CA1172403A - Liquid detergent/softener compositions - Google Patents
Liquid detergent/softener compositionsInfo
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- CA1172403A CA1172403A CA000388046A CA388046A CA1172403A CA 1172403 A CA1172403 A CA 1172403A CA 000388046 A CA000388046 A CA 000388046A CA 388046 A CA388046 A CA 388046A CA 1172403 A CA1172403 A CA 1172403A
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Abstract
ABSTRACT
Liquid detergent/softener compositions comprising nonionic and cationic surfactants with added co-surfactant which is either a zwitterionic or semi-polar nonionic surfactant at specific ratios of nonionic surfactant to co-surfactant at a critical product pH for improved body soil cleaning.
Liquid detergent/softener compositions comprising nonionic and cationic surfactants with added co-surfactant which is either a zwitterionic or semi-polar nonionic surfactant at specific ratios of nonionic surfactant to co-surfactant at a critical product pH for improved body soil cleaning.
Description
;;
LIQUID DETER~;ENT/SOFTENER COMPOS ITIONS
Larry ~. Hughe .. . . .. . .. . ... . . .. . . .
,., .~. .... , ~ .
Summary of The Invent1on The present invention relates to hea~-duty, essen-tially unbuilt~ stable liquid laundry detergent compositions, especially beneficial for clean.ing and softening fabrics.
The compositions are heavy-duty liquid detergent comp-ositions comprising:
(1) from about 5~ to about 20~ of ethoxylated nonionic detergent surfactant;
; (2) from about 5% to about 20% of a cosurfactant selected from the group of semipolar nonionic detergent surfactant, zwitterionic detergent surfactant, and mixtures thereof;
,, . ~$
~ ~7~2~(D3
LIQUID DETER~;ENT/SOFTENER COMPOS ITIONS
Larry ~. Hughe .. . . .. . .. . ... . . .. . . .
,., .~. .... , ~ .
Summary of The Invent1on The present invention relates to hea~-duty, essen-tially unbuilt~ stable liquid laundry detergent compositions, especially beneficial for clean.ing and softening fabrics.
The compositions are heavy-duty liquid detergent comp-ositions comprising:
(1) from about 5~ to about 20~ of ethoxylated nonionic detergent surfactant;
; (2) from about 5% to about 20% of a cosurfactant selected from the group of semipolar nonionic detergent surfactant, zwitterionic detergent surfactant, and mixtures thereof;
,, . ~$
~ ~7~2~(D3
- 2 -
(3) from about 2~ to about ~0~, preferably no more than about 10%, of a cationic -urfactant capable of im-parting softness andfor antistatic benefits to fabrics;
~ 4) from about 2% to about 10% of a pH buffering agent to provide a product pH of from about 9.5 to about 12; and (5) the balance water, perfumes, brighteners, etc.
the total of (1), (2) and (3) being in excess of about 20%, the ratio of (1) to (2) being from about 3:1 to about 1:3, pre~erably from about 1:1 to about 1:2, and the compo- ~
sition containing less than about 5% calcium ion sequester- ii ing or precipitating detergency builder. -~
~isclosur_ of- The Invention ~-The compositions of the present inven-tion comprise~ by weight, from about 15~ to about 70%, prefexably rom about 20~ to about 50%, and mos~ preferably ~rom about 20~ to abvut 30%, of a mixture of particularly de~ined nonionic, semipolar or zwitterionic, and cationic suractants in ~he ratios stated herein. Preferred compositions contain at least about 3~ of the cationic component, ikself, in order 2~ to assure the presence of a suficient amount to provide the desired cleaning and ~a~ ic conditioning benefits.
_ The compositions of the present invention contain the nonionic and semipolar or zwitterionic cosurfactants, defined more precisely hereinafter, within ratios of non-ionic to cosurfac-tant of from about 3:1 to about 1:3, preferably from about 1:1 to about 1:2, most preEerably about 1:1 in or~er to achieve the best de-~ergency and softening performance. Preferred composltions may also contain mixed nonionic surfactant systems.
It is preferred that the compositions of the present inven-tion are formulated so as to have a pH of at least about 9.5, preferably from about 10 to about 11, preferably less than about 12, in the product in order to optimize their overall cleaning performance. The cleaning results follow product pH even when the organic buffering capacity is relati~ely constant. The organic buffering agent is essential to th~ stability of the product~ Higher pH's ( - 11) do not provide any cleaning improvement while ~f ~il'7~L6D3 increasing safety risks. Alkalinity sources, such as potassium hydroxide, potassium carbonate, potassium bicar-bonate, sodium hydroxide, sodium carbonate and sodium bicarbonate, may be included in the compositions to adjust the product pH. However, it is essential that the major alkalinity source comprise an organic buffering agent~
preferably mono-, di-, or triethanolamine, more preferably monoetha,nola~ine. Monoethanolamine provides a benefit by its superior ability to solubilize the acids in body soils.
In these systems, surprisingly, overall performance may be enhanced by varying th~ pH of the product despit~ a rela-ti~ely constant pH during the laundering p~ocess~ Particu-larly preferred compositions hava a pH of at least ab~ut 1 in order to optimize the removal of greasy/oil~ and body soils. In addition to the higher pH in the product, t~ese preferred compositions should also have the abilit~ to maintain a pH in the laundry solution o from about 7.5 to about 10 throughout the washing operation (reserve alkalin-ity). Such a reserve alkalinity may be obtained by incor-porating the preferred organic compounds which buffer atpH's of from about 8 to~l, such as monoethanolaminet diethanolamine or trie-t~anolamine. ~ -Preerred composltqons of the present in~ention arealso essentially free of oily hydrocarbon materials and sol~ents, such as mineral oil, paraffin oil and kerosene, since thesè materials f which are themselves oil~ by nature, load the washing li~uor with excessive oily material, thereby diminishing the cleaning effectiveness of the compositions.
Monionic Component .
The nonionic detergent surfactants used in the composi-tions of the present invention are conventional in the art.
Preferred nonionic detergent surfactants are biodegradable and have the formula R(OC~H4)nOH, wherein R is a primary alkyl chain containing an average of from about 10 to about 18, preferably from about 10 to abou~ 16, carbon atoms, and n is an average of from about 2 to about 9, preferably from about 2 to about 7~ These nonionic surfactants have an HLB
thydrophilic-lipophilic balance) of from ahout 5 to about .' ~ . .. "
" , . . _ _ _ _ _ _ . _ _ _ . _ ~ , _ , _ _ _ . _ _ _ . _ . _ _ . . ~ _ . . . . , , . . . . . . . . . _ . . . _ . , . _ , . , . . . _ . _ , _ _ . _ _ , .
. . . , . . _ . _ _ . .
t
~ 4) from about 2% to about 10% of a pH buffering agent to provide a product pH of from about 9.5 to about 12; and (5) the balance water, perfumes, brighteners, etc.
the total of (1), (2) and (3) being in excess of about 20%, the ratio of (1) to (2) being from about 3:1 to about 1:3, pre~erably from about 1:1 to about 1:2, and the compo- ~
sition containing less than about 5% calcium ion sequester- ii ing or precipitating detergency builder. -~
~isclosur_ of- The Invention ~-The compositions of the present inven-tion comprise~ by weight, from about 15~ to about 70%, prefexably rom about 20~ to about 50%, and mos~ preferably ~rom about 20~ to abvut 30%, of a mixture of particularly de~ined nonionic, semipolar or zwitterionic, and cationic suractants in ~he ratios stated herein. Preferred compositions contain at least about 3~ of the cationic component, ikself, in order 2~ to assure the presence of a suficient amount to provide the desired cleaning and ~a~ ic conditioning benefits.
_ The compositions of the present invention contain the nonionic and semipolar or zwitterionic cosurfactants, defined more precisely hereinafter, within ratios of non-ionic to cosurfac-tant of from about 3:1 to about 1:3, preferably from about 1:1 to about 1:2, most preEerably about 1:1 in or~er to achieve the best de-~ergency and softening performance. Preferred composltions may also contain mixed nonionic surfactant systems.
It is preferred that the compositions of the present inven-tion are formulated so as to have a pH of at least about 9.5, preferably from about 10 to about 11, preferably less than about 12, in the product in order to optimize their overall cleaning performance. The cleaning results follow product pH even when the organic buffering capacity is relati~ely constant. The organic buffering agent is essential to th~ stability of the product~ Higher pH's ( - 11) do not provide any cleaning improvement while ~f ~il'7~L6D3 increasing safety risks. Alkalinity sources, such as potassium hydroxide, potassium carbonate, potassium bicar-bonate, sodium hydroxide, sodium carbonate and sodium bicarbonate, may be included in the compositions to adjust the product pH. However, it is essential that the major alkalinity source comprise an organic buffering agent~
preferably mono-, di-, or triethanolamine, more preferably monoetha,nola~ine. Monoethanolamine provides a benefit by its superior ability to solubilize the acids in body soils.
In these systems, surprisingly, overall performance may be enhanced by varying th~ pH of the product despit~ a rela-ti~ely constant pH during the laundering p~ocess~ Particu-larly preferred compositions hava a pH of at least ab~ut 1 in order to optimize the removal of greasy/oil~ and body soils. In addition to the higher pH in the product, t~ese preferred compositions should also have the abilit~ to maintain a pH in the laundry solution o from about 7.5 to about 10 throughout the washing operation (reserve alkalin-ity). Such a reserve alkalinity may be obtained by incor-porating the preferred organic compounds which buffer atpH's of from about 8 to~l, such as monoethanolaminet diethanolamine or trie-t~anolamine. ~ -Preerred composltqons of the present in~ention arealso essentially free of oily hydrocarbon materials and sol~ents, such as mineral oil, paraffin oil and kerosene, since thesè materials f which are themselves oil~ by nature, load the washing li~uor with excessive oily material, thereby diminishing the cleaning effectiveness of the compositions.
Monionic Component .
The nonionic detergent surfactants used in the composi-tions of the present invention are conventional in the art.
Preferred nonionic detergent surfactants are biodegradable and have the formula R(OC~H4)nOH, wherein R is a primary alkyl chain containing an average of from about 10 to about 18, preferably from about 10 to abou~ 16, carbon atoms, and n is an average of from about 2 to about 9, preferably from about 2 to about 7~ These nonionic surfactants have an HLB
thydrophilic-lipophilic balance) of from ahout 5 to about .' ~ . .. "
" , . . _ _ _ _ _ _ . _ _ _ . _ ~ , _ , _ _ _ . _ _ _ . _ . _ _ . . ~ _ . . . . , , . . . . . . . . . _ . . . _ . , . _ , . , . . . _ . _ , _ _ . _ _ , .
