US3594322A - Liquid detergent - Google Patents

Liquid detergent Download PDF

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Publication number
US3594322A
US3594322A US680946A US3594322DA US3594322A US 3594322 A US3594322 A US 3594322A US 680946 A US680946 A US 680946A US 3594322D A US3594322D A US 3594322DA US 3594322 A US3594322 A US 3594322A
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germicide
germicides
solution
solvent
grams
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US680946A
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James H Wilson
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Lever Brothers Co
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Lever Brothers Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D27/00—Connections between superstructure or understructure sub-units
    • B62D27/02—Connections between superstructure or understructure sub-units rigid

Definitions

  • the present invention relates to stable aqueous base germicidal compositions such as liquid detergent compositions having germicidal properties and to a method for their preparation.
  • liquid detergent compositions have been proposed for use in the cleaning of household artic les, such as dishes, glasses, fine china, linens and the like. These liquid detergents are quite popular and have been accepted widely because of their convenience and substantial cleansing properties.
  • formulation of liquid detergent compositions presents a number of special problems.
  • liquid detergent formulations are highly concentrated solutions of one or more detergents and various performance improving adjuvants. It is essential that the formulations be stable over a Wide range of environmental conditions. They should not be subject to deterioration due to precipitation of solid material or separation of liquid phases when exposed to severe storage conditions over a prolonged period of time. In order to provide stable concentrated solutions of several ingredients it is necessary to formulate the liquid detergent compositions within fairly strict specifications. It will be appreciated that any alteration of such rigidly balanced compositions by the admixture of an additional ingredient necessitates a rebalancing of the formulation or the employment of special formulating techniques in order to maintain a degree of stability and performance equivalent to the original formulations.
  • Synthetic detergents of the type generally employed in liquid detergent formulations are known to possess a certain degree of germicidal character. Unfortunately, however, they are not all equally effective against a wide variety of bacteria. It is therefore desirable to provide liquid detergent compositions which have a uniform degree of germicidal activity against a broad spectrum of bacteria. This can be accomplished through the incorporation in the detergent compositions of a germicidal agent. However, the simple addition of a germicide to a detergent formulation has not proven to be an effective means of providing stable homogeneous products in which the germicide remains dissolved.
  • halogenated organic germicides such as polybrominated salicylanilides
  • minated salicylanilides such as 3,4,S-tribromosalicylani lide, 3,S-dibromosalicylanilide, and -4,5-dibromosalicylanilide have very low solubility in most common solvents, such as water, ethyl alcohol, 'isopropyl alcohol, propylene glycol, glycerine, and the like.
  • Attempts to predissolve the germicide in various components of the composition or in mixtures of components have not been completely successful.
  • 3,4,S-tribromosalicylanilide was found to be insoluble in ammonium xylenesulfonate even at temperatures up to 200 F. This germicide is also insoluble in ethanol at temperatures up to F.
  • Attempts to predissolve the germicide in relatively dilute aqueous solutions of various nonionic detergents were unsuccessful in that While initial solubility was achieved at elevated temperatures the germicide came out of solution when the temperature was lowered to room temperature.
  • a further object of this invention is to prevent precipitation of initially dissolved organic germicides during subsequent processing and during storage.
  • solvents and preferably particular solvents within the classes are capable of dissolving slightly soluble halogenated germicides and imparting stability to water-containing solutions prepared by adding the initially dissolved germicide to a final formulation such as a Water-containing liquid detergent formulation.
  • These materials are referred to as selected solvents. They have been effective as solubilizing and solution-stabilizing materials for difiicult-to-dissolve germicides as herein described.
  • a particular solvent system is described as being alkaline, a pH of at least about 7 and preferably at least about 9.5 is intended.
  • Preferred mixtures are 1:1 mixtures of water and a glycol selected from the group consisting of ethylene glycol, propylene glycol, hexylene glycol, and 1,2- butylene glycol.
