~vith respect to this staîn can be improved andlor synergistic improvement obtained by addition of the nonionic surfactant, depending upon the ratio used.
EXA~IPLE V
Built Per,~ormance orl Clay Soil Hunter ~ iteness llnits (H~U~
Cotton Polycotton Polyester Commercial built anionic detergent composition 11.0 19.9 22~5 12-15 alkYIPIYglycoside TSC~2 13 alkylpolyethoxylate6.5 12.7 21.2 26.
*E3uilt with 25% sodium tripolyphosphate ~STP) and 10% sodi~
um carbonate, the total composi.ion be;ng used at 2 lev21 of 1200 ppm 20Test Condition: 60F water having 9 grains of m;xed hard-r-ess ancl miniwasher.
As can be seen from the above the mixed surfactant system of ~his invention provides ecluivalent or superior clay removal across a variety of fabric types as compared to rnore corlventional 25anionic surfactants.
", ~2~
EXAMPLE Vl (~12 15 alkyl 212-13 alky~
polyglyco- polyethoxy-sides 2 3 la te 6 . 5 ~ coconut alkyl Coconut alkyl dimethylamine dimethy!amine oxide ~1:1) oxide 11: i) Clay Removal, H~`IU
Cotton 14 . 6 1 I . 2 Polycotton 28 . 5 22 ~1 Polyester 59.û 55.2 Removal, %
Dirty motor oil 30 37 Chocolate syrup g3 ~3 1 S Grass 67 73 Bacon grease 57 53 ~A,lenstrual stain 83 73 Spaghetti sauce 50 E~oo'y Soil Removal, PSU~ vs.
Commercial Unbuilt Heavy-D~lty Liquid ~Control) ~1.56 ~I.i ~`~hi teness, Soler 2A
T-shi rt 78 77 Polycotton 86 8~;
Polyester 46 39 The sur~actant mixture ~vas 13~ of the formula and the huitd-er \vas sodium nitrilotriacetate at 18~. The test concli tions w~re 2100 ppm of the composition, 95F, 6 grains of mixed hardness.
*PSU equals Panel Score Units wherein expert ~raders assiyn 30 values based on 0 = no differe~ce; I = difference; anci ~ -- c1ear difference.
"
EXA;vlPLE Vl I
Unbuilt HDL Perforr~ance The invention vs. unbuilt commercial heavy-c~uty liquid detersent composition (HDL).
5Panel Score Units vs. Commercial Product Cotton Polyester Dirty motor oil ~0.3 +0,4 Bacon grease +1.0 ~0.8 C;ravy +1.4 +0.2 Spa~hetti sauce +0,3 ~,9 Grass +1.7 ~1.5 Chocolate syrup -O . 4 ~0 ~ 6 TEST CONDIT10N: 450 ppmactives, 95F~at~r h~ving 6 ~rains mixed hardness and a mini ~asher.
15Composieion of the invention: C12 13 atkylpolyethoXylat~/
C~;~ 15 alkylpolyglycoside2 3 at a ratio of 1:1.
EXAl`llPLE Vl 11 Formula Parts C12 15 alkYIPIY~llYcside2-3 13.3 2C Cl2_13 alkYIPIYethoxylate6 5 13.3 Sodium tripolyphosphate 12 . O
Na2C3 13.3 Polyacetaldehyd e deter3ency builder 28.8 Anionic bri~htener* 1.0 25*bis(anilino-hydroxyetnylmethylamino-trsazinylam~no)stilben~
disulfonat~ (sodium salt).
Fluorescer Effectiveness Filtered Unfiltered HWU H~`IUDelta FSol~r 2A
C~2 15 alkylpoly9lyco-side2 31Neodol 23-6.579 111 22 ~7 Commercial built anionic detergent ~control) 80 106 19 ~Q
. ~Z`~7~
Significant technical differences: HI~U=2; Soler 2~=2; and F=l .
EXAI~lPLE iX
~edeposit;on and ~Jhitenessl Brightness Test Cotton T-Shi rt The followin3 results using unbuilt mixtures of sur,ractants clearly demonstrate the effect of the alkylpolyglycn~icle in im-proving anionic brightener effectiveness in the preaence o~ non~
ionic surfactants. The data show clearly that at least about /~0%
10 of the sur~actant system should be alkylpoly~lycoside. Five to six H~YUs are a substantial improvement.
Cl;~_13 all~yl C12-13 alkylt)n~iltered*
polyglycoside2_3 polyethoxylate3 Hunter ~Yhiten~ss Units eefore~fter Detta Washin~~'lashing ( loss~
100 0 120 11~ 10 *To measure bri~htener effect Conditions: ~lini~,vasher, 6 grains mixed harc~ness, 100F, one cycle 30n pprn total surfactant, 15 ppm of the brightener of 25 Exampl~ Vl t I .