. . . , . . _ . _ _ . .
t
4~P3 14, preferably from about 6 to about 13. HLB, an indicator of a surfactant's hydxophilic or lipophilic nature, is defined in detail in Nonionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, pages 6~7-613~
Preferred nonionic surfactants for use in the present invention include the condensation product: of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of eth~lene oxide;
10 the condensation product of C12 15 alcohol wi~h 7 moles o~
- ethylene oxide; the condensation product of C12 15 alcohol with 9 moles of ethylene oxide; the condensation pxoduct of C14 15 alcohol with 2.25 moles of ethylene oxide; the condensation product o C14 15 alcohol with 7 moles of ethylene oxide; the condensation product of Cg_ll alcohol with 8 moles o~ ethylene oxide, which is stripped so as to remove unethoxylated and lower ethoxylate fractions; the condensation prod~ct of C12 13 alcohol with 6.5 moles of ethylene oxide, and this same alcohol ethoxylate which is stripped so as to remove unethoxylated and lower ethoxylate fractionsO A preferred~lass of such surfactants utilize alcohols which contai~-~bout 20~ 2-methyl branched isomers, and are commercially available, under the trademark"Neodol'~
from Shell Chemical Company. The condensation product of tallow alco~ol with 9 moles of ethylene oxide is also a preferred nonionic surfactant for use herein. Paxticularly preferred nonionic surfactants ~or use in the compositions of the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide, the conden-30 sation product o~ C12_13 alcohol with 6.5 moles of ethylene oxide, the condensation product of Clz_l5 alcohol with 7 moles of et~ylene oxide, the condensation pxoduct o~ C14 15 alcohol with 7 moles of ethylene oxide, and mixtures of those surfactants. In preferred nonionic surfactants the lower, e.g., the unethoxylated and monoethoxylated alcohols, are stripped to provide improved performance.
The compositions of the present invention may contain mixtures of nonionic surfactants falling within the above nonionic surfactant~definition, such as: a mixture Qf the ... , .; .. .,, .. _ . . . .,, .. . .. . ., . . .. . ................................ , . ........ ._ .. . _ . .. _. ~
... _ .. . .. ,.. _ _ . _. , . , . , . .. . .. . . _ . ., . _ _ . ,, . ., .. , .. ._ .. ... _ . . _ .. . .. . . . .. .
. _ - ~ ,t ~ . _ .. . . , , _ _ .. , . , . _ . _, . . . .. . . . . .
~ ~72~L~3 condensation product of C12 13 alcohol with 6.5 moles of - ethylene oxide~(Neodol 23-6.5~)~with the condensation product of C14 15 alcohol with 7 moles of Pthylene oxidel~(Neodol 45-7)",**in a ratio o from ahout 4:1 to 1:4, a mixture of the condensation product of Cl~ 15 alcohol with 7 moles of ethylene oxide with'iNeodol 45-7',*~n a ratio of from about 4:1 to ~bout 1:4 preferably about 1:1; or a mixture of the condensation product of Cg 11 alcohol with 8 moles of ethylene oxide, stripped to remove lower ethoxylate and non-ethoxylated fractions, with Neodol 45-7, in a ratio of higher ethoxylate to lower ethoxylate of from about 1:6 t~ --about 1:1, preferably about 1:3. ~he present invention can also contain nonionic surfactants, some o~ which do not ~all within the above preferred nonionic surfactant deflnit:ion (such as alcohol ethoxylates having an average of greater than about 9 ethylene oxide groups per molecule, secondary alcohol ethoxylates, or alkyl phenol sthoxylates). It is preerred however that a~ least one of the nonionic sur-factants contained in the mixture falls within the above definition of tlle prefe~rred nonionic surfactants. Where the nonionic surfactant mix~ure-contains a nonionic surfactant (or surfactants~ which falls outside o~ the above pre~erred nonionic definition, it is pre~erred that the ratio of the surfactant (or surfactants) within the definition to that which is outside the preferred definition be within the range of from about 1:1 to about 10:1. A specific example of such a surfactant mixture is a mixture of the conden-ion produc,t of C12_13 alcohol with 6.5 moles of ethyle~eoxide (e.g., Neodol 23 6.5) and the condensation product of a secondary C15 alcohol with 9 moles of ethylene oxid~
~e.g.,~Tergitol 15-S-9),' 1n a ratio of lower ethoxylate to higher ethoxylate nonionic of from about 1:1 to about 6:1;
or a mixture of'~eodol 23-6.5"and the condensation product of nonyl phenol with 7 moles of ethylene oxide, having a ratio of"Neodol"to nonyl phenol ethoxylate of a~out 4:1.
Preferred nonionic surfactant mixtures contain alkyl glyceryl ethers in addition to the preferred nonionic * Trademark ** Trademark *** Trademark .. .. _ ~ ... .. . _ .. ... . _ . . . . ...... _ . . . . . . . . .. _ .. . .... .. .
~ 724~P~
suractant. Particularly pre~erred are glyceryl ethers having the formulae R-OCH2-C~-C~2OH and R-O(CH2cH2O]ncH2cHcH2OH
OE~ . O~I
wherein R is an alkyl or alkenyl group of from about 8 to about 18, preferably about 8 to 12, carbon atoms or an al~a~yl group having from about 5 to 14 carbon in the alkyl chain, and n is from 1 to about 6, togeth~r with the non-ionic surfactant component of the present i~vention, in a ratio o~ noni.onic surfactant to glyceryl ether of rom about 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful in the present invention are aisclosed in U.S. Patent 4,0~8,713, ~ones, issued July 4, 1978a Other ~onionic surfactants well known in the detergency.
arts may be used, either alone or in combination with one or more of the preferre~ nionic suractants. Examples of such surfactants are Lis~ed in U.S~ Patent No. 3,717,630, Booth, issued February~-20, 1973, and U.S. Patent No. 3,332,880, Kessler et al, issued July 25, lg67~
Nonlimiting examples of suitable nonionic surfac~ants which may be used in conjunc-tion with the required nonionic surfactants, deined above, axe: polyethyiene oxide condensates o alkyl phenols, such as thel'Igepal~surfactants, marketed by the GAF Corporation, and the"Triton"surfactants, marketed by the Rohm and Haas Coinpany; condensation products o aliphatic alcohols with from a~out 10 to about 25 moles o~ ethylene oxide, where those alcohols are o~ a prlmary, branched or secondary alkyl chain structure; condensation products o ethylene oxide -with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, such as the"Pluronic"***.
surfactants, marketed by Wyandotte Chemical Corpo~ation; and condensation products o ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene `~ * Trademark ** Trademark *** Trademark _ .. _, . . .. , .. . , .. _ , .,, , ._ _ _ . _ , . . .. ., . ., .. _ _ . _ _, ,,,, ;, ' 3 ~ ~29~3 diamine, such as the"Tetronic"surfactants, marketed by Wyandotte Chemical Corporation.
Another pre~erred group of nonionic surfactants useful herein comprises a mixture of "surfactant'l and ethoxylated nonionic "cosurfactant", containing at least one nonionic surfactant falling within ~he definition of the preferred nonionic surfactants useful herein, as described in Canadian Patent No. 1,059,865, Collins, issued August 7, 1979.
Another preferred mixture o~ nonionic surfactants omPriSeS C12~13E6.5 a~d C14_1sEO7 in a ratio of 4 1 to 1:4 This mixture pxovides a desirable suds pattern during the wash and during rinsing as compared to either surfactant by itself.
Preferred compositions o the present invention are substantially free (less than about 2~, preferably less than about 1~, more preferably none) of fatty acid polyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylen~glycol 80~-distearate. Such additives offer no ad~a~tage, and possibly even result in a disadvantage, in terms-~f achieving the particulate soil removal and fabric conditioning benefits provided by the present in~ention.
The Cosurfactant ~a) Zwitterionic detergent surfactant Zwitterionic surfactants include derivatives of alipha~
tic quaternary ammonium, phosphonium, and sulfonium com-pounds in which the aliphatic moieties can be straight o~
branch chain~ wherein one of the aliphatic su~stituents contains from about 8 to 18 carbon atoms and one contains an anionic, p~eferably carboxylate or sulfonate, water-solubil-izing gxoup. Particulaxly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates dis-35 closed in U.5. Patent 3,92~,262, Laughlin et alf issued December 9, 1975; U.S. Patent 3,929,~78, Laughlin et al, issued December 30, 1975-o * Trademark .. , . . . .. , .. . _, _ . .. .. .. ... _ . .. . . . . . _ ........... ... . _, _ _ _, . .. .
1~7Z~3 The inclusion _ .
of these surfactants in the compositions s~lpplement the excellent clay soil removal performan~e with good body soil removal and improved softening performance.
Preerred zwitterionic detergents have th~ fonmula:
~2 R2 Rl- N~CH2R S03~ and Rl-N~-CH2R4Coo wherein Rl is an alkyl radical containing ~xom about 10 to about 18 carbon atoms, R2 and R3 are each selected from the group consisting o~ methyl, ethyl and hydroxy ethyl xadicals, R4 is selected from the group consisting o~ alkylene, poly-alkoxy, and hydroxy alk ~ ne radicals, preferably methylene~
ethylene, polyethoxy, ~y~roxy ethylene and propylene rad-icals and said hydroxyL~groups are attached only to second-ary carbon atoms.
23 Specific examples include:
(a) Betaine examples include N-coconut alkyl betaine;
N-hexadecylbetaine; 6(N-hexadecyl-N,N-dimethylammonio)-hexanoate; N-(2-coconutamido)ethylbetaine; and (N-hexadecyl-N,N-dimethylammonio)-3,6-dioxa-nonanoate.
(b) Sultaine detergents of particular interest are those in which the long alkyl chain (Rl) is a speci~ic C10-C18 alkyl or a mixture of alkyl chains derived from natur-ally occurring substances, whether hydrogenated or not~ and the short alkyl chains are methyl gxoups. Fox instance, where Rl is derived from tallow or coconut oil, R4 is an ethylene radical with a hydrox~l group substituted on the middle carbon atoms of the CH2R4 ~rouping, and R2 and R3 are methyl groups, the sultaine detergent is of particular interest. Other specific éxamples o~ preferred sultaine , . .... ...............
- . ................ .. .
