US3629126A - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

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Publication number
US3629126A
US3629126A US867965A US3629126DA US3629126A US 3629126 A US3629126 A US 3629126A US 867965 A US867965 A US 867965A US 3629126D A US3629126D A US 3629126DA US 3629126 A US3629126 A US 3629126A
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United States
Prior art keywords
percent
weight
water
liquid detergent
sulfobetaine
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Expired - Lifetime
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US867965A
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English (en)
Inventor
Walter Fries
Rolf Nagel Puchta
Wolfgang Gundel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013Liquid compositions with insoluble particles in suspension
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821Carboxylic acids; Esters thereof with monohydroxyl compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6523Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
    • C08G18/6529Compounds of group C08G18/3225 or polyamines of C08G18/38
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/92Sulfobetaines ; Sulfitobetaines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides

Definitions

  • Liquid detergent compositions comprising 40 to 70% water and 30 to 60% dissolved and suspended materials consisting essentially of the following in percent by weight based upon the total weight of the suspended and dissolved material: 1 to of at least one salt of a cellulose ether carboxylic acid, 5 to 20% of at least one member selected from the grou consisting of surface active amine oxides and surface active ether sulfates, O to 40% conventional detergent additives, 0 to 30% of wash active substances other than the amine oxides and/or ether sulfates and 0.5 to 25% of a mixture of 40 to 60% of at least one C to C fatty alcohol sulfate and 60 to 40% of at least one sulfobetaine.
  • This invention relates to liquid laundry detergents. It more particularly refers to such liquid detergents which contain suspended but undissolved therein substances which render the detergent composition suitable for use as a boiling water detergent.
  • Some of the attempted solutions to this problem include: combination of cellulose ether carboxylic acid salts and hydrogenated castor oil (see German Pat. 1,152,779); cellulose ether carboxylic acid salts and polyvinyl alcohol of polyvinyl pyrrolidone (see German Pat. 1,156,927); two different types of cellulose derivatives (see German Pat. 1,064,638); and combinations of cellulose ether carboxylic acid salts with bentonite and/or urea combined with the cleansing agents (see German Pat. 1,152,779).
  • one embodiment of this invention resides in the discovery that aqueous suspensions of cellulose ether carboxylic acid salt, particularly cellulose glycolic acid salt, have markedly improved sedimentation stability if there is present in the suspension system a mixture of at least one sulfobetaine and at least one C to C fatty alcohol sulfate.
  • the sulfobetaine portion of this mixture comprises at least one compound of at least one of the formulas:
  • R1 O SO wherein Ft is a hydrophobic moiety substituent, suitably 0f the straight or branched chain aliphatic or cycloaliphatic hydrocarbon type having about 8 to 24 carbon atoms, preferably containing about 12 to 18 carbon atoms; R and R are the same or different and are aliphatic residues containing up to about 5 carbon atoms; R and R are the same or different and may be hydrogen or aliphatic hydrocarbon residues containing up to about 3 carbon atoms; and n is the integer one (1) or two (2).
  • a typical liquid detergent composition contains various components to perform various given functions including: anionic surfactants and/or non-ionic surfactants; fatty alcohol sulfate other than the suspension stabilizer referred to above; hydrotropic substances; foam stabilizers; washactive substances such as soaps; and wash alkalis. All these components of liquid detergent compositions are known per se and are known for use in this art. Detergent additives such as water glass, bleach stabilizer, optical brighteners, organic dirt dispersants and perfumes can also be included.
  • the anionic surfactants are exemplified by soaps, alkylbenzene sulfonates, fatty alcohol sulfates, fatty acid monoglyceride sulfates, fatty alcohol monoglycerin ether sulfates, other sulfates of partial esters of higher fatty acids with polyhydric alcohols, fatty acid or fatty alcohol esters of oxalkyl sulfonic acids, e.g. fatty acid esters of hydroxy and dihydroxy propane sulfonic acid or of oxalkyl carboxylic acids, and/or fatty amides of amino sulfonic acids or amino carboxylic acids.
  • amine oxides which are oxidation products of tertiary amines.
  • tertiary amines have a higher alkyl radical containing about 8 to 22 (preferably 18) carbon atoms and two lower aliphatic radicals containing up to about 5 (preferably 13) carbon atoms.
  • the higher alkyl radical can be linked to the amine nitrogen through one or more hydroxy propyl groups.
  • the surfactant ether sulfates are sulfation products of ethoxylated fatty alcohols or alkyl phenols having about 1 to (preferably about 2 to 12) ethylene glycol moieties per molecule.