  • Polyethers such as polyethylene glycols.
  • Preferred materials include polyethylene glycols having from 2 to 6 carbon atoms, e.g., diethylene glycol, and the monobutyl ether of diethylene glycol. These materials can be combined with Water to provide a solvent system comprising from about 5 to about 60 Weight percent Water, and the pH can be adjusted with any suitable hydroxide.
  • Fatty acid alkanolamides having from about 6 to 18 carbon atoms in the fatty acid portion of the molecule.
  • Illustrative materials include lauric monoethanolamide, capric monoethanolamide and the like. Preferred materials are the lauric monoand diethanolamides.
  • Alkanolamines preferably the mono-, di-, and triethanol amines.
  • nonionic surface active agents containing at least about 25 weight percent of the surface active agent.
  • Preferred nonionics include alkyl phenols condensed with from about 5 to about 9 moles of ethylene oxide, particularly octyl and nonyl phenols.
  • Illustrative examples of available materials are the condensate of about 5 moles of ethylene oxide with octylphenol, the condensate of about 9 moles of ethylene oxide with nonylphenol, and alkyl phenoxy polyoxyethylene ethanol (Igepol CA 720).
  • Alkaline solutions of anionic surface active agents particularly alkyl benzene sulfonates and sulfated fatty alcohol-ethylene oxide condensates.
  • Suitable materials include the well-known alkyl sulfates, alkyloxysulfonates, alkylisethionates, alpha-sulfo soaps, sulfated rnonoglycerides and the like.
  • Particularly preferred anionics are dodecyl benzene sulfonates and condensates of ethylene xide and fatty alcohol sulfates.
  • solvents characterized by a solubilizing and solution stabilizing effect are preferred. These preferred solvents are: (I) lauric diethanolamide, (2) lauric monoethanolamide, (3) diethylene glycol, (4) diethylene glycol monobutylether, (5) alkaline mixtures of water and hexylene glycol containing up to about 50% water, (6) alkaline solutions of anionic detergents containing at least about 25 of the detergent, (7) aqueous solutions of nonylphenol condensed with from about 5 to about 9 moles of ethylene oxide, containing at least about 25% of the condensate, and (8) aqueous solutions of octyl phenol condensed with about 5 moles of ethylene oxide containing at least about 25 of the condensate.
  • the slightly soluble halogenated organic germicides which are contemplated are well-known materials.
  • Illustrative examples of such germicides are the normal and alkali metal (e.g., sodium and potassium) salt forms of 4' monobromosalicylanilide, 5-monobromosalicylanilide, 4',5 dibromosalicylanilide, 3,5 dibrornosalicylanilide, 3,4,5-tribromosalicylanilide, 3,3',4',5-tetrabromosalicylanilide, and trichlorocarbanilide.
  • the preferred halogenated organic germicides are 3,4,S-tribromosalicylanilide, 4',5- dibromosalicylanilide, the alkali metal salts of these materials, and mixtures thereof containing at least about 50 percent by weight of 3,4,S-tribromosalicylanilide or an alkali metal salt thereof.
  • halogenated organic germicides are employed in germicidally effective amounts, that is, in amounts which are sufficient to provide the desired degree of germicidal character in the final product.
  • germicidally effective amounts that is, in amounts which are sufficient to provide the desired degree of germicidal character in the final product.
  • the initial germicide solution i.e., in the selected solvent
  • aqueous formulation containing detergent components in order to provide a final formulation containing from about 0.05 to about 3 Weight percent and preferably from about 0.3 to about 1 weight percent of the germicide.
  • the solvent is present in suflicient quantity to completely dissolve all of the germicide employed. It will be appreciated that the amount of the solvent must be within the limits allowed by the final formulation. In general, the germicide can be dissolved in about several times its own weight of the solvent, and it is preferred to use from about a 5 to about 30 fold amount of the solvent, based on the amount of the germicide. If the resulting solution is found too viscous for easy handling, it can be thinned with some compatible co-solvent, such as a short chain alkanol, or a short chain alkylaryl sulfonate, such as ammonium xylene sulfonate.