.. .:
_ g- ~L~72~
detergents include 3~(N,N-dimethyl-N-hexadecylammonio)-2(polyethoxy)-ethane-1-sulonate, 3-(N,N-dimethyl-N-hexa-decyla~onio)-propane-l-sulfonate, 2-(N-methyl-N-ethyl-N-decylammo~io)-ethane-l-sulfonate, 4-(N,N-diethyl-N-tetra-decylammonio)butane-l-sulfonate, 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-2-hydroxy butane-l-sulfonate, 2-[N,N-di(2-hydroxyethyl)-N dodecylammonio]-ethane-l-sulfonate, 4-tN-methy~-N-(2-hydroxyethyl)-N-hexadecylammonio~-3-hydr butane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecylammonio) 10 2-hydroxypropane-1-sulfonate. Other specific examples -include compounds wherein different long alkyl chains are - -- -~
used to provide the corresponding decyl, dodecyl, tetra~-decyl, hexadecyI, and octadecyl homologs o~ the above compounds such as 3-~N,N dimethyl-N~tetradecylammonio)-propane-l-sulfona~e, 3-(N,N-dimethyl-N-octadecylammonio)-ethane~l sulfonate, etc. Still other specific examples include compounds where the short chains substituted on the nitrogen atom in the above compounds are replaced by the corresponding methyl, eth~l and hydroxy ethyl groups to 2~ providè the corresponding homologs of the above compounds.
~c~ Semipolar noni ~ic suxfactants Generically these surfactants have the formula R (R ~n~~~~
wherein X is N, S, or P with n being 2 when X is ~ or P and 1 when X is S, Rl is a long chain hyarophobic group and each R2 is a short chain h~drophobic or hydrophilic group.
Pre~erred are surfactants having the formula:
R6 . '.
R5-N~ O
R
wherein R is an organic radical containing from about l0 to about 24 carbon atoms, containing from 0 to about 3 ether linkages, containing from 0 to 1 hydroxy ~roup, and having one alkyl moiety which contains from about 10 to about 18 carbon atoms and no ether linkages; R6 and R7 are each ~, .. . .. . .... ,_ . . ~_ .. __ .. ,. _ .. . ... ... . .. . .... _.. _ ...... ... . . . .... ... .. . .
~t7Z4~3 selected from the group consisting of me-thyl, ethyl, hydroxy ethyl, propyl and hydroxy propyl radicals.
Specific examples include: .
dimethyldodeoylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyl~odecylamine oxlde, 3,6,9-~rioxaheptacosanyldi-methylamine oxide, b.is-(2-hydroxyethyl)dodecylamine oxide, ~.
10 an amine oxide prepared from an amine containing two 2- . -hydroxyethyl groups and a long chain group which is derived ~
from the condensation product of coconut alcohol and three moles o~ ethylene oxide, bis-(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecyl-amine oxide, dimethyloleylamine oxide, dimeth~l-(2-hydroxy-dodecyl)amine oxide~
The C12-C14 dimethyl or bis-~2-hydroxye-thyl) homologs of the above compounds are preferred. . Other examples include those compounds wherein the short alkyl chains in the above compounds are each replaced by the methyl, ethyl, hydroxyethyl, propyl and_hydroxy propyl radicals to form homologs of the abo~e c~mpounds. Still other examples include those compounds wherein decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl hydrocarbon groups replace the long alkyl chains in the above compounds to form the correspond-ing homologs of the above compounds.
Cationic Compon~nt The cationic surfactants used in the compositions of the present invention are pre~erably of the di-lony chain quaternary ammonium type, having two cha.ins each of which contains an average of from abou-t 10 to about 22, preferably from about 16 to about 18, carbon atoms. The remaining groups, if any, attached to the quaternary nitrogen atom, are preferably Cl to C4 alkyl or hydroxyalkyl groups.
35 Although it is preferred that the long chains be alkyl groups, these chains may contain heteroatoms or other linkages, such as hydroxy groups, double or triple carbon-... ... .... .... . . . . ...
Z~3 carbon bonds, and ester, amide, or ether linkages, as longas each chain falls within the carbon atom ranges required given above. Pre~erred cationic surfactants are those having the formula R
R4-N+-R2 X~
Rl whçrein.the Rl and R~ groups contain an average of from about 16 to about 22 carbon atoms, preerably as alkyl . -.
groups, and most pre~erably contain an aYerage of from about . .
16 to about 18 carbon atoms, R3 and R4 are Cl to C~ alkyl or hydroxyalkyl groups, and X is any compatible anion, par.ticu-larly one selected from.the group consisting oE halider hydroxide, methylsulfate, or acetate anions.
Mixtures o~ the above surfactants are also.useful in the present invention. Other cationic sur~actants include sulfonium, phosphonium, and mono- or tri-long chain ~uat ernary ammonium materials, as long as the amount of required cationic sur~actant is= ~ sent.
Examples of cationic surfactants which may be used include those described in U.S. Patent No. 4,259,217, Murphy, issued March 31, 1981, and Cockrell's U.S.
Patent 4,222,905 issued September 16, 980.
Preferred cationic surfactants include dital~owalkyl-dimethyl tox diethyl ox dihydroxyethyl) ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecyl-alkyl (C16; also known as distearyl) dimethyl (or diethyl, or dihydroxyethyl) ammonium chloride, dioctadecylalkyl (C18)- dimethylammonium chloride, dieicosylalkyl-(C20) dimethylammonium chloride, or mixtures of those sur~actants.
Particularly preferred cationic suractants are ditallow-alkyldimethylammonium chloride, ditallowalkyldimethyl-ammonium methyl sul~ate, and mixtures of those sur~actants, with ditallowalkyldimethylammonium chloride being especially preferred. ...
J`~ J
' _ ... .. . _. .. __ ,_ _~.. __,~ __~ _ _ __.__ _ _. _ .. __ _ .. _ . ~ .. _ .. _ _ .. _.. _ .. __ _. A .. .. __ ._.. ---- -- ' --_ .. . _ _ _. . _~ ~ __ _ .. _ ., _. ______ ._ _ _ _ _ . . _ . ... _ .. ~ .. _ .. _ . . _ ... _ .. _ __ _ _ __ _ _ _ _. _ . __ . _ _ . .. _ .. __ . _ _ _ ~ . _ .
_.. ~_ ~7;~Q3 Another particularly useful class of cationic surfac tant is that in which the two long chains of the cationic surfactant contain a significant amount of unsaturation, such as where at least about 20~/ preferably at leas* about 30%, of the long chains contain at least one double bond.
By increasing the percentage of chains containing the double bonds, t-he performance benefits of these cationic materials are increased. Compounds of this type have the formula R4 - N~ - R2 - ~
I
Rl wherein Rl and R2 contain an average of from about 16 to a~out 22 ~most preferahly from about 16 to about 18) carbon atoms, and at least about ~0~ of these chains contain at least one double bond; R3 and R4 are Cl to C4 alk~l or hydroxyalkyl groups, and X is any compatible anion, particu-larly one selected from the group consisting of halide, hydroxide, methylsulfat ~or acetate anions. Thus, ox example, a preferred cationic surfactant is di-partially hydrogenated tallow dimethylammonium halide (especially chloride or methyl sulfate), which is also known as di~
softened tallowalkyl dimethylammonium halide. A commer-cially available compound o~ this type is Adogen 470,*sold by ~shland Chemical Company, wherein about 30~ of the tallow chains are oleyl in character. Another method of fo~ning similar cationic materials is to synthesize a di-oleyl quaternary ammonlum compound and hydragenate it to the level of unsaturation desired. Compositions made with these cationics show several significant advantages over those made with more conventional cationics (such as ditallow-alkyldimethylammonium chloride, only about 2~ of the long chains of which contain double bonds); particularly ~hese compositions show improved particulate soil removal, especially at low wash temperatures, improved static control and remain in a stable single phase at temperatures down to about 40F.
* Trademark i .. ~ .. .. . , . ... . . . , ~ .. . . . ...
~1 ~7;~3 -The cationics of this invention are preferably low in unquaterni7ed amine content. ~lso, for odor reasons, it is preferable to use a solvent f~r the amine quaternization reaction which does not have an objectionable odor, e.g., a liquid nonionic detergent material, ethyl alcohol, etc.
Prefexably, the compounds in the formula should be stable, especially under the specific pH conditions.
The compositions of the present invention are prefer~
ably formulated so as to be substantially free of ethoxy-lated cationic surfactants which contain more than anaverags of about 1~, and preferably ~ree of those which contain more than an average of about 7, moles of ethylene oxide per mole of surfactant. ~hese compounds tend to be relatively non-biodegradable. It is to be noted that polyethoxylated cationic surfactants having relatively low le~els of ethoxylation, i-.e., those with less than 10, and particularly less than 7, ethylene oxide groups exhibit better biodegradability ~ aracteristics and may be advan-tageously included in t~ co~positions of the present invention.
The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their co~ventional art-estab--lish~d levels, as long as these ingredients are compatible -^
with the nonionic and cationic components required herein.
For example, the compositions may contain up to about 15~, prefera~ly up to about 5~, and most preferably from about 0.001 to about 2~, of a suds suppressor component. Typica-l suds suppressors useul in the compositions of the present invention include, but are not limitea to, those described below.
Preferred silicone-type suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al. The silicone material can be represented by alkylated poly-siloxane materials such as silica aerogels and xerogels and _ ._., . __ __ .. ..... _ ._ .. , . . .. . _ . , . _ _ _ , , ,, ~
.... . . .. . . . .. . .
~Z~
hydrophobic silicas of various types. The silicone material can be described as a siloxane having the formula:
~ sio~
I Jx ~ R' wherein x is from about ~0 to about 2,000, and R and R' are -~
each alkyl or aryl groups, especially methyl, ethyl r propyl, butyl and phenyl. Polydimethylsiloxanes ~R and R' are methyl, having a molecular weight within the xange of ~rom ab~ut 200 to about 200,000, and higher, are all use~ul as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl t or mi~ed alkyl and aryl hydrocaxbyl groups exhibi~
useful suds contxolling properties. Examples of such ingredients in~lude dieth~ -, dipxopyl-, dibutyl-, methyl-ethyl-, phenylmethyl-pol~siloxanes and the like. Additional useful silicone suds co~roll-ing agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica~
A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsila-nated) silica having a particle size in the range ~rom about lO millimicrons to 20 millimicrons and a specific surface area above about 50 m2~gm intimately admixed with dimethyl silicone fluid having a ~olecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about l9:1 to about 1:2. The silicone suds suppressing agent is ad~antageously releasab?y incorporated in a water-soluble or water-dispersible, sub-stantially non-surface-active, detergent-impermeable carrier.
Particularly useful suds supp~essors are the self-emulsifying silicone suds Cuppxessors~ described in U.S.
Patent 4,136,045, Gault et al, issued Januaxy 23, 19790 ~` q .`' !, ~
!~ ~' I, .',~
... _~ _ ._ _ _ .. _. ___ _ _ __, _, _____ ,_ . ... _ _.__ ____, _ _. __ _, . . . _. _.. __ . _._.. ... . .. _._ _._.. _.. _ _ .