EXAI;tPLE X
The alkylpolyglycosides improve the performance of very water soluble ~high HLB) nonionics.
Ratio Clay Cleanin~ Per~ormance 30C12_l3 alkyl-C12_l3 alkyl Hullter ~Yhi~eness lJnit~
plY91YCsid~2_3polyethoxylatel;~ Polyes.er Polycottor1 Cotton 100 0 25 . 9 27.0 3.?i ~,5 3 5 !~ o 2 8 A 85 0 ~ 3 . 6 2g .1~i . n ~ .
o loo 28 . 12 ~ 2 2 ~ I
~2~ 7~
-- 2~ --Conclitions: I~liniwasher, unbuilt, 6 grains at mixed hard-ness, 100F, 300 ppm total active.
As can be seen from the above data, the mixtures are clear-ly superior. From I to 2 H~iU are a substantial dif,erence in this 5 test.
EXA~ PLE X l ~Ikyl Polyglucosides Improve the Performance of Oil Soluble (Low HLB) Nonionic Deter~ent Surfactants (HWU) ~p,S.tJ.) 10Ratio Clay Removal Lipid Facial from Soi~ Removal Cl I alkyl- C 2 alkyl- Poly- from poly2gly3coside2 3 potyel~oxylate3ester Cotton Polycotton IOO 0 23.9 0.8 ~.2 24.9 -(~ .5 15 60 ~0 24.6 -11.9 0~6 8.8 -210 -0 4 100 -0 . 8 -27. 8 -o.~
Conditions: hliniwasher, Unbuilt, 6 grains mixed hardness, 100F, 300 ppm~LSD95 = 1.2 Hl'JU for clay and LSD~5 = .4 20 P. S. U . ~or facial soil. ) Clearly, the above results show the improvement from rnixin~7 conventional (ethoxylated) nonionic deter~ent surfactants l,vith all;ylpolyglycosides. The mixtures provide a substantial i~prove-ment in detergency.
EXAI~,lPLE X 11 Combina.lons of alkyl polyglucosides and semi- polar nonionic and/or amide detergent surfactants are compatible with ~nsatur ated soap, but not with saturated soap.
Formula C12_l3 alkYIPIY91YCside2_3 7.3 7.3 7.3 7.3 7.3 C12 j5 alkyldimethylamine oxide 3.3 3 3 3.3 3.3 3.3 Soclium oleate 2.2 - - ~ 4.
.., Sodium tallowate - 2.2 Sodium stearate - - 4.4 - -So~ium C14 15 al~yl polyethoxylate 1.45 1.4S - 2.9 2 25 su I fate Coconu-t diethanolamide 0.13 0.13 0.25 0.13 0.25 Soclium nitrilotriacetate 18.2 18.2 18.2 18.2 18.2 Sodium carbonate 2.8 2.8 2.8 2.8 2.8 Sodium toluene sulfonate 2 2 2 2 2 Ethyl alcohol 3 3 3 3 3 ~/ater - Balanc~-Compositions 1-3 and 5 were lower sudsing than formul~ 4 and were more compatible with washing machine surFaces (less corrosive). Composition 3 formed an unsightly soap scum in the rinse water despite the presence of rnaterials known to ;nhibit formation oF such scums. Composition 3 also formed a thiclc gel rather than a free flowing, clear liquid. It is clear that there rnust not be a substantial excess of saturated soap over unsatura-tecl. The soap must be at least about 40~ unsaturated soap.
It has additionally been cliscovered that the performance of these compositions is improved if the total fr-ee fatty alcohol containing from about 8 to about 20 carbon atoms is less than about 5~, preferably less than about 2~, most preferably less than about 1~.
~YHAT IS CLAlhlED IS~
Other adjunct components ~vhich may be inclucled in the compositions of the present invention, in their conventional art-established levels for use ~i.e., from 0 to a~o~3t 90%), include solvents, bleaching agents, bleach activators, soil-suspending a~ents, corrosion inhibit~rs, dyes, fillers, opticat brighteners, ~err~icides, pH adjusting agents ~ monoethanolamil-~, sodiu~3 carbonate, sodium hydroxid~, etc. ), enzy~es, ~nzyme-stabilizin~
agents, perfumes, fabric softening cornponents, stat;c control ag~nts, and the like.
Fatty acid amide detergent surfactants use~ul herein include those havin~ the formula:
O
p~6 -C-NP< 2 wherein R6 is an all;yl group containing from about 7 to about 21 (preferably From about 9 to about 17) carbon atoms and each P~
is selected from the group consisting of hydrogen, Cl ~ alkyl, Cl ~ hydroxy alkyl, and -(C2H~O)xH where x varies from about I to about 3.
Preferred amides are C8 20 ammonia amides, monoethanolammon-ium, diethanolamides, and isopropanol amides.