  • some compatible co-solvent such as a short chain alkanol, or a short chain alkylaryl sulfonate, such as ammonium xylene sulfonate.
  • the amount of the solubilizing and solution-stabilizing adjuvant can be conveniently referred to as a solubilizing amount and this term is intended to refer to an amount which is capable of providing initial solubility and continued solubility in the final formulation.
  • aqueous base compositions which may be detergents, soaps, disinfectants, sanitizers, and the like.
  • the pH of the final composition can be adjusted to meet the use requirements to a level at which germicide could not have been initially dissolved. In this manner, stable germicidal compositions having a pH from about 6 to about 8 and preferably from about 6 to 7 can be provided.
  • the germicide is added to and dissolved in the selected solvent.
  • suitable hydroxides such as ammonium hydroxide, an alkali metal hydroxide, e.g., sodium hydroxide, potassium hydroxide, and the like, can be used to raise the pH. Agitation or elevated temperatures can be employed to facilitate solution.
  • the pH of the solution may be reduced or the solution may be admixed with other components of the final formulation before the pH of the resulting final formulation is adjusted.
  • the pH can safely be adjusted to levels which are as low as about 6.0 without danger of loss of the germicide by the formation of insoluble precipitates.
  • the pH can be conveniently reduced by means of dilute sulfuric acid, dilute sulfonic acid, glacial acetic acid, and the like. It is to be understood that the pH need not be adjusted but may be left at relatively high levels as, for example, in heavy duty detergent formulations.
  • stable formulations as herein disclosed comprise from about 1 to about 20 weight percent and preferably about 2 to about 6 weight percent of the selected solvent or a mixture of selected solvents, from about 0.1 to about 3 weight percent and preferably from about 0.3 to about 1 weight percent of the germicide, from about 3 to about 35 weight percent and preferably 0 about 5 to about 15 weight percent of an organic detergent.
  • the formulation can also contain various perfumes, dyes, fillers, emollients, and other well-known additives and adjuvants, commonly employed in such formulations.
  • Sutiable liquid detergent formulations containing conventional organic detergent components with which the dissolved helogenated organic germicides can be blended are, for example, those comprising aqueous solutions of long chain alkylaryl sulfonates, short chain alkylaryl sulfonates, alkali metal phosphates, fatty alcohols, sulfated alcohol-ethylene oxide condensates, alkalies, dyes, brighteners, perfumes, and other compatible adjuvants.
  • Formulations in which the halogenated organic germicides are present in an amount of from 0.1 percent to 1 percent can be provided through the practice of this invention.
  • Such formulations may contain from about 5 to about 30 percent of a long chain alkylbenzene sulfonate preferably having from about 10 to 18, preferably about 12, carbons in the alkyl chain, about 3 to about 15 percent of a sulfated dodecylphenol condensed with ethylene oxide in a 1:6 mole ratio, about 3 to about 15 percent of a sulfated fatty alcohol condensed with ethylene oxide in a 1:35 mole ratio, up to about 11% of a fatty (C to C alcohol, about 2 to about 15 percent of lauric diethanolamide, about 8 to about 15 percent of a short chain alcohol such as ethanol, up to about 5 percent of @nylphenol condensed with ethylene oxide in a mole ratio of about 1:9, about 5 to about 15 percent of a polyphosphate, various perfumes, color
  • the above six formulations can be prepared by dissolving the 3,4,S-tribromosalicylanilide in the lauric diethanolamide at a temperature of about 80 C. The resulting solution can be cooled and then blended with the remaining components of the final formulation.