~ 7Z~
An example of such a compound is DB-544* commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
Microcrystalline waxes having a melting point in the range f,rom 35C-115C and a saponiication value of less than 100 represent additional examples o a preferred suds regulating component for use in the subject compositions, and are described in detail in U.S. Patent 4,056,481, Tate~
issued November 1, 1977~ r_ ~ ~
The microcrystalline waxes axe substantially water-insolu-ble, but are watex-dispersible in the presence of organic surfactants. Preferred microcxystalline waxes have a melting paint from about 65C to 100C, a molecular weight in the range fxom 400-1,000; and a penetration value oE a~
Ieast 6, measured at 77F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized microcrys~alline petrolatum waxes; Fischer-Tropsch and oxidi~ed Fischer-Trop~ç~~waxes; ozokerite; ceresin; montan wax; beeswax; candelil~, and carnauba wax.
Alkyl phosphate esters represent an additional pre-ferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monoleyl phosphates, which can contain di-and trioleyl phosphates.
The alkyl phosphate esters frequently contain some trialkyl phosphate Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.~.
monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
Fatty acids are an additional preferred suds suppress-ant herein. Examples include coconut, tallow, and marine fatty acids having chain lengths of from about 10 to about 30 carbon atoms.
Other adjunct components which may be included in the , * Trademark ~.
. . . ..
7~Q3 compositions of the present invention, in their conventional art-established levels for use (i.e., from about 0 to about 40%), include bleaching agents; bleach activa-tors; soil release agents ~particula~ly copolymers of ethylene tere-phthalate and polyethylene oxide terephthalate, such as~lilease T ~old by ICI, United Statesi as disclosed in U.S.
Patent No. 4~132l680r Nicol, issued January 2, 1979;
soil suspending agents; corrosion inhibitors; dyes; fillers; optical bright-eners; germicides; pH adjusting agents; alkalinity source~;hydrotxopes; enzymes; enzyme-stabilizing agents; perfumes;
solvents; carriers; suds modifiers, opacifiers; and the like. However, because o~ the numexous and di~erse per-, formance advantage~ of the present invention, co~ventional components, such as hydrotropes and deter~enc~ builders,will not be necessar~, giviny the compositions of the present invention an advantage over con~entional deter-gent/softener compositions. In fact, the compositions o~
the present invention give outstanding cla~ removal per-formance, even in a bu-EIder~free environment, and across a range of water haraness-conditions. Therefore, for en-vironmental reasons the compositions of the present inven tion contain less than about 5% se~uestexing aetergency builders. Preferred compositions are totally ~ree o phosphate matexials, without decreasing the pe~formance o~
the compositions. Further, in oxder to achieve optimal particulate soil removal performance, the compositions of the present invention contain less than about 5%, and are preferably substantially free of, silicate materials.
Preferred compositions of the present invention are also substantially free of carboxymethylcellulose in orde~ to optimize the clay removal performance!of the system.
Finally, while the compositions of the present invention ca~
contain small amounts of anionic materials, such as anionic surfactants and hydrotropes (e.g., alkali metal toluene sulfonatesJ, it is preferred that particular anionic materials be contained in amounts sufficiently small such * Trademark . . .. ...
7~3 that not more than about 50%, preferably not more than about 15%, and most preerably none o~ the cationic sur~actant, contained in the laundry solution, is complexed by the anionic material. Such a complexing of the anionic material
Preferred nonionic surfactants for use in the present invention include the condensation product: of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of eth~lene oxide;
10 the condensation product of C12 15 alcohol wi~h 7 moles o~
- ethylene oxide; the condensation product of C12 15 alcohol with 9 moles of ethylene oxide; the condensation pxoduct of C14 15 alcohol with 2.25 moles of ethylene oxide; the condensation product o C14 15 alcohol with 7 moles of ethylene oxide; the condensation product of Cg_ll alcohol with 8 moles o~ ethylene oxide, which is stripped so as to remove unethoxylated and lower ethoxylate fractions; the condensation prod~ct of C12 13 alcohol with 6.5 moles of ethylene oxide, and this same alcohol ethoxylate which is stripped so as to remove unethoxylated and lower ethoxylate fractionsO A preferred~lass of such surfactants utilize alcohols which contai~-~bout 20~ 2-methyl branched isomers, and are commercially available, under the trademark"Neodol'~
from Shell Chemical Company. The condensation product of tallow alco~ol with 9 moles of ethylene oxide is also a preferred nonionic surfactant for use herein. Paxticularly preferred nonionic surfactants ~or use in the compositions of the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide, the conden-30 sation product o~ C12_13 alcohol with 6.5 moles of ethylene oxide, the condensation product of Clz_l5 alcohol with 7 moles of et~ylene oxide, the condensation pxoduct o~ C14 15 alcohol with 7 moles of ethylene oxide, and mixtures of those surfactants. In preferred nonionic surfactants the lower, e.g., the unethoxylated and monoethoxylated alcohols, are stripped to provide improved performance.
The compositions of the present invention may contain mixtures of nonionic surfactants falling within the above nonionic surfactant~definition, such as: a mixture Qf the ... , .; .. .,, .. _ . . . .,, .. . .. . ., . . .. . ................................ , . ........ ._ .. . _ . .. _. ~
... _ .. . .. ,.. _ _ . _. , . , . , . .. . .. . . _ . ., . _ _ . ,, . ., .. , .. ._ .. ... _ . . _ .. . .. . . . .. .
. _ - ~ ,t ~ . _ .. . . , , _ _ .. , . , . _ . _, . . . .. . . . . .
~ ~72~L~3 condensation product of C12 13 alcohol with 6.5 moles of - ethylene oxide~(Neodol 23-6.5~)~with the condensation product of C14 15 alcohol with 7 moles of Pthylene oxidel~(Neodol 45-7)",**in a ratio o from ahout 4:1 to 1:4, a mixture of the condensation product of Cl~ 15 alcohol with 7 moles of ethylene oxide with'iNeodol 45-7',*~n a ratio of from about 4:1 to ~bout 1:4 preferably about 1:1; or a mixture of the condensation product of Cg 11 alcohol with 8 moles of ethylene oxide, stripped to remove lower ethoxylate and non-ethoxylated fractions, with Neodol 45-7, in a ratio of higher ethoxylate to lower ethoxylate of from about 1:6 t~ --about 1:1, preferably about 1:3. ~he present invention can also contain nonionic surfactants, some o~ which do not ~all within the above preferred nonionic surfactant deflnit:ion (such as alcohol ethoxylates having an average of greater than about 9 ethylene oxide groups per molecule, secondary alcohol ethoxylates, or alkyl phenol sthoxylates). It is preerred however that a~ least one of the nonionic sur-factants contained in the mixture falls within the above definition of tlle prefe~rred nonionic surfactants. Where the nonionic surfactant mix~ure-contains a nonionic surfactant (or surfactants~ which falls outside o~ the above pre~erred nonionic definition, it is pre~erred that the ratio of the surfactant (or surfactants) within the definition to that which is outside the preferred definition be within the range of from about 1:1 to about 10:1. A specific example of such a surfactant mixture is a mixture of the conden-ion produc,t of C12_13 alcohol with 6.5 moles of ethyle~eoxide (e.g., Neodol 23 6.5) and the condensation product of a secondary C15 alcohol with 9 moles of ethylene oxid~
~e.g.,~Tergitol 15-S-9),' 1n a ratio of lower ethoxylate to higher ethoxylate nonionic of from about 1:1 to about 6:1;
or a mixture of'~eodol 23-6.5"and the condensation product of nonyl phenol with 7 moles of ethylene oxide, having a ratio of"Neodol"to nonyl phenol ethoxylate of a~out 4:1.
Preferred nonionic surfactant mixtures contain alkyl glyceryl ethers in addition to the preferred nonionic * Trademark ** Trademark *** Trademark .. .. _ ~ ... .. . _ .. ... . _ . . . . ...... _ . . . . . . . . .. _ .. . .... .. .
~ 724~P~
suractant. Particularly pre~erred are glyceryl ethers having the formulae R-OCH2-C~-C~2OH and R-O(CH2cH2O]ncH2cHcH2OH
OE~ . O~I
wherein R is an alkyl or alkenyl group of from about 8 to about 18, preferably about 8 to 12, carbon atoms or an al~a~yl group having from about 5 to 14 carbon in the alkyl chain, and n is from 1 to about 6, togeth~r with the non-ionic surfactant component of the present i~vention, in a ratio o~ noni.onic surfactant to glyceryl ether of rom about 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful in the present invention are aisclosed in U.S. Patent 4,0~8,713, ~ones, issued July 4, 1978a Other ~onionic surfactants well known in the detergency.
arts may be used, either alone or in combination with one or more of the preferre~ nionic suractants. Examples of such surfactants are Lis~ed in U.S~ Patent No. 3,717,630, Booth, issued February~-20, 1973, and U.S. Patent No. 3,332,880, Kessler et al, issued July 25, lg67~
Nonlimiting examples of suitable nonionic surfac~ants which may be used in conjunc-tion with the required nonionic surfactants, deined above, axe: polyethyiene oxide condensates o alkyl phenols, such as thel'Igepal~surfactants, marketed by the GAF Corporation, and the"Triton"surfactants, marketed by the Rohm and Haas Coinpany; condensation products o aliphatic alcohols with from a~out 10 to about 25 moles o~ ethylene oxide, where those alcohols are o~ a prlmary, branched or secondary alkyl chain structure; condensation products o ethylene oxide -with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, such as the"Pluronic"***.
surfactants, marketed by Wyandotte Chemical Corpo~ation; and condensation products o ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene `~ * Trademark ** Trademark *** Trademark _ .. _, . . .. , .. . , .. _ , .,, , ._ _ _ . _ , . . .. ., . ., .. _ _ . _ _, ,,,, ;, ' 3 ~ ~29~3 diamine, such as the"Tetronic"surfactants, marketed by Wyandotte Chemical Corporation.
Another pre~erred group of nonionic surfactants useful herein comprises a mixture of "surfactant'l and ethoxylated nonionic "cosurfactant", containing at least one nonionic surfactant falling within ~he definition of the preferred nonionic surfactants useful herein, as described in Canadian Patent No. 1,059,865, Collins, issued August 7, 1979.
Another preferred mixture o~ nonionic surfactants omPriSeS C12~13E6.5 a~d C14_1sEO7 in a ratio of 4 1 to 1:4 This mixture pxovides a desirable suds pattern during the wash and during rinsing as compared to either surfactant by itself.
Preferred compositions o the present invention are substantially free (less than about 2~, preferably less than about 1~, more preferably none) of fatty acid polyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylen~glycol 80~-distearate. Such additives offer no ad~a~tage, and possibly even result in a disadvantage, in terms-~f achieving the particulate soil removal and fabric conditioning benefits provided by the present in~ention.