A special advanta~e of the combinat;~n of deter~ent surfac-tants herein is their superior compatibility ~vith anionic fluores-10 cent or optical bri~hteners. Nonionic ~urfactants, ~speciallyethoxylated nonionic detergent surfactants, normally climinish the effectiveness of such brighteners. K~ith th~ aclclition of the alkylpolyglycoside surfactant, the brightener t ffectiveness is drarilatically improved, especially on cotton. From ca~out 0~01 to l S about 2~, preferably from about 0 .1 to about 1~ optical bri~htener can be used.
Suitable brighteners include the following:
bis anilino ~ R) triazinyl amino stilbene sulfonate havin~ the formula:
H
X\ N~ N~
N ~ N 1~
l l C-R 50~ 2 ~herein hl is preferably Na, but can be any compatible cation such as potassium, amnlonium, s~bstituted ammonium, e.g, mono-, di-, and triethanolammoni--m, c~c.; X c~n be R2~ NH-where R is selected from H, phenyl, Cl ~ alkyl, or C~
hydroxyalkyl; morpholino-, hydroxy; 5 !
lZt~
Na 3 O NH-;
C 3 O N H ;
H~OCH2CH2)3CH2NH- O -NH-;
O35- O -NH-C~ -NH-;
or mixtures thereo~; and R can be H or SO3 In represented structures, R and X are:
R X
15 -N~C2H4H)2 ~J
-NH-O "
-N ~ O l' -N (CH3)CH CH20~ 1 -NHC2H~OC1 13 "
,, , . , . _ _ .. . . _ _ _ .
-~2~t~
-OH "
C2H40H Na35 0 -NH-N ~ O CH30- ~NII-H(ocH2cH2)3cH~NH- H(OCH2C~2)3C 2 {> -N~t-tO
(HOCH2CH2)2N- O--Na35 ~ -Nl~- O -I~H-tetrasodium 4,4'-bisl (4"-bis(2"'-hydroxyethyl)amino-6"-~3""-sulphenyl)amino-l" ,3" ,S"-tria2in-2"-yl)amino~-2 ,2'-stilbenedisulfo~
nate;
disodium-4-(6'-sulfonaphthol 1' ,2' ,dl tria201-2~yl)-2-stilbene-sul fonate;
disodium 4,4'-bisl (4"-(2"'-hydroxyethylamino)-6"-anilino-1'1 ,-3",5"-triazin-2"-yl)amino]-2,2'-stilbenedis(Jlfonate;
disodium 4,4'-bis[ (4"-(2"'-hydroxyeehoxy)-6"-anilino-1",3",-20 S''-tria2in-2''-yl)amino]-2,2'-stilbenedisulfonate;
disodium 4,4'-bis(4-phenyl-1,2,3-tria~ol-2-yi)-1,2'-stilbenecli-sulfonate;
sodium 4-(2H-naphtho[1,2-d]tria~ol-2-yl)stilbene-2-~ulfonate;
disocJium 4,4'-bis-(2-sulfostyryl)biph~nyl:
disodium 4-~2H-6-sulfonaphtho~1,2-dltria~ol-2-yl)stilben~2-sulfonate; and disodium 3,7-bis(2,4-dimethoxybenzamido)-?,~-dibenzothio^
phenedisulfonate-S ,5-dio)cide.
Other suitable bri~3hteners are disclosed in U . S. Pztents 30 3,537,993 Coward et al; issued Novemb~r 3, 1970 and 3,9$3,~80 Sundby, issued April 27, 1976, The compositions of the present inventior\ can be manu~
factured and used in a variety of forms such as solids, po~^/detos~
granules, pastes, and liquids. The compositions can be used ir~
35 the current U.S. Iaunderin~ processes by forming aqu~us ~.
IL7~
solution containincg from about 0.01% to about I~, pre-Ferably from about 0.05~ to about 0.5%, and most preferably frorn about 0.05 to about û.25% of the composition in ~vater and a~itating -the soil~d fabrics in that aqueous solution. The fabrics are then rinsed and 5 dried. ~Yhen used in this manner the preFerred compositions of the present invention yield exceptionally good detergency on a variety of fabrics.
I n a preferred embodiment a laundry detercJent, preferably, an aqueous heavy-duty liquid, contains ~a) from about l~i to about 20~ (preferably from about 4~s to about 10~3 of the alkylpoly-glycoside detergent surfactant; (b) from about l~ to abollt lO~i lpreferably from about 2% to about 6~) of an amine oxi~e deter-gent surfactant tc) from 1% to about lO~ (preferably from a~out l~
to about 6~) of a water-soluble soap of an unsaturated fatty acid containincJ from about 16 to about 22 carbon atoms; (d~ from 0~ to about 40~ (preferably from about lO~ to about 30~s~ o~ a water-soluble deter~ency builder, preferably selected from the ~;ro~p consisting of pyrophosphates, nitrilotriacetatesr and mixtures thereof; le) from about 0~ to about lO~ (preF~rably from about 0 to about 5~) of water-solu'~le synthetic anionic cletergent sur factant; and, preferably, and (f) the l~alance ~vater.