  • EXAMPLE 1 Four grams of a halogenated organic ger-micide containing about 98 weight percent 3,4',5-tribromosalicylanilide were added to 20 grams of lauric diethanolamide (pH of about 12.8) at a temperature of about 80 F., and the mixture stirred for about minutes. The resulting solution was then allowed to stand overnight at room temperature to allow entrapped air to escape. A clear, stable, and homogeneous solution was obtained.
  • EXAMPLE 2 Four grams of the halogenated organic germicide described in Example 1 were mixed with and dissolved in a mixture (pH about 12.8) of 20 grams of lauric diethanolamide and 10 grams of ethyl alcohol denatured with about 1 percent by volume of diethylphthalate at a temperature of 80 F. A clear, stable solution was obtained upon cooling.
  • EXAMPLE 3 Four grams of the halogenated organic germicide described in Example 1 were mixed with and dissolved in a blend (pH about 12.8) of 20 grams of lauric diethanolamide and 10 grams of 40% ammonium xylenesulfonate at a temperature of 80 F. Upon cooling, a clear, stable solution was obtained.
  • EXAMPLE 4 Twenty grams of a halogenated organic germicide containing about 98 weight percent 3,4',5 tribromosalicylanilide were added to 100 grams of lauric diethanolamide (pH about 12.8) and mixed for one hour at about 80 F. The germicide dissolved rapidly to provide a clear solution. The pH of the solution was then reduced to about 6.4 by the addition of grams of glacial acetic acid. After standing overnight, the solution was still clear and no evidence of precipitation was apparent.
  • EXAMPLE 5 Twelve grams of a halogenated organic germicide containing about 98 weight percent 3,4,5 tribromosalicylanilide were dissolved in 60 grams of triethanolamine at a temperature of about 80 F, and a pH of about 9.5. The resulting clear solution was diluted with 20 grams of water to provide a clear solution having a pH of about EXAMPLE 6
  • the undiluted solution of 3,4,5-tribromosalicylanilide described in Example 5 was incorporated into a liquid detergent composition comprising ammonium dodecylbenzene sulfonate, ammonium salt of a sulfated fatty alcohol condensed with ethylene oxide, lauric diethanolamide, ainmonium xylene sulfonate, perfume and water.
  • the pH of the final composition was then adjusted to about 6.2.
  • the resulting solution was clear. In these experiments, a clear solution was obtained whether the germicide was added to the detergent components prior to or after the addition of the lauric diethanolamide component of
  • a liquid detergent formulation comprising:
  • EXAMPLE 8 The solubility of 3,4,5-tribromosalicylanilide in alkaline anionic surfactant solutions of relatively high con centration is shown in the following series of formulations.
  • Constant agitation of the finished liquid detergent is unnecessary. Such agitation would be necessary if the germicide were present as suspended particles.
  • the use of a premixed solution of germicide in a selected solvent provides for the preparation of master-mixes which improves uniformity, reduces the effect of small weighing errors, and eliminates the necessity of multiple weighings of dry material.
  • a process for preparing stable aqueous liquid organic detergent solution compositions consisting essentially of a halogenated organic germicide selected from the group consisting of mono-, di-, triand tetrabrominated salicyl anilides and trichlorocarbanilide; said process comprising the .steps of (1) predissolving the germicide in a solubilizing amount of an alkaline solvent selected from the group consisting of:
  • fatty acid alkanol amides having from about 6 to about 18 carbon atoms in the fatty acid portion of the molecule
  • alkaline aqueous solutions of anionic sulfonated or sulfated surface active agents selected from the group consisting of alkyl benzene sulfonates, sulfated fatty alcohol-ethylene oxide condensates and sulfated dodecyl phenol-ethylene oxide condensates containing at least about 25 weight percent of the surface active agent; and
  • solubilizing amount of the alkaline solvent is from about 5 to about 30 fold the amount of the germicide.
