US3812041A - Non-gelling heavy duty liquid laundry detergent - Google Patents

Non-gelling heavy duty liquid laundry detergent Download PDF

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Publication number
US3812041A
US3812041A US00265721A US26572172A US3812041A US 3812041 A US3812041 A US 3812041A US 00265721 A US00265721 A US 00265721A US 26572172 A US26572172 A US 26572172A US 3812041 A US3812041 A US 3812041A
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United States
Prior art keywords
detergent
composition
detergents
water
ethylene oxide
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US00265721A
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English (en)
Inventor
J Inamorato
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Colgate Palmolive Co
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Colgate Palmolive Co
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Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US00265721A priority Critical patent/US3812041A/en
Priority to ZA00733245A priority patent/ZA733245B/xx
Priority to AU55744/73A priority patent/AU5574473A/en
Priority to AR248372A priority patent/AR197610A1/es
Priority to PH14695A priority patent/PH9950A/en
Priority to IT50554/73A priority patent/IT985361B/it
Priority to GB2740973A priority patent/GB1437011A/en
Priority to FR7321852A priority patent/FR2189505B1/fr
Priority to DE2330840A priority patent/DE2330840C2/de
Priority to CH882973A priority patent/CH597345A5/xx
Priority to SE7308589A priority patent/SE414186B/sv
Priority to BR4589/73A priority patent/BR7304589D0/pt
Priority to BE132546A priority patent/BE801241A/xx
Priority to OA54940A priority patent/OA04426A/xx
Priority to CA174,785A priority patent/CA990609A/en
Priority to DK347273A priority patent/DK145861C/da
Priority to NL7308769A priority patent/NL7308769A/xx
Application granted granted Critical
Publication of US3812041A publication Critical patent/US3812041A/en
Priority to HK806/79A priority patent/HK80679A/xx
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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

Definitions

  • a clear non-gelling liquid synthetic organic heavy duty laundry detergent composition comprising a nonionic detergent having the molecular configuration of the condensation product of a higher fatty alcohol and ethylene oxide, an anionic detergent higher fatty alkyl polyethenoxy sulfate, a brightening agent, water and a lower monohydric alcohol. Small proportions of sequestering agents and salt-forming bases may also optionally be present in the composition.
  • the detergent composition is a single phase clear stable liquid but may be made opaque, creamy or opalescent if desired. Furthermore, the composition is substantially neutral or only slightly alkaline when measured at a 1% concentration in water and cleans soiled laundry to a degree comparable with that obtained utilizing phosphate built alkaline detergents.
  • the liquid detergent composition is biodegradable.
  • This invention relates to a substantially neutral liquid detergent useful for heavy duty laundering of soiled clothing and other cloth or fabric articles. More particularly, this invention relates to a substantially builder-free clear biodegradable liquid detergent composition which functions comparably to conventional phosphate built or nitroliotriacetate built commercial heavy duty laundry detergents.
  • a detergent composition comprising only active synthetic organic detergents does not produce the same cleaning effect as a combination of these detergents and the polyphosphates.
  • the only substitute for the polyphosphates which appears to be approximately equal with regard to building and soil-suspending eflects are the nitrilotriacetic acids and acetates often referred to as NTA.
  • the present liquid'detergents are based on a combination of an ethoxamer sulfate and a nonionic detergent both of which are readily biodegradable. Utilization, however, of non-ionic detergents, although biodegradable, is
  • composition of the present invention may include a small amount of NTA, or the like, acting as a metal sequestrant, to prevent discoloration of the products and laundry washed, these small amounts of NTA and the like do not have any building effect on the overall composition.
  • such composition comprises a non-ionic detergent, at least 50% of the non-ionic detergent comprising a lower molecular weight non-ionic having the formula RO(C H O),,H, wherein R is an alkyl group, preferably a straight chain alkyl group having from 10 to 15 carbon atoms, R generally is in the form of a mixed alkyl and may comprise either one specific chain length or a mixture of up to all six, n is selected from 6 to 11' with the proviso that n' is from about /5 to about 3 of the average number of carbon atoms in R; the remainder vention to provide a non-gelling heavy of the non-ionic detergent comprises a higher molecular weight non-ionic having the formula RO (C H O),,H,' wherein R is an alkyl group preferably a straight chain alkyl group averaging from 14 to 20 carbon atoms and n is a number of from 10 to 14,
  • the novel liquid non-gelling detergent which is devoid of phosphate and nitrogenous builders of the present invention comprises from 25% to 75% weight percent of a non-ionic detergent, this non-ionic detergent comprising from 100% to 50% by weight of the non-ionic of a low molecular weight non-ionic of the formula RO(C H O),,H wherein R is an alkyl group preferably having a straight chain from 10 to 15 carbon atoms and n is a number from 6 to 11 with the proviso that n is from /5 to of the average number of carbon atoms in R, and from to 50% by weight of the non-ionic of a high molecular weight non-ionic of the formula RO(C H O),,H wherein R is an alkyl group preferably having a straight chain of from 14 to 20 carbon atoms and n is a number of from 10 to 14, n generally comprising 4 to 1 times the number of carbon atoms in R; from to 25 by weight of an ethoxamer sulfate
  • the synthetic organic detergents utilized in the present invention which provide the concentrated clear liquid detergent composition with its non-gelling characteristics comprise the lower molecular weight non-ionic condensation products of a fatty alcohol with ethylene oxide or ethylene glycol optionally containing a small proportion of propylene glycol. Normally, this condensation will be with ethylene oxide which is cheaper and does not require the removal of by-product water. Methods for the manufacture of such compounds are well known and these materials have been previously employed in detergent compositions, although generally their use has been limited to being part of the entire active organic detergent portion of light duty liquid detergents.
  • the low molecular weight non-ionics which provide the composition of the present invention with the non-gelling characteristics are of the formula RO(C H O),,H wherein R is an alkyl group preferably having a straight chain of from 10 to 15 carbon atoms and n is from 6 to 11 with the proviso that n is from Vs to V of the average number of carbon atoms in R.
  • R is an alkyl group preferably having a straight chain of from 10 to 15 carbon atoms and n is from 6 to 11 with the proviso that n is from Vs to V of the average number of carbon atoms in R.
  • mixed alkyls are employed and for the composition of the present invention to have the desired non-gelling characteristics it is preferred to utilize mixed alkyl chains wherein the chain length averages approximately 12.