Such deter~ent compositions provide excellent detergency, clo not clamage washing machines unacceptably, ~nd can be ~ormulatec3 to provide different sudsing patterns by varyin~ the arnount and 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 surfact~nts.
Sodium, potassium, ammonium, and alkanolammonium cations are preferred .
All percentages, parts, and ratios herein are ~y weiyht unless otherwise specified.
The following examples illustrate the compositions and me~hc,d of the present invention.
EXAI~IPLE I
Unbuilt Co~bina ion oF
Cl2-l5 alkyi C12 13 al~ yl ilunter ~`Jni;en2ss Uni~s ~HWU) 55i~c~spolye hox~- Polyester ~
2-3 6.5 Colton Blend ppm in ~la,hCotton (i.e. Poiycotton) Polyester 500 - 9.4 15.4 2.g ~~
400 lO0 6.'1 15.5 4.
300 200 6.3 17.1 7.1 lO200 300 4.4 17.6 7.1 lO0 400 2 .7 1 6 . 3 7 . 1 - 500 -0.3 15.~ 6.8 Test Condi-tion: 95F ~,vater havin~ 6 ~rains c~f mixed 12ar ~-ness and a mini~ ~asher.
As can be seen from th~ ~bove results~ th~ ~llcylpolyglycc--side surFactant has an unexpected problem ~Jith cleanin~ poly-~ster. In general, the alkylpoly~lycosides are consiclere~ non-ionic surfactant replacements, but, surprisin~ly, they ach;eve their best laundry results in combination ~ith nonionic sur~ac-20 tants, especially those that are optimi~ed for cleanin~7 relativ~ly hyclrophobic surfaces. The alkyl polyglycosicles in these examplos were clerived from glucose. S;milar resul ts are obtainecl wit~ the other all;yl ~Iycosides describod herein.
EXAI'ilPLE I I
(Unbuilt ~tix;ures) C12 15 alkyl Cl2_13 Y
polyglyco- polyetho~cy-~ Dirty l~lotor Oil P~erno~a) sides2 3 late3from Polyester Fabri :s 30û ppm 0 ppm 1~) 302L'0 ppm 60 ppm 20 l~0 ppm 120 ppm 27 0 pp~ 300 ppm 17 Same conditions as in Example 1.
As can be seen from the above data, despite ~h~ gener~lly 35 inferior results obtain~d in cleanin9 relatively ~ydrophobic sur-'7~
faces with an aikylpoly~lycoside surfactant, the mixtures o- an alkylpoly~3lycoside and a nonionic surfactant provicles syner~3istic results.
Whiteness .~laintenance ( Redeposition ~est) C12 13 alkyl Hunter ~,'lhit~ness Units (H~'~IU}
C12_15 alkylpolyethoxy- White polyglyco- lat~3 Cot~on l,'Jhite SVhite side2 3Neodol 23-3 T-shirt Polycotton Polyester 300ppm 0 73 G8 3fi 240ppm 60 74 70 ~9 15 180ppm 120 7~ 73 ~}0 60ppm 240 73 73 0 300 71 ~3 ~9 The solutions ~Yere unbuilt and used the same conditions as Examples 1 and 11, the grades bein~ the avera~3e for the two 20 types of soils.
As can be seen from the above data, there is ~ syner~istic improvement in redeposition on cotton For the mixtures of surfac-EXAI`ilPLE IV
25 C12 15 alkyl Ci2-13 alkyl polyglyco- polethoxy% I`ilenstrual Stain Remov~l side2 3 late3 frorn polycotton 300ppm o 50 240ppr~ O0 G0 30 180ppr;) 120 ~3 60ppm 240 7n Oppm 300 63 Same test conditions as in previous examples ~ h unh~
solutions .
,, ~2~
-- 21~ --As can be seen from the above, the un~xpectedly poor showin~3 of the alkylpolyglycQside ~vith respect to this staîn can be improved andlor synergistic improvement obtained by addition of the nonionic surfactant, depending upon the ratio used.
EXA~IPLE V
Built Per,~ormance orl Clay Soil Hunter ~ iteness llnits (H~U~
Cotton Polycotton Polyester Commercial built anionic detergent composition 11.0 19.9 22~5 12-15 alkYIPIYglycoside TSC~2 13 alkylpolyethoxylate6.5 12.7 21.2 26.