The Cosurfactant ~a) Zwitterionic detergent surfactant Zwitterionic surfactants include derivatives of alipha~
tic quaternary ammonium, phosphonium, and sulfonium com-pounds in which the aliphatic moieties can be straight o~
branch chain~ wherein one of the aliphatic su~stituents contains from about 8 to 18 carbon atoms and one contains an anionic, p~eferably carboxylate or sulfonate, water-solubil-izing gxoup. Particulaxly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates dis-35 closed in U.5. Patent 3,92~,262, Laughlin et alf issued December 9, 1975; U.S. Patent 3,929,~78, Laughlin et al, issued December 30, 1975-o * Trademark .. , . . . .. , .. . _, _ . .. .. .. ... _ . .. . . . . . _ ........... ... . _, _ _ _, . .. .
1~7Z~3 The inclusion _ .
of these surfactants in the compositions s~lpplement the excellent clay soil removal performan~e with good body soil removal and improved softening performance.
Preerred zwitterionic detergents have th~ fonmula:
~2 R2 Rl- N~CH2R S03~ and Rl-N~-CH2R4Coo wherein Rl is an alkyl radical containing ~xom about 10 to about 18 carbon atoms, R2 and R3 are each selected from the group consisting o~ methyl, ethyl and hydroxy ethyl xadicals, R4 is selected from the group consisting o~ alkylene, poly-alkoxy, and hydroxy alk ~ ne radicals, preferably methylene~
ethylene, polyethoxy, ~y~roxy ethylene and propylene rad-icals and said hydroxyL~groups are attached only to second-ary carbon atoms.
23 Specific examples include:
(a) Betaine examples include N-coconut alkyl betaine;
N-hexadecylbetaine; 6(N-hexadecyl-N,N-dimethylammonio)-hexanoate; N-(2-coconutamido)ethylbetaine; and (N-hexadecyl-N,N-dimethylammonio)-3,6-dioxa-nonanoate.
(b) Sultaine detergents of particular interest are those in which the long alkyl chain (Rl) is a speci~ic C10-C18 alkyl or a mixture of alkyl chains derived from natur-ally occurring substances, whether hydrogenated or not~ and the short alkyl chains are methyl gxoups. Fox instance, where Rl is derived from tallow or coconut oil, R4 is an ethylene radical with a hydrox~l group substituted on the middle carbon atoms of the CH2R4 ~rouping, and R2 and R3 are methyl groups, the sultaine detergent is of particular interest. Other specific éxamples o~ preferred sultaine , . .... ...............
- . ................ .. .
.. .:
_ g- ~L~72~
detergents include 3~(N,N-dimethyl-N-hexadecylammonio)-2(polyethoxy)-ethane-1-sulonate, 3-(N,N-dimethyl-N-hexa-decyla~onio)-propane-l-sulfonate, 2-(N-methyl-N-ethyl-N-decylammo~io)-ethane-l-sulfonate, 4-(N,N-diethyl-N-tetra-decylammonio)butane-l-sulfonate, 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-2-hydroxy butane-l-sulfonate, 2-[N,N-di(2-hydroxyethyl)-N dodecylammonio]-ethane-l-sulfonate, 4-tN-methy~-N-(2-hydroxyethyl)-N-hexadecylammonio~-3-hydr butane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecylammonio) 10 2-hydroxypropane-1-sulfonate. Other specific examples -include compounds wherein different long alkyl chains are - -- -~
used to provide the corresponding decyl, dodecyl, tetra~-decyl, hexadecyI, and octadecyl homologs o~ the above compounds such as 3-~N,N dimethyl-N~tetradecylammonio)-propane-l-sulfona~e, 3-(N,N-dimethyl-N-octadecylammonio)-ethane~l sulfonate, etc. Still other specific examples include compounds where the short chains substituted on the nitrogen atom in the above compounds are replaced by the corresponding methyl, eth~l and hydroxy ethyl groups to 2~ providè the corresponding homologs of the above compounds.
~c~ Semipolar noni ~ic suxfactants Generically these surfactants have the formula R (R ~n~~~~
wherein X is N, S, or P with n being 2 when X is ~ or P and 1 when X is S, Rl is a long chain hyarophobic group and each R2 is a short chain h~drophobic or hydrophilic group.
Pre~erred are surfactants having the formula:
R6 . '.
R5-N~ O
R
wherein R is an organic radical containing from about l0 to about 24 carbon atoms, containing from 0 to about 3 ether linkages, containing from 0 to 1 hydroxy ~roup, and having one alkyl moiety which contains from about 10 to about 18 carbon atoms and no ether linkages; R6 and R7 are each ~, .. . .. . .... ,_ . . ~_ .. __ .. ,. _ .. . ... ... . .. . .... _.. _ ...... ... . . . .... ... .. . .
~t7Z4~3 selected from the group consisting of me-thyl, ethyl, hydroxy ethyl, propyl and hydroxy propyl radicals.
Specific examples include: .
dimethyldodeoylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyl~odecylamine oxlde, 3,6,9-~rioxaheptacosanyldi-methylamine oxide, b.is-(2-hydroxyethyl)dodecylamine oxide, ~.
10 an amine oxide prepared from an amine containing two 2- . -hydroxyethyl groups and a long chain group which is derived ~
from the condensation product of coconut alcohol and three moles o~ ethylene oxide, bis-(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecyl-amine oxide, dimethyloleylamine oxide, dimeth~l-(2-hydroxy-dodecyl)amine oxide~
The C12-C14 dimethyl or bis-~2-hydroxye-thyl) homologs of the above compounds are preferred. . Other examples include those compounds wherein the short alkyl chains in the above compounds are each replaced by the methyl, ethyl, hydroxyethyl, propyl and_hydroxy propyl radicals to form homologs of the abo~e c~mpounds. Still other examples include those compounds wherein decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl hydrocarbon groups replace the long alkyl chains in the above compounds to form the correspond-ing homologs of the above compounds.
Cationic Compon~nt The cationic surfactants used in the compositions of the present invention are pre~erably of the di-lony chain quaternary ammonium type, having two cha.ins each of which contains an average of from abou-t 10 to about 22, preferably from about 16 to about 18, carbon atoms. The remaining groups, if any, attached to the quaternary nitrogen atom, are preferably Cl to C4 alkyl or hydroxyalkyl groups.
35 Although it is preferred that the long chains be alkyl groups, these chains may contain heteroatoms or other linkages, such as hydroxy groups, double or triple carbon-... ... .... .... . . . . ...
Z~3 carbon bonds, and ester, amide, or ether linkages, as longas each chain falls within the carbon atom ranges required given above. Pre~erred cationic surfactants are those having the formula R
R4-N+-R2 X~
Rl whçrein.the Rl and R~ groups contain an average of from about 16 to about 22 carbon atoms, preerably as alkyl . -.
groups, and most pre~erably contain an aYerage of from about . .
16 to about 18 carbon atoms, R3 and R4 are Cl to C~ alkyl or hydroxyalkyl groups, and X is any compatible anion, par.ticu-larly one selected from.the group consisting oE halider hydroxide, methylsulfate, or acetate anions.
Mixtures o~ the above surfactants are also.useful in the present invention. Other cationic sur~actants include sulfonium, phosphonium, and mono- or tri-long chain ~uat ernary ammonium materials, as long as the amount of required cationic sur~actant is= ~ sent.
Examples of cationic surfactants which may be used include those described in U.S. Patent No. 4,259,217, Murphy, issued March 31, 1981, and Cockrell's U.S.
Patent 4,222,905 issued September 16, 980.
Preferred cationic surfactants include dital~owalkyl-dimethyl tox diethyl ox dihydroxyethyl) ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecyl-alkyl (C16; also known as distearyl) dimethyl (or diethyl, or dihydroxyethyl) ammonium chloride, dioctadecylalkyl (C18)- dimethylammonium chloride, dieicosylalkyl-(C20) dimethylammonium chloride, or mixtures of those sur~actants.
Particularly preferred cationic suractants are ditallow-alkyldimethylammonium chloride, ditallowalkyldimethyl-ammonium methyl sul~ate, and mixtures of those sur~actants, with ditallowalkyldimethylammonium chloride being especially preferred. ...
J`~ J
' _ ... .. . _. .. __ ,_ _~.. __,~ __~ _ _ __.__ _ _. _ .. __ _ .. _ . ~ .. _ .. _ _ .. _.. _ .. __ _. A .. .. __ ._.. ---- -- ' --_ .. . _ _ _. . _~ ~ __ _ .. _ ., _. ______ ._ _ _ _ _ . . _ . ... _ .. ~ .. _ .. _ . . _ ... _ .. _ __ _ _ __ _ _ _ _. _ . __ . _ _ . .. _ .. __ . _ _ _ ~ . _ .
_.. ~_ ~7;~Q3 Another particularly useful class of cationic surfac tant is that in which the two long chains of the cationic surfactant contain a significant amount of unsaturation, such as where at least about 20~/ preferably at leas* about 30%, of the long chains contain at least one double bond.
By increasing the percentage of chains containing the double bonds, t-he performance benefits of these cationic materials are increased. Compounds of this type have the formula R4 - N~ - R2 - ~
I
Rl wherein Rl and R2 contain an average of from about 16 to a~out 22 ~most preferahly from about 16 to about 18) carbon atoms, and at least about ~0~ of these chains contain at least one double bond; R3 and R4 are Cl to C4 alk~l or hydroxyalkyl groups, and X is any compatible anion, particu-larly one selected from the group consisting of halide, hydroxide, methylsulfat ~or acetate anions. Thus, ox example, a preferred cationic surfactant is di-partially hydrogenated tallow dimethylammonium halide (especially chloride or methyl sulfate), which is also known as di~
softened tallowalkyl dimethylammonium halide. A commer-cially available compound o~ this type is Adogen 470,*sold by ~shland Chemical Company, wherein about 30~ of the tallow chains are oleyl in character. Another method of fo~ning similar cationic materials is to synthesize a di-oleyl quaternary ammonlum compound and hydragenate it to the level of unsaturation desired. Compositions made with these cationics show several significant advantages over those made with more conventional cationics (such as ditallow-alkyldimethylammonium chloride, only about 2~ of the long chains of which contain double bonds); particularly ~hese compositions show improved particulate soil removal, especially at low wash temperatures, improved static control and remain in a stable single phase at temperatures down to about 40F.
* Trademark i .. ~ .. .. . , . ... . . . , ~ .. . . . ...
~1 ~7;~3 -The cationics of this invention are preferably low in unquaterni7ed amine content. ~lso, for odor reasons, it is preferable to use a solvent f~r the amine quaternization reaction which does not have an objectionable odor, e.g., a liquid nonionic detergent material, ethyl alcohol, etc.
Prefexably, the compounds in the formula should be stable, especially under the specific pH conditions.