  • the ethylene oxide content can vary within this range as long as the amount of ethylene oxide in the final product is within the parameter of from /s to of the average number of carbon atoms in the alkyl group. Since it is critical to maintain the proper balance of fatty alkyl chain length and ethylene oxide chain length within the above-noted ranges in order to obtain good detersive properties together with the nongelling property and compatibility with other materials, it has been found and is a preferred embodiment of the present invention to utilize a non-ionic detergent of the above formula wherein R is a mixed straight chain alkyl having from 10 to 15 carbon atoms, the average number of carbon atoms averaging approximately 12, and n is from 6 to 9 with the proviso that n is from V5 to V5 of the average number of carbon atoms in R.
  • Neodol 25-7 (R equals mixed 12-15 carbon atom alkyl, n equals 11 average value) made by Shell Chemical Company and Pluorofac B-26, the reaction product of a linear alcohol with a mixture of ethylene and propylene oxides, made by Wyandotte Chemical Company.
  • the non-ionic detergent portion of the heavy duty liquid detergent of the present invention may also contain up to 50% of a high molecular weight non-ionic detergent of the formula RO(C H O) H wherein R is a straight chain alkyl of from 14 to 20 carbon atoms and n is from 10 to 14 with the proviso that n is from tol times the average number of carbon atoms in R.
  • these higher molecular weight non-ionics are also produced by reacting mixed alkyls with ethylene oxide chains which include different chain lengths within the 10 to 14 ethylene oxide radical range.
  • the alkyl group will be from 14 to 16 carbon atoms and usually the average carbon content of preferred compounds are from 14 to 15 and in the most preferred higher molecular weight non-ionic detergent compositions for use with the lower molecular weight nonionies, the alkyl groups will be over 14 to 15 carbon atom chain lengths.
  • Neodol 45-11 (R equals mixed 14 to 15 carbon atom alkyls, n equals 11 average value) made by Shell Chemical Company.
  • the desired hydrophilic-lipophilic balance is maintained by keeping n equal to about to 1 times R.
  • the hydrophilic-lipophilic portions of the high molecular weight and low molecular non-ionic detergents described above for best detergency and biodegradability it is important that such portions be of certain configurations.
  • the ethylene oxide chain will be linear and terminated by a free hydroxyl.
  • some mixed chains of ethylene oxide and propylene oxide may be utilized although pure ethylene oxide chains are generally preferred.
  • the alkyl groups also most preferably will be linear although a minor degree of slight branching such as at a carbon next to or two carbons removed from the terminal carbon of a straight chain and away from the ethoxy chain, may be tolerated provided that such branched alkyl portion is of no more than 3 carbon atoms in length. Usually, the portion of carbon atoms in such branched configuration will be quite minor, rarely being more than 20 or 10% of the entire alkyl content of carbon atoms.
  • linear alkyls which are terminally joined to the ethylene oxide chains are highly preferred and result in best detergency, biodegradability and other important properties including non-gelling characteristics, medial or secondary joinder to the ethylene oxide in the chain may occur in a minor proportion of such alkyls and generally such proportion will be less than 20% and preferably less than 10% thereof.
  • the ethylene oxide chain consists essentially of ethylene oxide, generally over 80% and preferably over thereof.
  • composition of the present invention also includes an anionic detergent.
  • anionic detergent is a sulfated ethoxylated higher fatty alcohol of the formula RO(C H O),,SO M
  • R is at fatty alkyl of from to 20 carbon atoms
  • n is from 2 to 6, being from A to /3 of the number of carbon atoms in R
  • M is a solubilizing salt-forming cation such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino.
  • this anionic detergent is most readily biodegradable and of better detergency when the fatty alkyl is terminally joined to the polyoxyethylene chain, which, of course, is terminally joined to the sulfur-forming sulfate group.
  • medial joinder of the alkyl group to the polyoxyethylene chain should be minimal, less than 10%, and even such joinder then should be preferably concentrated near the end of the alkyl chain.
  • the preferred alkyls are of 12 to carbon atoms and those which are most preferred are mixed alkyls containing 12, 13, 14 and 15 carbon atom chains. The mixture is preferably one containing at least 10% of each chain length and no more than 50% of any one chain length.
  • the ethylene oxide content of the anionic detergent is such that n is from 2 to 6 and is preferably from 2 to 4, generally averaging about 3, especially when R is a mixed 12 to 15 carbon atom alkyl.
  • n is from 2 to 6 and is preferably from 2 to 4, generally averaging about 3, especially when R is a mixed 12 to 15 carbon atom alkyl.
  • the salt-forming cation may be any suitable solubilizing metal or radical but will most frequently be alkali metal or ammonium.
  • alkyl-amine or lower alkanolamine groups are present, alkyls and alkanols thereof will usually contain one to four carbon atoms and the amines and alkanolamines may be mono-, dior tri-substituted, e.g. monoethanolamine, diisopropanolamine, trimethylamine.
  • compositions which include a mixed 12 to 15 carbon atom alcohol-ethylene oxide sulfate, when compared to other higher alcohol-ethylene oxide sulfates, such as a mixed 14 to 15 carbon atom alcohol-ethylene oxide sulfate of the same ethylene chain length.
  • the preferred detergent is available from Shell Chemical Company and is'identified by them as Neodol 3S, the sodium salt, normally sold as a 60% active material, including about 40% of aqueous solvent medium, of which a minor proportion is ethanol.
  • Neodol 25-38 is the sodium salt
  • the potassium salt and other suitable soluble salts may also be used either in partial or complete substitution for that of sodium.
  • Examples of the higher alcohol polyethenoxy sulfates which may be used as the anionic detergent constituent of the present liquid composition or as partial substitutes for this include: mixed C normal primary alkyl triethenoxy sulfate, sodium salt; myristyl triethenoxy sulfate, potassium salt; n-decyl diethenoxy sulfate, diethanolamine salt; lauryl diethenoxy sulfate, ammonium salt; palmityl tetraethenoxy sulfate, sodium salt; mixed C1445 normal primary alkyl mixed triand tetraethenoxy sulfate, sodium salt; stearyl pentaethenoxy sulfate, trimethylamine salt and mixed C1048 normal primary alkyl triethenoxy sulfate, potassium salt.
  • Minor proportions of the corresponding branched chain and medially alkoxylated detergents such as those described above but modified to have ethoxylation at a medial carbon atom, e.g. one located four carbons from the end of the chain, may be employed but the carbon atom content of the higher alkyl will be the same.
  • the joinder of a normal alkyl may be at a secondary carbon one or two carbon atoms removed from the end of the chain. In either case, only the minor proportions previously mentioned will be present.