*E3uilt with 25% sodium tripolyphosphate ~STP) and 10% sodi~
um carbonate, the total composi.ion be;ng used at 2 lev21 of 1200 ppm 20Test Condition: 60F water having 9 grains of m;xed hard-r-ess ancl miniwasher.
As can be seen from the above the mixed surfactant system of ~his invention provides ecluivalent or superior clay removal across a variety of fabric types as compared to rnore corlventional 25anionic surfactants.
", ~2~
EXAMPLE Vl (~12 15 alkyl 212-13 alky~
polyglyco- polyethoxy-sides 2 3 la te 6 . 5 ~ coconut alkyl Coconut alkyl dimethylamine dimethy!amine oxide ~1:1) oxide 11: i) Clay Removal, H~`IU
Cotton 14 . 6 1 I . 2 Polycotton 28 . 5 22 ~1 Polyester 59.û 55.2 Removal, %
Dirty motor oil 30 37 Chocolate syrup g3 ~3 1 S Grass 67 73 Bacon grease 57 53 ~A,lenstrual stain 83 73 Spaghetti sauce 50 E~oo'y Soil Removal, PSU~ vs.
Commercial Unbuilt Heavy-D~lty Liquid ~Control) ~1.56 ~I.i ~`~hi teness, Soler 2A
T-shi rt 78 77 Polycotton 86 8~;
Polyester 46 39 The sur~actant mixture ~vas 13~ of the formula and the huitd-er \vas sodium nitrilotriacetate at 18~. The test concli tions w~re 2100 ppm of the composition, 95F, 6 grains of mixed hardness.
*PSU equals Panel Score Units wherein expert ~raders assiyn 30 values based on 0 = no differe~ce; I = difference; anci ~ -- c1ear difference.
"
EXA;vlPLE Vl I
Unbuilt HDL Perforr~ance The invention vs. unbuilt commercial heavy-c~uty liquid detersent composition (HDL).
5Panel Score Units vs. Commercial Product Cotton Polyester Dirty motor oil ~0.3 +0,4 Bacon grease +1.0 ~0.8 C;ravy +1.4 +0.2 Spa~hetti sauce +0,3 ~,9 Grass +1.7 ~1.5 Chocolate syrup -O . 4 ~0 ~ 6 TEST CONDIT10N: 450 ppmactives, 95F~at~r h~ving 6 ~rains mixed hardness and a mini ~asher.
15Composieion of the invention: C12 13 atkylpolyethoXylat~/
C~;~ 15 alkylpolyglycoside2 3 at a ratio of 1:1.
EXAl`llPLE Vl 11 Formula Parts C12 15 alkYIPIY~llYcside2-3 13.3 2C Cl2_13 alkYIPIYethoxylate6 5 13.3 Sodium tripolyphosphate 12 . O
Na2C3 13.3 Polyacetaldehyd e deter3ency builder 28.8 Anionic bri~htener* 1.0 25*bis(anilino-hydroxyetnylmethylamino-trsazinylam~no)stilben~
disulfonat~ (sodium salt).
Fluorescer Effectiveness Filtered Unfiltered HWU H~`IUDelta FSol~r 2A
C~2 15 alkylpoly9lyco-side2 31Neodol 23-6.579 111 22 ~7 Commercial built anionic detergent ~control) 80 106 19 ~Q
. ~Z`~7~
Significant technical differences: HI~U=2; Soler 2~=2; and F=l .
EXAI~lPLE iX
~edeposit;on and ~Jhitenessl Brightness Test Cotton T-Shi rt The followin3 results using unbuilt mixtures of sur,ractants clearly demonstrate the effect of the alkylpolyglycn~icle in im-proving anionic brightener effectiveness in the preaence o~ non~
ionic surfactants. The data show clearly that at least about /~0%
10 of the sur~actant system should be alkylpoly~lycoside. Five to six H~YUs are a substantial improvement.
Cl;~_13 all~yl C12-13 alkylt)n~iltered*
polyglycoside2_3 polyethoxylate3 Hunter ~Yhiten~ss Units eefore~fter Detta Washin~~'lashing ( loss~
100 0 120 11~ 10 *To measure bri~htener effect Conditions: ~lini~,vasher, 6 grains mixed harc~ness, 100F, one cycle 30n pprn total surfactant, 15 ppm of the brightener of 25 Exampl~ Vl t I .
EXAI;tPLE X
The alkylpolyglycosides improve the performance of very water soluble ~high HLB) nonionics.
Ratio Clay Cleanin~ Per~ormance 30C12_l3 alkyl-C12_l3 alkyl Hullter ~Yhi~eness lJnit~
plY91YCsid~2_3polyethoxylatel;~ Polyes.er Polycottor1 Cotton 100 0 25 . 9 27.0 3.?i ~,5 3 5 !~ o 2 8 A 85 0 ~ 3 . 6 2g .1~i . n ~ .
o loo 28 . 12 ~ 2 2 ~ I
~2~ 7~
-- 2~ --Conclitions: I~liniwasher, unbuilt, 6 grains at mixed hard-ness, 100F, 300 ppm total active.