The compositions of the present invention are prefer~
ably formulated so as to be substantially free of ethoxy-lated cationic surfactants which contain more than anaverags of about 1~, and preferably ~ree of those which contain more than an average of about 7, moles of ethylene oxide per mole of surfactant. ~hese compounds tend to be relatively non-biodegradable. It is to be noted that polyethoxylated cationic surfactants having relatively low le~els of ethoxylation, i-.e., those with less than 10, and particularly less than 7, ethylene oxide groups exhibit better biodegradability ~ aracteristics and may be advan-tageously included in t~ co~positions of the present invention.
The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their co~ventional art-estab--lish~d levels, as long as these ingredients are compatible -^
with the nonionic and cationic components required herein.
For example, the compositions may contain up to about 15~, prefera~ly up to about 5~, and most preferably from about 0.001 to about 2~, of a suds suppressor component. Typica-l suds suppressors useul in the compositions of the present invention include, but are not limitea to, those described below.
Preferred silicone-type suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al. The silicone material can be represented by alkylated poly-siloxane materials such as silica aerogels and xerogels and _ ._., . __ __ .. ..... _ ._ .. , . . .. . _ . , . _ _ _ , , ,, ~
.... . . .. . . . .. . .
~Z~
hydrophobic silicas of various types. The silicone material can be described as a siloxane having the formula:
~ sio~
I Jx ~ R' wherein x is from about ~0 to about 2,000, and R and R' are -~
each alkyl or aryl groups, especially methyl, ethyl r propyl, butyl and phenyl. Polydimethylsiloxanes ~R and R' are methyl, having a molecular weight within the xange of ~rom ab~ut 200 to about 200,000, and higher, are all use~ul as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl t or mi~ed alkyl and aryl hydrocaxbyl groups exhibi~
useful suds contxolling properties. Examples of such ingredients in~lude dieth~ -, dipxopyl-, dibutyl-, methyl-ethyl-, phenylmethyl-pol~siloxanes and the like. Additional useful silicone suds co~roll-ing agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica~
A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsila-nated) silica having a particle size in the range ~rom about lO millimicrons to 20 millimicrons and a specific surface area above about 50 m2~gm intimately admixed with dimethyl silicone fluid having a ~olecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about l9:1 to about 1:2. The silicone suds suppressing agent is ad~antageously releasab?y incorporated in a water-soluble or water-dispersible, sub-stantially non-surface-active, detergent-impermeable carrier.
Particularly useful suds supp~essors are the self-emulsifying silicone suds Cuppxessors~ described in U.S.
Patent 4,136,045, Gault et al, issued Januaxy 23, 19790 ~` q .`' !, ~
!~ ~' I, .',~
... _~ _ ._ _ _ .. _. ___ _ _ __, _, _____ ,_ . ... _ _.__ ____, _ _. __ _, . . . _. _.. __ . _._.. ... . .. _._ _._.. _.. _ _ .
~ 7Z~
An example of such a compound is DB-544* commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
Microcrystalline waxes having a melting point in the range f,rom 35C-115C and a saponiication value of less than 100 represent additional examples o a preferred suds regulating component for use in the subject compositions, and are described in detail in U.S. Patent 4,056,481, Tate~
issued November 1, 1977~ r_ ~ ~
The microcrystalline waxes axe substantially water-insolu-ble, but are watex-dispersible in the presence of organic surfactants. Preferred microcxystalline waxes have a melting paint from about 65C to 100C, a molecular weight in the range fxom 400-1,000; and a penetration value oE a~
Ieast 6, measured at 77F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized microcrys~alline petrolatum waxes; Fischer-Tropsch and oxidi~ed Fischer-Trop~ç~~waxes; ozokerite; ceresin; montan wax; beeswax; candelil~, and carnauba wax.
Alkyl phosphate esters represent an additional pre-ferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monoleyl phosphates, which can contain di-and trioleyl phosphates.
The alkyl phosphate esters frequently contain some trialkyl phosphate Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.~.
monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
Fatty acids are an additional preferred suds suppress-ant herein. Examples include coconut, tallow, and marine fatty acids having chain lengths of from about 10 to about 30 carbon atoms.
Other adjunct components which may be included in the , * Trademark ~.
. . . ..
7~Q3 compositions of the present invention, in their conventional art-established levels for use (i.e., from about 0 to about 40%), include bleaching agents; bleach activa-tors; soil release agents ~particula~ly copolymers of ethylene tere-phthalate and polyethylene oxide terephthalate, such as~lilease T ~old by ICI, United Statesi as disclosed in U.S.
Patent No. 4~132l680r Nicol, issued January 2, 1979;
soil suspending agents; corrosion inhibitors; dyes; fillers; optical bright-eners; germicides; pH adjusting agents; alkalinity source~;hydrotxopes; enzymes; enzyme-stabilizing agents; perfumes;
solvents; carriers; suds modifiers, opacifiers; and the like. However, because o~ the numexous and di~erse per-, formance advantage~ of the present invention, co~ventional components, such as hydrotropes and deter~enc~ builders,will not be necessar~, giviny the compositions of the present invention an advantage over con~entional deter-gent/softener compositions. In fact, the compositions o~
the present invention give outstanding cla~ removal per-formance, even in a bu-EIder~free environment, and across a range of water haraness-conditions. Therefore, for en-vironmental reasons the compositions of the present inven tion contain less than about 5% se~uestexing aetergency builders. Preferred compositions are totally ~ree o phosphate matexials, without decreasing the pe~formance o~
the compositions. Further, in oxder to achieve optimal particulate soil removal performance, the compositions of the present invention contain less than about 5%, and are preferably substantially free of, silicate materials.
Preferred compositions of the present invention are also substantially free of carboxymethylcellulose in orde~ to optimize the clay removal performance!of the system.
Finally, while the compositions of the present invention ca~
contain small amounts of anionic materials, such as anionic surfactants and hydrotropes (e.g., alkali metal toluene sulfonatesJ, it is preferred that particular anionic materials be contained in amounts sufficiently small such * Trademark . . .. ...
7~3 that not more than about 50%, preferably not more than about 15%, and most preerably none o~ the cationic sur~actant, contained in the laundry solution, is complexed by the anionic material. Such a complexing of the anionic material
5- with the cationic surfactant, decreases the overall cleaning and fabr,ic conditioning performance of the composition.
Compositions of the present invention may contain from about 0.005% to about 3%, prefexably ~rom about 0.01% to about 1%, of an optical briyhtener. Nonionic brighteners 10 .are preferred because of their compatibility with the . .
nonionic and cationlc surfactants utilized.herein. Suitable and preferred bxlghteners are disclosed.in Coward 2t al.'s U.S. Patent 3,537,g93 issued November 3, 1970, i~
Nonionic brighteners include tho~e of the coumarin and benzoxazo~.classes;-a particularly preferred brightener being 4-me~ 7-diethyl amino coumarin, commer-cially available under the trad~E~ks"Tinopal SWW"from Ciba-Geigy Corp., Ardsley, N.Y.,"Hiltamine Arctic ~hite SOL', a~ailable from Hilton-Davis Chemical Co., Cincinnati, Ohio, and'.'Calcofluor White SD".available-from.American Cyana.mid, 2S Wayne, N.J. Other brighteners useful herein include bis-(benzoxazol-2-yl)triophenes, 1,2-bis(benzoxazol~2-yl)ethy-lenes, 1,4-bis~benzoxazol-2-yl)naphthalenes, 4,4'-bis (benzoxazol-2-yl)-s~ilbenes, 2-~styxyl)benzoxazoles, 2 (styryljnaphthoxazole, or 2-(4-phen~lstilben-4'-yl)-5-tertbutyl benzoxazole.
Preferred compositions of the pressnt invention can contain from about 0.05% to about 1.5%, pxeferably from about 0.05% to about 1~, and most preferably rom about 0~1%
to about 0.8%, of polyacids capable of orming water-soluble calcium complexes, such as organo-phosphonic acids, particu-larly alkylene-polyamino-polyalkylene phosphonic acids.
These materials include ethylenediamine tetramethylene ~ .
.~.,' . , , .. . . . _ _ __ _ .. . . , ,,, .,.. ,. . ,, _. _ . . . . . _ .. __.. _ , . . ... . .. , __,~,_ ..... . ~ . .. .. ._ ~:17~46P3 - 18 - .
phosphonic acid, hexamethylene diaminetetramethylene pho~-phonic acid, diethylene triaminepentamethylene phosphonic acid, and aminotrimethylene phosphonic acid.
Other preferred embodiments of the present invention include an alkaline proteolytic enzyme having an isoelectric point of,greater than about 8. The enzyme is present in an : amount from 0.001% to about 2%, preferably from about 0.005%
to about 0~8%, especially from about 0.02~ to about 0.2%, and axe particularly useful.when usea in conjunction with - . 10 the polyacids, described above~ The most preferred proteo-: lytic enz~me preparations for use in this invention are - derived from bacillus subtilis, such asl'~lcalase', manu-factured by No~o Industri A/S, and"Maxatase', manufactuxed by . GistBrocades N.~. These most preferred enzyme specie~ have an isoelectric point in the range from about 8.5 to a:bout 9~2.
.: These polyacid and.enzyme components, as well as the j beneits they provide, are discussed in detail in U.S~
Patent 4,100,262, ~rnau~ alï issued August 29, 1978, and 20 U.S~ Patent 4,111,855, -~rrat et al, issued September 5, 1978, - :: .
Compositions which include these components are particularly il; ., useful for the hand-laundering of fine fabrics, such as - wool.
. 25 In a particularl~ preferred embodiment, the composi-: tions of the present invention contain up to about 20% of a lower alkyl (Cl to C4) alcohol, particularly ethanol.
The compositions of the present invention are used in the laundering process by for~ing an aq~eous.solution con--taining from about 0.01 (lOQ parts per million) to about 0.3% (3,000 parts per million), preferably from about 0.03~
to about 0.2%, and most pre~erably from abou~ 0.05. to about : 0.15%, of the organic detergent surfactant mixture, and agitating the soiled.fabrics in that solution.. The fabrics are then rinsed and dried. When used in this manner, the compositions of the present invention yield exceptionally good detergency and also provide fabric softening, static * Trademark ** Trademark.
'; , ~,'~
. ..
~7~3 .
- control, color fidelity, and dye transfer inhibition to the laundered fabrics, without requiring the use of any of the other conventionally-used fabric softening and/or static control laundry additives.
All percentages, parts, and ratios used herein are by weight u,nless otherwise speciied.
The following nonlimiting examples illustxate the , compositions and the method of the present invention.
EXAMPLES
10 , I II III IV V VI ~II VIII
~ :;
C12 5 alkyl polyethoxylate (6.5) 4.5 6.0 9.012.0 13.5 9.020.0 4.5 C 2 alkyl di-~ethylamine oxide 13.5 12.0 9.06.0 4.5 9.020.0 4.5 Citric acid ~ 5.0 - 5.0 Ditallowalkyl-;~ dimethyl ammon- -ium chloride 4.0 4.0 4.04.0 4.0 4.0 4.0 4.0 Ethyl alcohol 6.0 ~ - 6.06.0 6.0 - 6.0 6.0 -; Monoethanol- -~ -amine 3.6-3~6 3.63.6 3.6 3.6 3.6 3.6 .