  • higher fatty acid esters of polyethylene glycols for example, there may be used higher fatty acid esters of polyethylene glycols, block copolymers of ethylene oxide and propylene oxide, higher alkyl-di-lower alkyl amine oxides, the sodium salts of the sulfuric acid derivatives of higher fatty alcohol condensation products with ethylene oxide, triethanolamine lauryl sulfate, straight chain alkyl sulfonates, sodium lauroyl sarcoside, cetyl trimethylammonium bromide, benzethonium chloride, dimethyl dibenzyl ammonium chloride, N-higher alkyl N,N- di-lower alkyl aminopropane sulfonates, amidosulfobetaines, betaines and amidobetaines.
  • the fluorescent or optical brighteners or whiteners employed are important constituents of modern detergents which give washed laundry and materials a bright appearance so that the laundry is not only clean but also looks clean. Due to the variety of synthetic fibers incorporated in the textiles which are made into clothing and other items of laundry and the importance of substantivity of the brightener compound to the fibers, many different fluorescent brightening compounds have been made, which may be incorporated in the present detergent compositions, often in mixtures. Of course, brighteners, suitable for use on cotton, and brighteners which are stable in the presence of oxidizing bleaches are also of importance.
  • compositions of the present invention it is generally important to utilize a mixture of brighteners which will have good brightening effects on cotton, nylons, polyesters, and blends of such materials and which, additionally, are bleach stable.
  • a good description of such types of optical brighteners is given in the articles, Optical Brighteners and Their Evaluation, by Per S. Stensby, a reprint of articles published in Soap and Chemical Specialties in April, May, July, August and September 1967, especially at pp. 3-5 thereof.
  • the cotton brighteners frequently referred to as CC/ DAS brighteners because of their derivation from the reaction product of cyanuric chloride and the disodium salt of diamino-stilbene disulfonic acid in molar proportion of 1:2 are bistriazinyl derivatives of 4,4'-diaminostilbene-2,2'-disulfonic acid.
  • the CC/DAS 7 is reacted with two moles of aniline or sulfanilic or metanilic acid and the product is additionally substituted on the 'triazine rings.
  • Such compounds are of the general formula: I
  • X may be either hydrogen or SO Na and the Rs may be those derived from aniline, morpholine, N-methylethanol amine or diethanolamine.
  • a bleach stable brightener usually a benzidine sulfone disulfonic acid, a naphthatriazolylstilbene sulfonic acid or a benzimidazolyl derivative will be used. These compounds are of the formulas:
  • R may be hydrogen, lower alkyl, lower alkanol, lower aminoalkanol, anilino, morpholino, etc.
  • the polyamide brighteners, especially good for nylons, are usually either aminocoumarin or diphenyl pyrazoline derivatives. Unfortunately, neither of these is especially stable in the presence of chlorine bleaches.
  • the compounds are of the formulas given below and the R and the R groups thereof may be previously listed as substituents on the optical brighteners discussed earlier, while X and Y may include such substituents as halogens and lower alkyls.
  • polyester brighteners which are becoming of more importance as polyesters are being used to a greater extent in an increasing proportion of textiles are usually of one of the following formulas, wherein R, X andY have the meaning previously given and Z may be selected from the group of X and Y substituents. These brighteners also usually serve to 'whiten polyamides.
  • the brighteners are used in their acid forms or as salts. They may be employed as solids or in solutions and may be cut with a carrier powder. Although the chemical and physical forms can affect brightening actions, if the compounds are used in soluble forms brightening activities for the same compounds on an active ingredient basis will be equivalent. In the present compositions and in the wash waters resulting, the brighteners are maintained sufiiciently soluble so as to be effective and uniformly substantive to the materials of hte laundry being washed.
  • the brighteners that are used in the present systems are: Calcofiuor White ALF (American Cyanamid); ALF-N (American Cyanamid); SOF A-200l (CIBA); CDW (Hilton-Davis); Phorwite RKH (Verona); CSL, powder, acid (American Cyanamid); PE 766 (Verona); Blancophor PD (GAF) UNPA (Geigy) Tinopal RBS (Geigy); and RES 200 (Geigy).
  • the acid or nonionic forms of the brighteners tend to be solubilized by alcohols of the present formulas, while the salts tend to be water soluble. *lhus, a combination of such solvents and the detergent combination serve to keep the fluorescent brighteners dissolved.
  • the lower alkanol employed is preferably either ethanol of isopropanol but can be any lower monohydric alcohol. Of the two preferred alcohols ethanol is most preferred because of a slightly greater solubilizing power and more pleasant odor. If ethanol is used, it will normally be denatured and of the denatured alcohols those identified as SD40 or 3A are preferred. However, other denatured alcohols may also be used. The alcohols need not be anhydrous and the small proportions of water normally present with them are considered to be part of the water components of the liquid detergents.
  • the alcohol may be replaced with dihydric or trihydric lower alcohols which, in addition to having solubilizing powers and reducing the flash point of the product, also can act as anti-freezing constituents and may improve compatibilities of the solvent system with particular product components.
  • the most preferred group includes the lower polyols of 2 to 3 carbon atoms, e.g. ethylene glycol, propylene glycol and glycerol, but the lower alkyl (C -C etheric derivatives of such compounds known as Cellosolves, may also be employed, generally to only a minor extent.
  • the water used is preferably deionized so that it will be low in content of ions which can form insoluble compounds.
  • ordinary tap water can be used providing that the hardness thereof is sufiiciently low so that in the formula employed there is no detrimental precipitation out of salts on standing.
  • hardness will be less important and in such cases even waters with hardnesses over 300 parts per million equivalent calcium carbonate can be acceptable.
  • the water hardness should be less than p.p.m. and most preferably, less than 50 p.p.m.
  • the sequestering agent when used, may be any suitable compound, including the aminopolycarboxylic acids and hydroxycarboxylic acids.
  • Other sequestering or water-softening agents of the inorganic type such as certain phosphates may be used in very small amounts if desired but are not present in amounts suflicient to have a builder function.
  • Adjuvants may be present in the liquid detergent to give it additional properties, either functional or aesthetic.
  • soil suspending or anti-redeposition agents may be used such as, polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropylmethyl cellulose; enzymes, e.g. protease amylases; thickeners, e.g., gums, alginates, agar agar; hydrotropes, e.g. sodium xylene snlfonate, ammonium benzene sulfonate; foam improvers, lauric myristic diethanolamide; foam destroyers, e.g. silicones, bactericides, e.g.