As can be seen from the above data, the mixtures are clear-ly superior. From I to 2 H~iU are a substantial dif,erence in this 5 test.
EXA~ PLE X l ~Ikyl Polyglucosides Improve the Performance of Oil Soluble (Low HLB) Nonionic Deter~ent Surfactants (HWU) ~p,S.tJ.) 10Ratio Clay Removal Lipid Facial from Soi~ Removal Cl I alkyl- C 2 alkyl- Poly- from poly2gly3coside2 3 potyel~oxylate3ester Cotton Polycotton IOO 0 23.9 0.8 ~.2 24.9 -(~ .5 15 60 ~0 24.6 -11.9 0~6 8.8 -210 -0 4 100 -0 . 8 -27. 8 -o.~
Conditions: hliniwasher, Unbuilt, 6 grains mixed hardness, 100F, 300 ppm~LSD95 = 1.2 Hl'JU for clay and LSD~5 = .4 20 P. S. U . ~or facial soil. ) Clearly, the above results show the improvement from rnixin~7 conventional (ethoxylated) nonionic deter~ent surfactants l,vith all;ylpolyglycosides. The mixtures provide a substantial i~prove-ment in detergency.
EXAI~,lPLE X 11 Combina.lons of alkyl polyglucosides and semi- polar nonionic and/or amide detergent surfactants are compatible with ~nsatur ated soap, but not with saturated soap.
Formula C12_l3 alkYIPIY91YCside2_3 7.3 7.3 7.3 7.3 7.3 C12 j5 alkyldimethylamine oxide 3.3 3 3 3.3 3.3 3.3 Soclium oleate 2.2 - - ~ 4.
.., Sodium tallowate - 2.2 Sodium stearate - - 4.4 - -So~ium C14 15 al~yl polyethoxylate 1.45 1.4S - 2.9 2 25 su I fate Coconu-t diethanolamide 0.13 0.13 0.25 0.13 0.25 Soclium nitrilotriacetate 18.2 18.2 18.2 18.2 18.2 Sodium carbonate 2.8 2.8 2.8 2.8 2.8 Sodium toluene sulfonate 2 2 2 2 2 Ethyl alcohol 3 3 3 3 3 ~/ater - Balanc~-Compositions 1-3 and 5 were lower sudsing than formul~ 4 and were more compatible with washing machine surFaces (less corrosive). Composition 3 formed an unsightly soap scum in the rinse water despite the presence of rnaterials known to ;nhibit formation oF such scums. Composition 3 also formed a thiclc gel rather than a free flowing, clear liquid. It is clear that there rnust not be a substantial excess of saturated soap over unsatura-tecl. The soap must be at least about 40~ unsaturated soap.
It has additionally been cliscovered that the performance of these compositions is improved if the total fr-ee fatty alcohol containing from about 8 to about 20 carbon atoms is less than about 5~, preferably less than about 2~, most preferably less than about 1~.
~YHAT IS CLAlhlED IS~
Claims (15)
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 1 1/2 to about 10;
(B) from about 1% to about 90% of a nonionic detergent surfactant; and (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.
(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 1 1/2 to about 10;
(B) from about 1% to about 90% of a nonionic detergent surfactant; and (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.
2. The composition of Claim 1 wherein Component (A) has the formula R2O(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, 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.
4. The composition of Claim 3 wherein the nonionic surfactant has the formula R(OC2H4)nOH, wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12.
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 1 wherein the nonionic surfactant has an HLB of from about 5 to about 17.
7. The composition of Claim 6 wherein the nonionic surfactant has the formula R(OC2H4)nOH, wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12.
8. The composition of Claim 7 wherein x is from about 1 1/2 to about 3.
9. The composition of Claim 1 wherein the detergency builder is present at a level of from about 10% 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 metaphosphates, nitrilotriacetates, citrates, and polyacetal carboxylates.
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 metaphosphates, nitrilotriacetates, citrates, and polyacetal carboxylates.
10. The process of cleaning mixed hydrophobic and hydrophilic fabrics in an aqueous detergent solution containing from about 0.01% to about 1% of the detergent composition of Claim 1.
11. The composition of Claim 1 wherein for Component (A) z is a moiety derived from a reducing saccharide selected from the group consisting of glucose, galactose, and mixtures thereof and x is a number from 1 1/2 to about 3, and Component (B) is a polyethoxylate nonionic detergent surfactant wherein the ratio of (A) to (B) is greater than 1:1
12. The composition of Claim 11 wherein Component (A) has the formula R2O(CnH2nO)t(glycosyl)x where R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, n is 2 or 3, t is from 0 to about 10, and the glycosyl moiety is derived from glucose.