Water and minors Balance ;~ The compositions of Examples I, III, IV, and V were tested in a conventional top-loading automatic washing ; machine using 5-1/2 pounds of soiled laundry and test ; swatches in 17-1/2 gallons of water at 95F. One set of swatches was washed in water with 2 grains hardness and another set was washed in water of 6 grains hardness and the results averaged.
The clay removal grades given are the average of the two hardnesses and three fabric swatch types (cotton, ~ 35 polyester and polyester/cotton~ in Hunter Whiteness units ; versus a control which con-tained 24% of a mixture of non-io~ic surfactantS (C12~13 E6,5 and C14-15 E7) the cationic surfactant.
~ The facial soil removal grades are the average of the ':~
.. . . . . .
~ . _ .
il~ 3 .
different hardness treatments in which the swatches are split and one half is washed in the treatment while the other half is washed in the control product. Skilled graders compare the two ~alves using a 0-4 scale in which 0 represents no di~ference and 4 represents a very large difference.
Sof-tness is ranked against the control by skilled graders using the same 0-4 scale.
The results are as follows:
Nonionic to Clay Facial Soil Fabric -~-Fxample Ratio ~emoval Removal Softness V 3:1 -G.60 -0.96 ~0.73 III 1:1 -0.30 ~1.23 ~1~62 II 1:2 -6.25 ~0.44 ~2~01 I 1:3 -9.25 ~0.72 ~2.37 Reads: (-), test pxoduct was poorer than control ~+), test product was better than control , . . .
As can be seen fr ~ the above, increasing the semipolar nonionic surfactant (or_~zwitterionic surfactant) improves the facial swatch cleaning and so~tening despite the use of less cationic surfactant. However, surprisîngly, the lower levels give the same superior clay removal and the highex levels (~1:1) do not give an unacceptable reduc-tion in clay removal.
When, in the above example, 3(lauryldimethylammonio)-2-hydroxypropane-1-sulfonate is substituted for the amine : oxide Ind/or diethanolamine or txiethanolamine is substi--tuted for the monoethanolamine, substantially equivalent results are obtained.
Similar cleaning results are obtained when the cationic suractant in Compositions I-VXII is replaced, in whole or ; in part, by ditallowalkyldimethylammonium methyl sulfater ditallowalkyldime-thylammonium iodide, dihexadecylalkyl-dimethylammonil~m chloride, dihexadecyla~kyldihydroxylethyl-ammonium methyl sulfate, dioctadecylalkyldimethylammonium chloride, dieicosylalkyl methyl ethyl ammonium chloride, . .. . ..... . . . . ...... .. ....
Z~3 dieicosylalkyl dimethylammonium bromide, or mixtures of these surfactants.
Substantially similar results are also obtained where the nonionic surfactant in Compositions I-VIIX is replaced, in whole or in part, by the condensation product of C14 15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14 15 alcohol with 7 moles of ethylene oxide;
the condensation product of C12 15 alcohol with 9 moles of ethylene oxide; the condensation product of C12 13 alcohol -with 6O5 moles of eth~lene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated ractions; the condensation pxoduct of coconu-t alcohol with 5 moles o~
ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C12 15 alcohol with 7 moles of ethylene oxide; the conden-sation product of tallow alcohol with 9 moles of ethylene oxide; a 1:1 by weight mixture o the condensation product of C12 15 alcohol with 7 moles of ethylene oxide and the ; condensation product of ~l4 15 alcohol with 7 moles of ethylene oxide; and othe=r mixtures of those surfactants.
Similar performanc~ is also obtained where there is about 1% of a suppressor component in the above compbsition selected from the group consisting of dimethyl-, diethyl-, dipropyl-, dibutyl-, methyle-thyl-, phenylmethyl polysil-oxane, and mixtures thereof; a petrolatum or oxidized petrolatum wax; a Fischer-Txopsch or oxidized Fischer-Tropsch wax; ozokerite; ceresin; montan wax; beeswax;
candelilla; or carnauba wax.
EXAMPLE IX
The product oE Example III was formulated at product pH's of 7.5, 8.5, 9.5, 10.5, and 11~5 using acetic acid and NaOH to adjust the pH. These products were tested as hereinbefore described. For facial swatch soil, the results were as follows, with the product having a pH of 7.5 arbitrarily assigned the role of the control.
Facial Soil Removal - 7.5- 0 -.. ... ___. _~_._ .. _ .. _ ... . _ .. . . . . ......... .,.. _ .. . . .... .... . _ _ _ _ . .. .... .. . . ....
2~!~P3 , 8.5 ~0.30 9.5 ~0.90 :~ 10.5 ~1,88 11~5 ~1.83 Softening results and clay c:Leaning were essentially unaffected and stains were affected in various ways with the overall result being an improvement with pH on stains considered more important.
. .
.~ .
.;, .
.. . . .
. .
:: i ~, .' ..
~ .
. .' .
~ .
'' .,"~
' .. ...... .. ~ . . ... ~ . . . . . . .. . ................. . .. ..
Compositions of the present invention may contain from about 0.005% to about 3%, prefexably ~rom about 0.01% to about 1%, of an optical briyhtener. Nonionic brighteners 10 .are preferred because of their compatibility with the . .
nonionic and cationlc surfactants utilized.herein. Suitable and preferred bxlghteners are disclosed.in Coward 2t al.'s U.S. Patent 3,537,g93 issued November 3, 1970, i~
Nonionic brighteners include tho~e of the coumarin and benzoxazo~.classes;-a particularly preferred brightener being 4-me~ 7-diethyl amino coumarin, commer-cially available under the trad~E~ks"Tinopal SWW"from Ciba-Geigy Corp., Ardsley, N.Y.,"Hiltamine Arctic ~hite SOL', a~ailable from Hilton-Davis Chemical Co., Cincinnati, Ohio, and'.'Calcofluor White SD".available-from.American Cyana.mid, 2S Wayne, N.J. Other brighteners useful herein include bis-(benzoxazol-2-yl)triophenes, 1,2-bis(benzoxazol~2-yl)ethy-lenes, 1,4-bis~benzoxazol-2-yl)naphthalenes, 4,4'-bis (benzoxazol-2-yl)-s~ilbenes, 2-~styxyl)benzoxazoles, 2 (styryljnaphthoxazole, or 2-(4-phen~lstilben-4'-yl)-5-tertbutyl benzoxazole.
Preferred compositions of the pressnt invention can contain from about 0.05% to about 1.5%, pxeferably from about 0.05% to about 1~, and most preferably rom about 0~1%
to about 0.8%, of polyacids capable of orming water-soluble calcium complexes, such as organo-phosphonic acids, particu-larly alkylene-polyamino-polyalkylene phosphonic acids.
These materials include ethylenediamine tetramethylene ~ .
.~.,' . , , .. . . . _ _ __ _ .. . . , ,,, .,.. ,. . ,, _. _ . . . . . _ .. __.. _ , . . ... . .. , __,~,_ ..... . ~ . .. .. ._ ~:17~46P3 - 18 - .
phosphonic acid, hexamethylene diaminetetramethylene pho~-phonic acid, diethylene triaminepentamethylene phosphonic acid, and aminotrimethylene phosphonic acid.
Other preferred embodiments of the present invention include an alkaline proteolytic enzyme having an isoelectric point of,greater than about 8. The enzyme is present in an : amount from 0.001% to about 2%, preferably from about 0.005%
to about 0~8%, especially from about 0.02~ to about 0.2%, and axe particularly useful.when usea in conjunction with - . 10 the polyacids, described above~ The most preferred proteo-: lytic enz~me preparations for use in this invention are - derived from bacillus subtilis, such asl'~lcalase', manu-factured by No~o Industri A/S, and"Maxatase', manufactuxed by . GistBrocades N.~. These most preferred enzyme specie~ have an isoelectric point in the range from about 8.5 to a:bout 9~2.
.: These polyacid and.enzyme components, as well as the j beneits they provide, are discussed in detail in U.S~
Patent 4,100,262, ~rnau~ alï issued August 29, 1978, and 20 U.S~ Patent 4,111,855, -~rrat et al, issued September 5, 1978, - :: .
Compositions which include these components are particularly il; ., useful for the hand-laundering of fine fabrics, such as - wool.
. 25 In a particularl~ preferred embodiment, the composi-: tions of the present invention contain up to about 20% of a lower alkyl (Cl to C4) alcohol, particularly ethanol.
The compositions of the present invention are used in the laundering process by for~ing an aq~eous.solution con--taining from about 0.01 (lOQ parts per million) to about 0.3% (3,000 parts per million), preferably from about 0.03~
to about 0.2%, and most pre~erably from abou~ 0.05. to about : 0.15%, of the organic detergent surfactant mixture, and agitating the soiled.fabrics in that solution.. The fabrics are then rinsed and dried. When used in this manner, the compositions of the present invention yield exceptionally good detergency and also provide fabric softening, static * Trademark ** Trademark.
'; , ~,'~
. ..
~7~3 .
- control, color fidelity, and dye transfer inhibition to the laundered fabrics, without requiring the use of any of the other conventionally-used fabric softening and/or static control laundry additives.
All percentages, parts, and ratios used herein are by weight u,nless otherwise speciied.
The following nonlimiting examples illustxate the , compositions and the method of the present invention.
EXAMPLES
10 , I II III IV V VI ~II VIII
~ :;
C12 5 alkyl polyethoxylate (6.5) 4.5 6.0 9.012.0 13.5 9.020.0 4.5 C 2 alkyl di-~ethylamine oxide 13.5 12.0 9.06.0 4.5 9.020.0 4.5 Citric acid ~ 5.0 - 5.0 Ditallowalkyl-;~ dimethyl ammon- -ium chloride 4.0 4.0 4.04.0 4.0 4.0 4.0 4.0 Ethyl alcohol 6.0 ~ - 6.06.0 6.0 - 6.0 6.0 -; Monoethanol- -~ -amine 3.6-3~6 3.63.6 3.6 3.6 3.6 3.6 .
Water and minors Balance ;~ The compositions of Examples I, III, IV, and V were tested in a conventional top-loading automatic washing ; machine using 5-1/2 pounds of soiled laundry and test ; swatches in 17-1/2 gallons of water at 95F. One set of swatches was washed in water with 2 grains hardness and another set was washed in water of 6 grains hardness and the results averaged.