  • tribromosalicylanilide hexachlorophene
  • fungicides dyes; pigments (water dispersible); preservatives; ultraviolet absorbers; fabric softeners; pearlescing agents; opacifying agent, e.g. behenic acid; polystyrene suspensions, and perfumes.
  • opacifying agent e.g. behenic acid
  • polystyrene suspensions and perfumes.
  • such materials will be selected for the properties desired in the finished product and to be compatible with the other constituents thereof.
  • the pH of the heavy duty liquid detergent composition will normally be substantially neutral or only slightly alkaine.
  • the composition of the present invention contains a minimum of akaline material per se, since the particulate soil removal of the particular non-ionic and anionic detergents utilized is enhanced in approximately neutral solutions. However for various reasons, such as solubilizing and neutralizing various brighteners used, a small amount of an alkaline material may be included.
  • Suitable alkaline materials include mono-, diand trialkanolamines, alkylamines, ammonium and alkali hydroxides.
  • the preferred alkali materials are the alkanolamines, especially the trialkanolamines and most especially triethanolamine.
  • a pH reading of the liquid detergent using a glass electrode and a reference calomel electrode indicates a maximum pH of about 8.
  • the pH reading obtained may be false.
  • a better indication is obtained by measuring the pH of a 25 solution in water. This should usually be in the range of about 6.8 to 8.8. In water containing items to be laundered the pH will normally be within the same range.
  • the proportion of the various components of the present heavy duty liquid detergents are important to the obtainment of a uniform product and acceptable heavy duty laundering action. In the absence of a significant builder content, it is very important that the product contain a significant proportion of detergents. So as to promote solubility of the fluorescent brighteners and other constituents and make a clear, homogeneous and readily pourable liquid product, from 25 to 75% of the total liquid detergent concentrate should be non-ionic fatty alcohol-ethylene oxide condensation products in a mixture of from 100% to 50% by weight of non-ionic of low molecular weight non-ionic and from to 50% by weight of high molecular weight non-ionic as described above. The preferred range is from 30 to 60% of total nonionics and in the most preferred embodiment of the invention about 40% is employed.
  • the non-ionic mixture comprise a significant portion of low molecular weight non-ionic since the non-gelling properties of this material are more effective at higher concentrations. According, it is preferred to utilize a non-ionic mixture of from 100% to 75% by weight of the non-ionic of low molecular weight non-ionic and from 0 to 25% by weight of the non-ionic of high molecular weight nonionic, and it is most preferred to use all low molecular weight non-ionic.
  • the quantity of the anionic ethoxamer sulfate detergent should be within the range of about 5 to 20% and preferably about A of the total non-ionic content, i.e. preferably 10%. Suitable weight ratios of total non-ionic to anionic ranges from about 15:1 to 1:1 with 8:1 to 2:1 preferred and 5 :1 to 3 :1 most preferred.
  • the concentration of fluorescent or optical brightener or whitening agent in the product will be from about 0.5 to 5% on an active ingredient basis, preferably about 1 to 3% and most preferably about 2%. Such quantities are readily solubilized in the clear liquid product and contribute substantially to brightening of fabrics in the laundry. Generally, 25% and preferably at least 50% of the optical brightener content will be a brightener for cotton. It is preferred to use about 51 to 90% of a cotton brightener, with the balance being one or more of polyamide brighteners, polyester brighteners, and chlorinestable brighteners.
  • the lower alcohol will generally be present in a sufficient proportion to aid in stabilizing or dissolving various constituents of the product such as the brighteners.
  • the proportion employed will generally be from 5 to 35%, preferably from 5 to 25
  • the quantity of alcohol present normally is from 5 to 20% but when the supplementing polyol is used the content of alcohol may be reduced to from 5 to 15%, preferably about 5 to 10%.
  • the proportion of polyol will generally be from 5 to 15 most preferably 10%.
  • the percentage of water utilized will also generally be from 5 to 35% and a preferred range is from 5 to 25 with a most preferred range being from 15 to 20%. Similar considerations prevail in determining the proportion of water to be employed as do in the case of the alcohols.
  • the non-building proportion of sequestrant when used, may range from 0.2 to 3,%, preferably from 0.5 to 1.5%, and most preferably 0.8%.
  • the quantities or proportions thereof employed will vary. Generally, however, it may be said that the total thereof should not exceed 10% and will preferably be maintained less than 5% and more preferably less than about 3%. Individual components should usually not exceed 5% preferably 3% and more preferably 1% of the product. The use of more of such compounds will often significantly change the properties of the liquid detergent and, therefore, is to be avoided.
  • the heavy duty liquid detergents of the present invention can be made by simple manufacturing techniques which do not require any complicated equipment or expensive operations.
  • the optical brighteners may be slurried in the monohydric alcohol or mixture of monohydric and polyhydric alcohol. If initially slurried in the monohydric alcohol, subsesequently the polyhydric alcohol, if used, may be added to this. Then water and, if necessary, a small amount of base such as triethanolamine is added, which helps to partially dissolve the previously suspended material but not yield a clear solution. Addition of the detergent combination causes the remainder of the brightener to dissolve to make a clear solution.
  • the sequestrant if used, may be added as the acid or salt (preferably the sodium, potassium or amine salt) and agitation is continued until the solution becomes clarified, which will normally take about 5 to 10 minutes.
  • perfume and dye may be added to give the product its final desired appearance and odor. All of the operations may 'be effected at room temperature, although suitable temperatures within the range of 10 to C. may be employed, as desired. Additions of adjuvants may be efiected at suitable points in the process but for the most part these will be added to the final product.
  • the product obtained will usually have a pH within the range of from 6.5 to 8, e.g.
  • the viscosity of the product at 25 C. will usually be from 20 to 200 centipoises, preferably from 50 to 150 cps., and will be in the higher part of this range if a polyhydric alcohol is used in replacement of some lower monohydric alcohol.
  • the present compositions are versatilely simple and eificient. Compared to present heavy duty laundry detergent powders, much smaller volumes of the present liquids may be employed to obtain cleaning of soiled laundry.
  • a typical and preferred formulation of this invention containing about 40% of the fatty alcohol-ethylene oxide condensate and ethoxamer sulfate, only about 2 ounces or A cup of liquid need to be used for a full top-loading automatic machine tube of d wash, in which the water volume might be from 15 to 18 gallons.
  • the concentration of liquid detergent in the wash water is on the order of 0.1%, 1 gram per liter or 1,000 parts per million.