13. The composition of Claim 12 wherein the nonionic surfactant has an HLB of from 5 to about 17.
14. The composition of Claim 13 wherein the nonionic surfactant has the formula R(OC2H4)nOH, wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12.
15. The composition of Claim 14 wherein the Component (A) the alkyl portion of R2 has from about 12 to about 14 carbon atoms, n is 2, t is 0, and x is from about 1.6 to about 2.7.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30664081A | 1981-09-28 | 1981-09-28 | |
| US306,640 | 1981-09-28 | ||
| US37169182A | 1982-04-26 | 1982-04-26 | |
| US371,691 | 1982-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1200171A true CA1200171A (en) | 1986-02-04 |
Family
ID=26975278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000412243A Expired CA1200171A (en) | 1981-09-28 | 1982-09-27 | Detergent compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0075995B1 (en) |
| BR (1) | BR8205646A (en) |
| CA (1) | CA1200171A (en) |
| DE (1) | DE3276373D1 (en) |
| GR (1) | GR76286B (en) |
| IE (1) | IE53899B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE21926T1 (en) * | 1982-05-10 | 1986-09-15 | Procter & Gamble | LOW-PHOSPHATE LAUNDRY DETERGENT COMPOSITIONS. |
| EP0105556A1 (en) * | 1982-09-30 | 1984-04-18 | THE PROCTER & GAMBLE COMPANY | Liquid detergent composition containing nonionic and ionic surfactants |
| FR2557134B1 (en) * | 1983-12-23 | 1986-11-28 | Produits Ind Cie Fse | ADDITIVE FOR ALKALINE CLEANING BATHS, COMPLETE PRODUCT CONTAINING SAME AND USE |
| US4720399A (en) * | 1984-06-01 | 1988-01-19 | Colgate-Palmolive Company | Process for manufacture of particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders |
| US4725455A (en) * | 1984-06-01 | 1988-02-16 | Colgate-Palmolive Company | Process for manufacturing particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and polyphosphate builders |
| US4627931A (en) * | 1985-01-29 | 1986-12-09 | A. E. Staley Manufacturing Company | Method and compositions for hard surface cleaning |
| USH269H (en) | 1985-03-11 | 1987-05-05 | A. E. Staley Manufacturing Company | Disinfectant and/or sanitizing cleaner compositions |
| US4668422A (en) * | 1985-05-31 | 1987-05-26 | A. E. Staley Manufacturing Company | Liquid hand-soap or bubble bath composition |
| IL81354A (en) * | 1986-01-30 | 1990-11-05 | Colgate Palmolive Co | Liquid detergent having improved softening properties |
| IL81353A (en) * | 1986-01-30 | 1990-08-31 | Colgate Palmolive Co | Liquid softergent having improved detergency containing alkyl glycoside |
| DE3708330A1 (en) * | 1987-03-14 | 1988-09-22 | Henkel Kgaa | LIQUID, ALKALINE CLEANER CONCENTRATES |
| JPH02500111A (en) * | 1987-05-18 | 1990-01-18 | スタリー コンチネンタル インコーポレイテッド | Low foaming detergent composition |
| GB8716949D0 (en) * | 1987-07-17 | 1987-08-26 | Ici Plc | Composition |
| MY103951A (en) * | 1988-01-12 | 1993-10-30 | Kao Corp | Detergent composition |
| US4800038A (en) * | 1988-01-21 | 1989-01-24 | Colgate-Palmolive Company | Acetylated sugar ethers as bleach activators detergency boosters and fabric softeners |
| GB8803037D0 (en) * | 1988-02-10 | 1988-03-09 | Unilever Plc | Aqueous detergent compositions & methods of forming them |
| US5230835A (en) * | 1988-08-04 | 1993-07-27 | Kao Corporation | Mild non-irritating alkyl glycoside based detergent compositions |
| DE68925390T2 (en) * | 1988-08-04 | 1996-06-05 | Kao Corp | Detergent composition |
| EP0377807B1 (en) * | 1988-12-07 | 1994-02-09 | Henkel Kommanditgesellschaft auf Aktien | Highly alkaline phosphate-free liquid detergent |
| AU5709090A (en) * | 1989-06-30 | 1991-01-03 | Amway Corporation | Built liquid detergent compositions |
| JPH078991B2 (en) * | 1989-07-18 | 1995-02-01 | 花王株式会社 | Neutral liquid detergent composition |
| DE4015655A1 (en) * | 1990-05-16 | 1991-11-21 | Basf Ag | New alkyl:mono- and alkyl:poly:glucoside ether carboxylate cpds. |