The clay removal grades given are the average of the two hardnesses and three fabric swatch types (cotton, ~ 35 polyester and polyester/cotton~ in Hunter Whiteness units ; versus a control which con-tained 24% of a mixture of non-io~ic surfactantS (C12~13 E6,5 and C14-15 E7) the cationic surfactant.
~ The facial soil removal grades are the average of the ':~
.. . . . . .
~ . _ .
il~ 3 .
different hardness treatments in which the swatches are split and one half is washed in the treatment while the other half is washed in the control product. Skilled graders compare the two ~alves using a 0-4 scale in which 0 represents no di~ference and 4 represents a very large difference.
Sof-tness is ranked against the control by skilled graders using the same 0-4 scale.
The results are as follows:
Nonionic to Clay Facial Soil Fabric -~-Fxample Ratio ~emoval Removal Softness V 3:1 -G.60 -0.96 ~0.73 III 1:1 -0.30 ~1.23 ~1~62 II 1:2 -6.25 ~0.44 ~2~01 I 1:3 -9.25 ~0.72 ~2.37 Reads: (-), test pxoduct was poorer than control ~+), test product was better than control , . . .
As can be seen fr ~ the above, increasing the semipolar nonionic surfactant (or_~zwitterionic surfactant) improves the facial swatch cleaning and so~tening despite the use of less cationic surfactant. However, surprisîngly, the lower levels give the same superior clay removal and the highex levels (~1:1) do not give an unacceptable reduc-tion in clay removal.
When, in the above example, 3(lauryldimethylammonio)-2-hydroxypropane-1-sulfonate is substituted for the amine : oxide Ind/or diethanolamine or txiethanolamine is substi--tuted for the monoethanolamine, substantially equivalent results are obtained.
Similar cleaning results are obtained when the cationic suractant in Compositions I-VXII is replaced, in whole or ; in part, by ditallowalkyldimethylammonium methyl sulfater ditallowalkyldime-thylammonium iodide, dihexadecylalkyl-dimethylammonil~m chloride, dihexadecyla~kyldihydroxylethyl-ammonium methyl sulfate, dioctadecylalkyldimethylammonium chloride, dieicosylalkyl methyl ethyl ammonium chloride, . .. . ..... . . . . ...... .. ....
Z~3 dieicosylalkyl dimethylammonium bromide, or mixtures of these surfactants.
Substantially similar results are also obtained where the nonionic surfactant in Compositions I-VIIX is replaced, in whole or in part, by the condensation product of C14 15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14 15 alcohol with 7 moles of ethylene oxide;
the condensation product of C12 15 alcohol with 9 moles of ethylene oxide; the condensation product of C12 13 alcohol -with 6O5 moles of eth~lene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated ractions; the condensation pxoduct of coconu-t alcohol with 5 moles o~
ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C12 15 alcohol with 7 moles of ethylene oxide; the conden-sation product of tallow alcohol with 9 moles of ethylene oxide; a 1:1 by weight mixture o the condensation product of C12 15 alcohol with 7 moles of ethylene oxide and the ; condensation product of ~l4 15 alcohol with 7 moles of ethylene oxide; and othe=r mixtures of those surfactants.
Similar performanc~ is also obtained where there is about 1% of a suppressor component in the above compbsition selected from the group consisting of dimethyl-, diethyl-, dipropyl-, dibutyl-, methyle-thyl-, phenylmethyl polysil-oxane, and mixtures thereof; a petrolatum or oxidized petrolatum wax; a Fischer-Txopsch or oxidized Fischer-Tropsch wax; ozokerite; ceresin; montan wax; beeswax;
candelilla; or carnauba wax.
EXAMPLE IX
The product oE Example III was formulated at product pH's of 7.5, 8.5, 9.5, 10.5, and 11~5 using acetic acid and NaOH to adjust the pH. These products were tested as hereinbefore described. For facial swatch soil, the results were as follows, with the product having a pH of 7.5 arbitrarily assigned the role of the control.
Facial Soil Removal - 7.5- 0 -.. ... ___. _~_._ .. _ .. _ ... . _ .. . . . . ......... .,.. _ .. . . .... .... . _ _ _ _ . .. .... .. . . ....
2~!~P3 , 8.5 ~0.30 9.5 ~0.90 :~ 10.5 ~1,88 11~5 ~1.83 Softening results and clay c:Leaning were essentially unaffected and stains were affected in various ways with the overall result being an improvement with pH on stains considered more important.
. .
.~ .
.;, .
.. . . .
. .
:: i ~, .' ..
~ .
. .' .
~ .
'' .,"~
' .. ...... .. ~ . . ... ~ . . . . . . .. . ................. . .. ..
Claims (11)
1. A heavy-duty liquid detergent composition comprising:
(1) from about 5% to about 20% of ethoxylated nonionic detergent surfactant;
(2) from about 5% to about 20% of a cosurfactant selected from the group of semipolar nonionic detergent surfactant, zwitterionic detergent surfactant t and mixtures thereof;
(3) from about 2% to about 20% of a cationic sur-factant capable of imparting softness and/or antistatic benefits to fabrics;
(4) from about 2% to about 10% of a pH buffering agent to provide a pH in use of from about 9.5 to about 11.5 and the total of (1), (2) and (3) being in excess of about 20%, the ratio of (1) to (2) being from about 1:1 to about 1:3, and the composition containing less than about 5%
calcium ion sequestering or precipitating detergency .
builder.
(1) from about 5% to about 20% of ethoxylated nonionic detergent surfactant;
(2) from about 5% to about 20% of a cosurfactant selected from the group of semipolar nonionic detergent surfactant, zwitterionic detergent surfactant t and mixtures thereof;
(3) from about 2% to about 20% of a cationic sur-factant capable of imparting softness and/or antistatic benefits to fabrics;
(4) from about 2% to about 10% of a pH buffering agent to provide a pH in use of from about 9.5 to about 11.5 and the total of (1), (2) and (3) being in excess of about 20%, the ratio of (1) to (2) being from about 1:1 to about 1:3, and the composition containing less than about 5%
calcium ion sequestering or precipitating detergency .
builder.
2. A composition according to Claim 1 wherein the cationic surfactant has the formula wherein the R1 and R2 groups contain an average of from about 16 to about 22 carbon atoms, R3 and R4 are C1 to C4 alkyl or hydroxyalkyl groups, and X is an anion selected from the group consisting of halide, hydroxide, methyl sulfate, or acetate. .
3. A composition according to Claim 2 wherein R1 and R2 are alkyl groups.
4. A composition according to Claim 3 wherein the nonionic surfactant has the general formula R(OCH2H4)nOH, wherein R is a primary alkyl chain containing - 24 - .
an average of from about 10 to about 16 carbon atoms and n is an average of from about 2 to about 9.
an average of from about 10 to about 16 carbon atoms and n is an average of from about 2 to about 9.
5. A composition according to Claim 4 wherein the ratio of (1) to (2) is from about 1:1 to about 1:2.
6. A composition according to Claim 5 wherein the nonionic surfactant is selected from the group consisting of the condensation product of C14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C12-15 alcohol with 7 moles of ethylene oxide; the con-densation product of C12-15 alcohol with 9 moles of ethylene oxide; the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, and the same product which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the condensation product of C9-11 alcohol with 8 moles of ethylene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the con-densation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; and mixtures thereof.
7. The composition of Claim 1 wherein (2) is selected from:
(a) zwitterionic detergents having the formula:
and wherein R1 is an alkyl radical containing from about 10 to about 18 carbon atoms, R2 and R3 are each selected from the group consisting of methyl, ethyl and hydroxy ethyl radicals, R4 is selected from the group consisting of alkylene, poly-alkoxy, and hydroxy alkylene radicals, and said hydroxyl groups are attached only to secondary carbon atoms;
(b) semi-polar nonionic surfactants having the formu- wherein R5 is an organic radical containing from about 10 to about 24 carbon atoms, containing from O to about 3 ether linkages, containing from O to 1 hydroxy group, and having one alkyl moiety which contains from about 10 to about 18 carbon atoms and no ether linkages; R6 and R7 are each selected from the group consisting of methyl, ethyl, hydroxy ethyl, propyl and hydroxy propyl radicals; and (c) mixtures thereof.
(a) zwitterionic detergents having the formula:
and wherein R1 is an alkyl radical containing from about 10 to about 18 carbon atoms, R2 and R3 are each selected from the group consisting of methyl, ethyl and hydroxy ethyl radicals, R4 is selected from the group consisting of alkylene, poly-alkoxy, and hydroxy alkylene radicals, and said hydroxyl groups are attached only to secondary carbon atoms;
(b) semi-polar nonionic surfactants having the formu- wherein R5 is an organic radical containing from about 10 to about 24 carbon atoms, containing from O to about 3 ether linkages, containing from O to 1 hydroxy group, and having one alkyl moiety which contains from about 10 to about 18 carbon atoms and no ether linkages; R6 and R7 are each selected from the group consisting of methyl, ethyl, hydroxy ethyl, propyl and hydroxy propyl radicals; and (c) mixtures thereof.
8. The composition of Claim 7 wherein the ratio of (1) to (2) is from about 1:1 to about 1:2.
9. The composition of Claim 7 wherein (2) is the zwitter-ionic detergent.
10. The composition of Claim 7 wherein (2) is the semi-polar nonionic surfactant .
11. The compositions of Claims 1 or 7 wherein the product pH is from about 10 to about 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19785280A | 1980-10-17 | 1980-10-17 | |
| US197,852 | 1980-10-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1172403A true CA1172403A (en) | 1984-08-14 |
Family
ID=22730999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000388046A Expired CA1172403A (en) | 1980-10-17 | 1981-10-16 | Liquid detergent/softener compositions |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS57126896A (en) |
| CA (1) | CA1172403A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298195A (en) * | 1992-03-09 | 1994-03-29 | Amway Corporation | Liquid dishwashing detergent |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA856296B (en) * | 1984-08-31 | 1987-03-25 | Colgate Palmolive Co | Hot water wash cycle detergent-softener compositions |
| JPS6270498A (en) * | 1985-09-25 | 1987-03-31 | 花王株式会社 | Neutral liquid detergent composition |
| EP0826767B1 (en) * | 1996-07-24 | 2003-03-05 | Sunstar Inc. | Laundry detergent composition |
| JP7133426B2 (en) * | 2018-10-10 | 2022-09-08 | 日華化学株式会社 | Polyester clothing anti-dye transfer cleaning composition and cleaning method using the same. |
-
1981
- 1981-10-15 JP JP16491781A patent/JPS57126896A/en active Pending
- 1981-10-16 CA CA000388046A patent/CA1172403A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298195A (en) * | 1992-03-09 | 1994-03-29 | Amway Corporation | Liquid dishwashing detergent |
| US5443757A (en) * | 1992-03-09 | 1995-08-22 | Amway Corporation | Liquid dishwashing detergent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57126896A (en) | 1982-08-06 |
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