  • the proportion employed will be from 0.7 to 1.5 grams per liter, which may correspond to 0.3 to 0.6 g./l. of the mixture of fatty alcohol-ethylene oxide condensation products, from 0.075 to 0.15 g./l. of ethoxamer sulfate, from 0.01 to 0.05 -g./l. of the fluorescent or optical brightener, from 0.05 to 0.4 g./l. of lower monohydric alcohol and from 0.005 to 0.03 g./l. of organic sequestrant.
  • the proportions of other constituents of the liquid compositions may vary accordingly.
  • wash water of reasonable hardness and at an elevated temperature the present invention is also useful in laundering clothes and other items in hard waters and in extremely soft waters, as well as in waters at room temperature or below.
  • water hardnesses may range from 0 to over 300 parts per million as calcium carbonate and washing temperatures may be from 10 C. to 80 C.
  • the temperatures will be from room temperature, 20 to C., to 70 C.
  • washing will ordinarily be effected in an automatic washing machine, with the washing followed by rinse and spin or draining or wringing operations, it is contemplated that the detergent may also be used for hand washing of laundry.
  • the concentration in water of the liquid detergent will often be increased and sometimes it may be full strength to assist in washing out otherwise difficult to remove soils or stains. After completion of the washing and spinning operations, it will be general practice to dry the laundry in an automatic dryer soon thereafter but such particular drying operation is not necessary.
  • the liquid composition gels within a short period of time when exposed to the atmosphere. Furthermore, the liquid detergents without sufficient low molecular weight non-ionic, i.e. at least 50% of the non-ionic detergents, to retard or eliminate this gelling do not disperse properly in water after exposure to the atmosphere. If the liquid detergent gels and does not disperse properly in water, this causes the brighteners to be concentrated in small areas causing uneven and splotchy brightening.
  • composition of the present invention will now be more fully illustrated by the following specific examples which are illustrative and in no way limitative of the present composition wherein all parts and percentages are by weight and temperatures in degrees Fahrenheit unless otherwise noted.
  • EXAMPLE 1 A clear, liquid detergent having the following formula is prepared by slurrying the mixture of optical brighteners in SD-40 alcohol followed by the addition of water and triet hanolamine with stirring. Subsequently, the Neodol 25-7 and the Neodol 25-3S is added and after a few minutes of agitation at moderate speed the solution becomes clear.
  • the pH of a 25% solution of the above formulation in water is about 7.0.
  • This liquid detergent which is a sparkling, clear, free-flowing liquid is then packed in polyethylene plastic bottles of substantially cubic shape and of one quart capacity and is ready for use. Storage tests indicate that this product Will be stable for several years without precipitation of insoluble salts, settling into a plurality of phases, clouding or other disadvantageous effects on appearance or function.
  • Detergency and brightening power of the liquid detergent composition is evaluated in control tests wherein the experimental formula is compared with various commercial heavy duty ecology type laundry detergents.
  • cloths are intentionally soiled with a mud soil and washed in identical washing machines (Terg-o-tometer)"using the same Water and recommended amounts of the experimental and various controlled detergents.
  • the soiled cloths are collected and divided so that'the experimental and controlled formulas are used to Wash similarly soiled loads of laundry. Such testing is repeated and the whiteness of the various washed cloths are compared each time by Reflectometer. Results of these tests in both hot and cold washing water conditions are listed in Table 1.
  • Example 1 cleans better at a lower concentration than other commercially available ecology type, i.e. biodegradable and non-phosphate containing, detergent compositions. Furthermore, the formulation of Example 1 cleans better at a lower wash water concentration as exhibited in Table 1 14 which shows that a concentration of only 0.09 is necessary as opposed to up to 0.3 for some other ecology type detergents.
  • the present formulation can be utilized in a concentration which corresponds to approximately cup per 16-gallon automatic washing machine tube and that at such concentration the liquid detergent favorably compares with other washing products wherein concentrations corresponding to 1% cups of spray-dried heavy duty laundry detergents must be used.
  • Reflectometer readings of Whiteness when the formulation of Example 1 is compared against various laundry detergents built with polyphosphates show no significant difference between the detergents.
  • subjective evaluations of the product in consumer tests using a panel of housewives result in a significant preference for the liquid detergent.
  • Example 1 Since no builder is utilized, it has been theorized that particulate soil could accumulate on washed items, however, subsequent to repeated washings shows that the laundry detergent of Example 1 compares quite favorably with the phosphate detergents with regard to particulate soil removal.
  • EXAMPLE 2 A series of liquid detergent compositions are produced utilizing the basic formula of Example 1 where in the Neodol 25-7 is replaced with the following non-ionic detergents:
  • Samples (A) through (D) do not gel within 18 hours and are dispersed readily upon pouring into both hot and'cold water.
  • Samples 3(E) and 15 (F) became gelled within minutes exposure to the atmosphere and are not readily dispersible in hot or cold water.
  • EXAMPLE 4 Examples 2(A) through (F) and (K) and (L) are repeated varying the total amount of non-ionic detergent from 40% to the following with a concomitant increase or decrease in total amount of water and alcohol:
  • A C ether sulfate containing 2 moles of condensed ethylene oxide
  • B C ether sulfate containing 2 moles of condensed ethylene oxide
  • C C ether sulfate containing 5 moles of condensed ethylene oxide
  • D C ether sulfate containing 3 moles of condensed ethylene oxide
  • E C ether sulfate containing 6 moles of condensed ethylene oxide.
  • composition of the present invention has been illustrated by way of the foregoing specific examples, the composition of the present invention is to be in no way limited thereto but to be construed as broadly as any and all equivalents and as properly defined in the following appended claims.
  • a clear, non-gelling, heavy duty liquid detergent composition devoid of phosphate and nitrogenous builders and which consists essentially of:
  • a detergent mixture of at least one non-ionic detergent and an anionic detergent in a weight ratio ranging from :1 to 1:1 said nonionic detergent comprising from 100 to 50% by weight based on the weight of the non-ionic detergent of a (3 43 fatty alcohol ethoxylate containing from 6 to 11 moles of condensed ethylene oxide, with the proviso that the number of moles of condensed ethylene oxide is from to an of the average number of carbon atoms in the fatty alcohol and from 0 to 50% by weight of a C -C fatty alcohol ethoxylate containing from 10 to 14 moles of condensed ethylene oxide the number of moles of ethylene oxide being M to 1 times the number of carbon atoms in the fatty alcohol, said anionic detergent comprising a sulfated ethoxylated C -C fatty alcohol containing about 2 to 6 moles of condensed ethylene oxide;
  • said fatty moiety comprises mixed alkyl containing from 12 to 15 carbon atoms and wherein at least 10% and not more than 50% of each member of said mixed alkyl is present.