  • a stable aqueous liquid organic detergent solution composition consisting essentially of a blend of (A) from about 2 to about 15 parts by weight of a solution of a halogenated organic germicide selected from the group consisting of mono-, di-, triand tetrabrominated salicylanilides and trichlorocarbanilide dissolved in a solubilizing amount of an alkaline solvent selected from the group consisting of (1) fatty acid alkanol amides having from about 6 to about 18 carbon atoms in the fatty acid portion of the molecule;
  • alkaline aqueous solutions of nonionic alkyl phenol-ethylene oxide condensate surface active agents selected from the group consisting of octyl and nonyl phenols condensed with from 5 to 9 moles of ethylene oxide containing at least about 25 weight percent of the surface active agent; and
  • alkaline aqueous solutions of anionic sul-fonated or sulfated surface active agents selected from the group consisting of dodecyl benzene sulfonates, sulfated fatty alcohol-ethylene oxide condensates and sulfated alkyl phenol-ethylene oxide condensates containing at least about 25 weight percent of the surface active agent; and
  • composition as defined by claim 6 wherein the germicide is 3,4,5-tribromosalicylanilide.
  • composition as defined by claim 6 wherein the alkaline solvent is lauric diethanolamide.
  • composition as defined by claim 6 wherein the solubilizing amount of the solvent is from about 5 to about 30 fold the amount of the germicide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Transportation (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US680946A 1965-04-21 1967-11-06 Liquid detergent Expired - Lifetime US3594322A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925227A (en) * 1972-05-31 1975-12-09 American Home Prod Novel laundering compositions
US3933671A (en) * 1974-02-27 1976-01-20 The Procter & Gamble Company Germicidal cleaning composition and method
US3992332A (en) * 1974-08-22 1976-11-16 Hemson Joseph Zenon Liquid composition for fabric treatment
US4383028A (en) * 1981-08-03 1983-05-10 Lorin W. Boots Photographic chemistry
US5922768A (en) * 1998-05-01 1999-07-13 Colgate-Palmolive Co. Carbanilide compositions
WO2002005643A3 (en) * 2000-07-14 2003-07-17 Procter & Gamble Biocide compositions and methods and systems employing same
US20040072908A1 (en) * 2000-07-14 2004-04-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same
EP3124585B1 (en) 2015-07-30 2018-08-22 The Procter and Gamble Company Water-soluble unit dose article

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51109911A (en) * 1975-03-25 1976-09-29 Sadaaki Nishimura Kyoryokubofu bokabiseisenzai

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925227A (en) * 1972-05-31 1975-12-09 American Home Prod Novel laundering compositions
US3933671A (en) * 1974-02-27 1976-01-20 The Procter & Gamble Company Germicidal cleaning composition and method
US3992332A (en) * 1974-08-22 1976-11-16 Hemson Joseph Zenon Liquid composition for fabric treatment
US4383028A (en) * 1981-08-03 1983-05-10 Lorin W. Boots Photographic chemistry
US5922768A (en) * 1998-05-01 1999-07-13 Colgate-Palmolive Co. Carbanilide compositions
WO1999057238A1 (en) * 1998-05-01 1999-11-11 Colgate-Palmolive Company Stable carbanilide composition
WO2002005643A3 (en) * 2000-07-14 2003-07-17 Procter & Gamble Biocide compositions and methods and systems employing same
JP2004503568A (ja) * 2000-07-14 2004-02-05 ザ、プロクター、エンド、ギャンブル、カンパニー 殺生物剤組成物及び殺生物剤組成物使用にあたっての方法及びシステム
US20040072908A1 (en) * 2000-07-14 2004-04-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same
US7319112B2 (en) 2000-07-14 2008-01-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same
EP3124585B1 (en) 2015-07-30 2018-08-22 The Procter and Gamble Company Water-soluble unit dose article

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LU50950A1 (en)) 1966-10-21
CH471887A (de) 1969-04-30
BE679866A (en)) 1966-10-21
NL6605236A (en)) 1966-10-24
GB1138456A (en) 1969-01-01

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