| DE4026809A1 (en) * | 1990-08-24 | 1992-02-27 | Henkel Kgaa | Liq. aq. washing compsn. - contains anionic surfactant, nonionic surfactant and alkyl poly:glycoside as thickener, improving washing |
| WO1992003527A1 (en) * | 1990-08-22 | 1992-03-05 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing agent with increased viscosity |
| DE4029035A1 (en) * | 1990-09-13 | 1992-03-19 | Huels Chemische Werke Ag | LAUNDRY DETERGENT |
| GB9025248D0 (en) * | 1990-11-20 | 1991-01-02 | Unilever Plc | Detergent compositions |
| DE4039223A1 (en) * | 1990-12-08 | 1992-06-11 | Huels Chemische Werke Ag | LIQUID DETERGENT |
| DE4039229A1 (en) * | 1990-12-08 | 1992-06-11 | Huels Chemische Werke Ag | COSMETIC CLEANING LIQUID |
| DE4101070A1 (en) * | 1991-01-16 | 1992-07-23 | Huels Chemische Werke Ag | WASHING POWDER |
| DE4124247A1 (en) * | 1991-07-22 | 1993-01-28 | Henkel Kgaa | METHOD FOR STABILIZING AQUEOUS ZEOLITE SUSPENSIONS |
| US5476610A (en) * | 1991-07-22 | 1995-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Process for stabilizing aqueous zeolite suspensions |
| DE4210365C2 (en) * | 1992-03-30 | 1995-06-08 | Henkel Kgaa | Use of cleaning agents for hard surfaces |
| DE4236506A1 (en) * | 1992-10-29 | 1994-05-05 | Henkel Kgaa | Process for the preparation of aqueous solutions of anionic surfactants with improved low-temperature stability |
| WO1995006702A1 (en) * | 1993-09-02 | 1995-03-09 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous detergent mixtures |
| DE19543990C2 (en) * | 1995-11-25 | 2000-07-20 | Cognis Deutschland Gmbh | Liquid primary products for washing, rinsing and cleaning agents |
| US5866530A (en) * | 1995-11-25 | 1999-02-02 | Henkel Kommanditgesellschaft Auf Aktien | Non-aqueous liquid mixtures of alkyl polyglycoside and alkyl polyalkylene glycol ether useful in various detergent applications |
| GB9606913D0 (en) | 1996-04-02 | 1996-06-05 | Unilever Plc | Surfactant blends processes for preparing them and particulate detergent compositions containing them |
| EP0849354A1 (en) | 1996-12-20 | 1998-06-24 | Unilever Plc | Softening compositions |
| SE510989C2 (en) | 1997-10-29 | 1999-07-19 | Akzo Nobel Nv | Highly alkaline compositions containing a hexyl glycoside as a hydrotrope |
| WO2015101454A1 (en) | 2013-12-30 | 2015-07-09 | Unilever N.V. | Detergent composition |
| WO2023213524A1 (en) | 2022-05-06 | 2023-11-09 | Unilever Ip Holdings B.V. | Detergent composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3219656A (en) * | 1963-08-12 | 1965-11-23 | Rohm & Haas | Alkylpolyalkoxyalkyl glucosides and process of preparation therefor |
| DE1617119A1 (en) * | 1966-11-18 | 1971-02-18 | Henkel & Cie Gmbh | Low-foaming stain treatment agent for textiles |
| US3772269A (en) * | 1969-07-24 | 1973-11-13 | Ici America Inc | Glycoside compositions and process for the preparation thereof |
| US3721633A (en) * | 1969-10-06 | 1973-03-20 | Atlas Chem Ind | Aqueous built liquid detergents containing alkyl glycosides |
| DE2148279A1 (en) * | 1970-09-30 | 1972-04-06 | Unilever N V , Rotterdam (Nieder lande) | Builders for detergents |
| GR76189B (en) * | 1981-07-13 | 1984-08-03 | Procter & Gamble |
-
1982
- 1982-09-20 GR GR69311A patent/GR76286B/el unknown
- 1982-09-22 EP EP82201171A patent/EP0075995B1/en not_active Expired
- 1982-09-22 DE DE8282201171T patent/DE3276373D1/en not_active Expired
- 1982-09-27 CA CA000412243A patent/CA1200171A/en not_active Expired
- 1982-09-27 IE IE233482A patent/IE53899B1/en not_active IP Right Cessation
- 1982-09-28 BR BR8205646A patent/BR8205646A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0075995A3 (en) | 1984-03-07 |
| BR8205646A (en) | 1983-08-30 |
| DE3276373D1 (en) | 1987-06-25 |
| EP0075995A2 (en) | 1983-04-06 |
| GR76286B (en) | 1984-08-04 |
| IE822334L (en) | 1983-03-28 |
| IE53899B1 (en) | 1989-04-12 |
| EP0075995B1 (en) | 1987-05-20 |
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