  • composition of claim 1 wherein the total nonionic detergent comprises 40% by weight of the composition and said anionic detergent comprises 10% by weight of the composition.
  • composition of claim 1 wherein the non-ionic detergent comprises a mixed C1z-C15 fatty alcohol ethoxylate containing about 7 moles of condensed ethylene oxide.
  • the detergent composition of claim 1 which further includes from about 0.5 to 5% of a bleach stable, at least partially water soluble fiourescent or optical brightener.
  • B 4,4' bis[(4 anilino 6 [bis(2 hydroxy-ethyl) amino] S triazine 2 yl)amino] 2,2 stilbenedisulfonic acid, disodium salt.
  • D 2-(1,3-isoindazole) 2 (naphth[l,2-d]oxazole) stilbene.
  • the detergent composition of claim 1 including from about 0.2 to 3% of aminopolycarboxylic acid or hydroxy carboxylic acid sequestering agent.
  • the detergent composition of claim 1 containing an alkaline material selected from the group consisting of mono-, diand trialkanolamines, alkylamines, ammonium and alkali hydroxides.
  • a process of laundering which comprises contacting cloth or fabric with aqueous media containing from 0.7 to 1.5 g./l. of the composition of claim 1, said containing being carried out at a temperature of from about 10 to C.

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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)
  • Detergent Compositions (AREA)
US00265721A 1972-06-23 1972-06-23 Non-gelling heavy duty liquid laundry detergent Expired - Lifetime US3812041A (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
US00265721A US3812041A (en) 1972-06-23 1972-06-23 Non-gelling heavy duty liquid laundry detergent
ZA00733245A ZA733245B (en) 1972-06-23 1973-05-14 Liquid laundry detergent
AU55744/73A AU5574473A (en) 1972-06-23 1973-05-16 Liquid laundry detergent liquid laundry detergent
AR248372A AR197610A1 (es) 1972-06-23 1973-06-01 Composicion detergente liquida
PH14695A PH9950A (en) 1972-06-23 1973-06-05 Liquid laundry detergent
IT50554/73A IT985361B (it) 1972-06-23 1973-06-08 Composizione detergente liqui da per bucato
GB2740973A GB1437011A (en) 1972-06-23 1973-06-08 Liquid detergent compositions
FR7321852A FR2189505B1 (de) 1972-06-23 1973-06-15
DE2330840A DE2330840C2 (de) 1972-06-23 1973-06-16 Klares, nichtgelierendes, in Wasser im wesentlichen neutral reagierendes flüssiges Grobwaschmittel
CH882973A CH597345A5 (de) 1972-06-23 1973-06-18
SE7308589A SE414186B (sv) 1972-06-23 1973-06-19 Detergentkomposition innehallande en anjonaktiv detergent och en blandning av tva icke-jonaktiva detergenter
BR4589/73A BR7304589D0 (pt) 1972-06-23 1973-06-20 Composicao detergente transparente, nao gelificavel e para servico pesado
OA54940A OA04426A (fr) 1972-06-23 1973-06-21 Détergent liquide pour le lavage du linge.
BE132546A BE801241A (fr) 1972-06-23 1973-06-21 Detergent liquide pour le lessivage
CA174,785A CA990609A (en) 1972-06-23 1973-06-22 Liquid laundry detergent
DK347273A DK145861C (da) 1972-06-23 1973-06-22 Klart ikke-gelerende kraftigt virkende flydende rensemiddel
NL7308769A NL7308769A (de) 1972-06-23 1973-06-22
HK806/79A HK80679A (en) 1972-06-23 1979-11-22 Liquid detergent compositions

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AR (1) AR197610A1 (de)
AU (1) AU5574473A (de)
BE (1) BE801241A (de)
BR (1) BR7304589D0 (de)
CA (1) CA990609A (de)
CH (1) CH597345A5 (de)
DE (1) DE2330840C2 (de)
DK (1) DK145861C (de)
FR (1) FR2189505B1 (de)
GB (1) GB1437011A (de)
HK (1) HK80679A (de)
IT (1) IT985361B (de)
NL (1) NL7308769A (de)
OA (1) OA04426A (de)
PH (1) PH9950A (de)
SE (1) SE414186B (de)
ZA (1) ZA733245B (de)

Cited By (44)

* Cited by examiner, † Cited by third party
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US3931033A (en) * 1973-12-14 1976-01-06 Henkel & Cie G.M.B.H. Liquid foam-regulated nonionic detergent compositions
US3935129A (en) * 1973-10-25 1976-01-27 Jabalee Walter J Liquid cleaning compositions
US3935130A (en) * 1972-07-19 1976-01-27 Kabushiki Kaisha Tsumura Juntendo Detergent composition for cleaning bathtubs
US3985670A (en) * 1973-06-01 1976-10-12 Henkel & Cie G.M.B.H. Liquid regulated-foam detergent compositions
US3985687A (en) * 1974-12-26 1976-10-12 Colgate-Palmolive Company Liquid detergent compositions of controlled viscosities
US3994818A (en) * 1975-03-04 1976-11-30 Shell Oil Company Substantially non-aqueous low foaming liquid non-ionic detergent composition
US3998750A (en) * 1975-06-30 1976-12-21 The Procter & Gamble Company Liquid detergent composition
US4079078A (en) * 1974-06-21 1978-03-14 The Procter & Gamble Company Liquid detergent compositions
US4083793A (en) * 1973-05-23 1978-04-11 Henkel Kommanditgesellschaft Auf Aktien Washing compositions containing aluminosilicates and nonionics and method of washing textiles
US4092273A (en) * 1974-10-03 1978-05-30 Colgate-Palmolive Company Liquid detergent of controlled viscosity
US4105592A (en) * 1974-06-21 1978-08-08 The Procter & Gamble Company Liquid detergent compositions
US4110262A (en) * 1976-03-08 1978-08-29 The Procter & Gamble Company Liquid detergent composition
US4123378A (en) * 1975-09-16 1978-10-31 Ciba-Geigy Ag Stain removing agents and process for cleaning and optionally dyeing textile material
US4129514A (en) * 1976-03-24 1978-12-12 Rhone-Poulenc Industries Surface-active composition based on non-ionic surfactants
US4133779A (en) * 1975-01-06 1979-01-09 The Procter & Gamble Company Detergent composition containing semi-polar nonionic detergent and alkaline earth metal anionic detergent
US4166048A (en) * 1975-09-22 1979-08-28 Kao Soap Co., Ltd. High foaming detergent composition having low skin irritation properties
US4201686A (en) * 1978-01-09 1980-05-06 Lever Brothers Company Aqueous liquid detergent compositions containing mixtures of nonionic surfactants
US4368147A (en) * 1974-10-03 1983-01-11 Colgate-Palmolive Company Liquid detergent of controlled viscosity
US4409136A (en) * 1977-01-31 1983-10-11 Colgate Palmolive Company Molecular sieve zeolite-built detergent paste
US4412944A (en) * 1980-02-12 1983-11-01 Alcolac, Inc. High foaming, low eye irritation cleaning compositions containing ethoxylated anionic (C13-C30) sulphates
US4427410A (en) 1974-09-06 1984-01-24 Colgate-Palmolive Company Fabric softening composition containing molecular sieve zeolite
US4436653A (en) 1981-04-06 1984-03-13 The Procter & Gamble Company Stable liquid detergent compositions
US4559169A (en) * 1984-08-17 1985-12-17 The Procter & Gamble Company Stable liquid detergents containing anionic surfactant and monosulfonated brightener
US4610796A (en) * 1974-09-06 1986-09-09 The Colgate-Palmolive Co. Fabric softener composition containing molecular sieve zeolite
US4744916A (en) * 1985-07-18 1988-05-17 Colgate-Palmolive Company Non-gelling non-aqueous liquid detergent composition containing higher fatty dicarboxylic acid and method of use
AU581905B2 (en) * 1984-07-03 1989-03-09 Procter & Gamble Company, The Stable liquid detergents containing anionic surfactant and monosulfonated brightener
US4970029A (en) * 1984-07-03 1990-11-13 The Procter & Gamble Company Stable liquid detergent containing anionic surfactant and monosulfonated brightener
US4978475A (en) * 1988-02-26 1990-12-18 The Procter & Gamble Company Stable liquid detergents containing anionic surfactant and monosulfonated brightener
AU626955B2 (en) * 1988-11-24 1992-08-13 Henkel Kommanditgesellschaft Auf Aktien Paste-like, phosphate-free detergent with reduced frothing tendency
US5589448A (en) * 1993-02-17 1996-12-31 The Clorox Company High water liquid enzyme prewash composition
US5789364A (en) * 1993-02-17 1998-08-04 The Clorox Company High water liquid enzyme prewash composition
US6632783B1 (en) * 2000-05-10 2003-10-14 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Liquid detergent package with transparent/translucent bottle labels with UV absorbers
US20080146482A1 (en) * 2006-12-06 2008-06-19 The Procter & Gamble Company Liquid laundry detergent having improved brightener stability
US20080312121A1 (en) * 2005-09-08 2008-12-18 Kirk Herbert Raney Liquid Surface Active Compositions
WO2020259947A1 (en) * 2019-06-28 2020-12-30 Unilever Plc Detergent composition
WO2020259948A1 (en) * 2019-06-28 2020-12-30 Unilever Plc Detergent composition
US11046915B2 (en) 2018-12-21 2021-06-29 Henkel IP & Holding GmbH Use of polyglycols to control rheology of unit dose detergent compositions
US11118141B2 (en) 2018-12-21 2021-09-14 Henkel IP & Holding GmbH Use of alkoxylated polyamines to control rheology of unit dose detergent compositions
US11242499B2 (en) 2019-08-21 2022-02-08 Henkel IP & Holding GmbH Use of glycol ethers and alkyl alcohol blends to control surfactant composition rheology
US11306279B2 (en) 2019-08-21 2022-04-19 Henkel Ag & Co. Kgaa Use of glycol ether to control rheology of unit dose detergent pack
US11414625B2 (en) 2019-12-07 2022-08-16 Henkel Ag & Co. Kgaa Use of tertiary amines and alkyl alcohol blends to control surfactant composition rheology
US11629313B2 (en) 2019-12-07 2023-04-18 Henkel Ag & Co. Kgaa Use of tertiary amine to control rheology of unit dose detergent pack
US11773261B2 (en) 2019-08-21 2023-10-03 Henkel Ag & Co. Kgaa Use of poloxamers and alkyl alcohol blends to control surfactant composition rheology
US12084633B2 (en) 2020-12-15 2024-09-10 Henkel Ag & Co. Kgaa Unit dose laundry detergent compositions containing soil release polymers

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DE2559224A1 (de) * 1975-01-03 1976-07-15 Procter & Gamble Europ Fluessige detergensgemische
DE2559225A1 (de) * 1975-01-03 1976-07-15 Procter & Gamble Europ Fluessiges wasch- und reinigungsmittel sowie seine anwendung
DE2703998C3 (de) * 1977-02-01 1981-10-01 Henkel KGaA, 4000 Düsseldorf Flüssiges Waschmittelkonzentrat mit geringem Schaumvermögen
AU627734B2 (en) * 1988-06-13 1992-09-03 Colgate-Palmolive Company, The Stable and homogeneous concentrated all purpose cleaner
KR900016443A (ko) * 1989-04-26 1990-11-13 오노 알버어스 표면 활성 조성물 및 그 제조방법

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BE548158A (de) * 1955-05-27
FR1472561A (fr) * 1965-03-30 1967-03-10 Henkel & Cie Gmbh Agent liquide pour le traitement des taches sur textiles
DE1279273B (de) * 1965-03-30 1968-10-03 Henkel & Cie Gmbh Fluessige Fleckenbehandlungskonzentrate zur lokalen Direktbehandlung verschmutzter Textilteile
ZA722326B (en) * 1971-05-04 1973-11-28 Colgate Palmolive Co Liquid detergent and laundering process

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935130A (en) * 1972-07-19 1976-01-27 Kabushiki Kaisha Tsumura Juntendo Detergent composition for cleaning bathtubs
US4083793A (en) * 1973-05-23 1978-04-11 Henkel Kommanditgesellschaft Auf Aktien Washing compositions containing aluminosilicates and nonionics and method of washing textiles
US3985670A (en) * 1973-06-01 1976-10-12 Henkel & Cie G.M.B.H. Liquid regulated-foam detergent compositions
US3935129A (en) * 1973-10-25 1976-01-27 Jabalee Walter J Liquid cleaning compositions
US3931033A (en) * 1973-12-14 1976-01-06 Henkel & Cie G.M.B.H. Liquid foam-regulated nonionic detergent compositions
US4105592A (en) * 1974-06-21 1978-08-08 The Procter & Gamble Company Liquid detergent compositions
US4079078A (en) * 1974-06-21 1978-03-14 The Procter & Gamble Company Liquid detergent compositions
US4427410A (en) 1974-09-06 1984-01-24 Colgate-Palmolive Company Fabric softening composition containing molecular sieve zeolite
US4610796A (en) * 1974-09-06 1986-09-09 The Colgate-Palmolive Co. Fabric softener composition containing molecular sieve zeolite
US4092273A (en) * 1974-10-03 1978-05-30 Colgate-Palmolive Company Liquid detergent of controlled viscosity
US4368147A (en) * 1974-10-03 1983-01-11 Colgate-Palmolive Company Liquid detergent of controlled viscosity
US3985687A (en) * 1974-12-26 1976-10-12 Colgate-Palmolive Company Liquid detergent compositions of controlled viscosities
US4133779A (en) * 1975-01-06 1979-01-09 The Procter & Gamble Company Detergent composition containing semi-polar nonionic detergent and alkaline earth metal anionic detergent
US3994818A (en) * 1975-03-04 1976-11-30 Shell Oil Company Substantially non-aqueous low foaming liquid non-ionic detergent composition
US3998750A (en) * 1975-06-30 1976-12-21 The Procter & Gamble Company Liquid detergent composition
US4123378A (en) * 1975-09-16 1978-10-31 Ciba-Geigy Ag Stain removing agents and process for cleaning and optionally dyeing textile material
US4166048A (en) * 1975-09-22 1979-08-28 Kao Soap Co., Ltd. High foaming detergent composition having low skin irritation properties
US4110262A (en) * 1976-03-08 1978-08-29 The Procter & Gamble Company Liquid detergent composition
US4129514A (en) * 1976-03-24 1978-12-12 Rhone-Poulenc Industries Surface-active composition based on non-ionic surfactants
US4409136A (en) * 1977-01-31 1983-10-11 Colgate Palmolive Company Molecular sieve zeolite-built detergent paste
US4201686A (en) * 1978-01-09 1980-05-06 Lever Brothers Company Aqueous liquid detergent compositions containing mixtures of nonionic surfactants
US4412944A (en) * 1980-02-12 1983-11-01 Alcolac, Inc. High foaming, low eye irritation cleaning compositions containing ethoxylated anionic (C13-C30) sulphates
US4436653A (en) 1981-04-06 1984-03-13 The Procter & Gamble Company Stable liquid detergent compositions
AU581905B2 (en) * 1984-07-03 1989-03-09 Procter & Gamble Company, The Stable liquid detergents containing anionic surfactant and monosulfonated brightener
US4970029A (en) * 1984-07-03 1990-11-13 The Procter & Gamble Company Stable liquid detergent containing anionic surfactant and monosulfonated brightener
US4559169A (en) * 1984-08-17 1985-12-17 The Procter & Gamble Company Stable liquid detergents containing anionic surfactant and monosulfonated brightener
US4744916A (en) * 1985-07-18 1988-05-17 Colgate-Palmolive Company Non-gelling non-aqueous liquid detergent composition containing higher fatty dicarboxylic acid and method of use
US4978475A (en) * 1988-02-26 1990-12-18 The Procter & Gamble Company Stable liquid detergents containing anionic surfactant and monosulfonated brightener
AU626955B2 (en) * 1988-11-24 1992-08-13 Henkel Kommanditgesellschaft Auf Aktien Paste-like, phosphate-free detergent with reduced frothing tendency
US5589448A (en) * 1993-02-17 1996-12-31 The Clorox Company High water liquid enzyme prewash composition
US5789364A (en) * 1993-02-17 1998-08-04 The Clorox Company High water liquid enzyme prewash composition
US6632783B1 (en) * 2000-05-10 2003-10-14 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Liquid detergent package with transparent/translucent bottle labels with UV absorbers
US20080312121A1 (en) * 2005-09-08 2008-12-18 Kirk Herbert Raney Liquid Surface Active Compositions
US20080146482A1 (en) * 2006-12-06 2008-06-19 The Procter & Gamble Company Liquid laundry detergent having improved brightener stability
US11046915B2 (en) 2018-12-21 2021-06-29 Henkel IP & Holding GmbH Use of polyglycols to control rheology of unit dose detergent compositions
US11118141B2 (en) 2018-12-21 2021-09-14 Henkel IP & Holding GmbH Use of alkoxylated polyamines to control rheology of unit dose detergent compositions
WO2020259947A1 (en) * 2019-06-28 2020-12-30 Unilever Plc Detergent composition
WO2020259948A1 (en) * 2019-06-28 2020-12-30 Unilever Plc Detergent composition
CN113891930A (zh) * 2019-06-28 2022-01-04 联合利华知识产权控股有限公司 洗涤剂组合物
US11242499B2 (en) 2019-08-21 2022-02-08 Henkel IP & Holding GmbH Use of glycol ethers and alkyl alcohol blends to control surfactant composition rheology
US11306279B2 (en) 2019-08-21 2022-04-19 Henkel Ag & Co. Kgaa Use of glycol ether to control rheology of unit dose detergent pack
US11773261B2 (en) 2019-08-21 2023-10-03 Henkel Ag & Co. Kgaa Use of poloxamers and alkyl alcohol blends to control surfactant composition rheology
US11414625B2 (en) 2019-12-07 2022-08-16 Henkel Ag & Co. Kgaa Use of tertiary amines and alkyl alcohol blends to control surfactant composition rheology
US11629313B2 (en) 2019-12-07 2023-04-18 Henkel Ag & Co. Kgaa Use of tertiary amine to control rheology of unit dose detergent pack
US12084633B2 (en) 2020-12-15 2024-09-10 Henkel Ag & Co. Kgaa Unit dose laundry detergent compositions containing soil release polymers

Also Published As

Publication number Publication date
DE2330840C2 (de) 1985-02-21
CA990609A (en) 1976-06-08
CH597345A5 (de) 1978-03-31
DK145861B (da) 1983-03-21
NL7308769A (de) 1973-12-27
GB1437011A (en) 1976-05-26
PH9950A (en) 1976-06-14
BE801241A (fr) 1973-10-15
AU5574473A (en) 1974-11-21
IT985361B (it) 1974-11-30
FR2189505B1 (de) 1977-05-13
AR197610A1 (es) 1974-04-23
HK80679A (en) 1979-11-30
SE414186B (sv) 1980-07-14
FR2189505A1 (de) 1974-01-25
ZA733245B (en) 1975-01-29
OA04426A (fr) 1980-02-29
BR7304589D0 (pt) 1974-08-29
DK145861C (da) 1983-09-05
DE2330840A1 (de) 1974-01-17

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