  • the alkyl groups of the alkyl phenol and the fatty alcohol suitably contain about 8 to 22 (preferably 10 to 18) carbon atoms.
  • non-ionic surfactants are exemplified by addition products of ethylene oxide to fatty alcohols, fatty acids or partial esterification or etherification products thereof with polyhydric alcohols; addition products of ethylene oxide to high molecular weight sulfonic and/or carboxylic acids or acid amides; and addition products of ethylene oxide to higher molecular weight polypropylene glycol.
  • the anionic surfactant may be combined with the nonionic surfactant where the combination has an hydrophobic radical such as an aliphatic hydrocarbon radical having about 8 to 24 carbon atoms, preferably 10 to 16 carbon atoms.
  • the additional fatty alcohol sulfate generally contains less than about 16 carbon atoms, preferably 10 to 14 carbon atoms, and most preferably 12 to 14 carbon atoms such as fatty alcohols prepared from coconut or palmkernel oil fatty acids.
  • hydrotropic substances referred to above are exemplified by alkali sulfonates of aromatic hydrocarbon residues including benzene, toluene, xylene, naphthalene and other similar residues.
  • foam stabilizers can be used including higher molecular weight carboxylic or sulfonic acid amides substituted or unsubstituted on the amide nitrogen.
  • amides include fatty acid amides, alkyl sulfonic acid amides or alkylbenzene sulfonic acid amides.
  • substituent may be derived from monoethanol amine or like substances or the substituent may be a mono or polyalkylol or polyglycol residue.
  • the reaction products of the above substituted or unsubstituted acid amides with about 1 or 5 moles of ethylene oxide have been found to be suitable for this application.
  • the wash-active substances include soaps, synthetic detergents of the sulfate or sulfonate type and surface active polyethylene glycol ethers. It has been found desirable to utilize combinations of wash-active substances in order to invoke the foam suppressing properties of each with respect to the other whereby the total foaming propensity of the composite wash-active component is substantially reduced. Where required or desired, additional foam suppressors, such as for example addition products of propylene oxide to surface active polyethylene glycol ethers which are water-soluble at room temperature, may be used.
  • Anionic wash-active substances are preferably used in the form of a readily water-soluble salt or organic base. These include sodium or potassium as the most common examples of salts and mono-, dior trialkanol (particularly ethanol) amine as the most common examples of useful organic bases. Of course, mixtures of salts and/or bases can be used.
  • Wash alkalis generally include pyroor tripolyphosphates in the form of readily water-soluble salts or organic bases of the same character as described above. Also included in this group of components are chelating agents such as for example nitrilo-triacetic acid or ethylene diamine tetra-acetic acid in their salt or other soluble form.
  • liquid detergent components which can be employed in compositions of this invention include water-glass and solubilizers such as toluene sulfonate, xylene sulfonate, etc.
  • the preferred medium for the compositions of this invention is water. It has been found to be practical however to, in some cases, replace a part of the water with any of a number of water-soluble organic solvents such as for example lower alkanols having about 1 to 4 carbon atoms.
  • compositions according to this invention are made up of about 40 to 70 percent by Weight, preferably to percent, of the solvent medium, water or water containing up to about 20 percent by weight of a soluble cosolvent as referred to above. It is preferred to use at most about 10 percent and most preferred to use 1 to 8 percent of the cosolvent.
  • the remainder of the liquid detergent composition 30 to 60 percent by Weight and preferably 40 to 50 percent is made up of the dissolved and suspended matter.
  • This portion of the liquid detergent composition includes the above recited components in the following proportions by weight based upon the total weight of suspended or dissolved matter:
  • Amine oxide or surfactant ether sulfate or combinations of both about 5 to 20 (preferably 10 to 16) percent, most preferably at least as much as the fatty alcohol sulfate as hereinafter stated:
  • lPyroand tripolyphosphates as well as related materials alone or in combination with each other, about 20 to 50 (preferably 30 to 40) percent;
  • Cellulose ether carboxylic acid salt about 1 to 5 (preferably 1 to 2) percent:
  • wash-active substances than those referred to hereinbefore as amine oxides or surfactant ether sulfates, such as for example wash-active sulfates or sulfonates, about 0 to 30 (preferably 15 to 25) percent.
  • sulfobetaines there were used reaction products of dimethyl fatty amines with propanesultone, such as described in the aforementioned German provisional patent 1,135,606. These products are referred to below as sulfobetaines.
  • sulfobetaines containing hydroxy groups such as described in German provisional patent 1,162,966 and as obtained by reaction of dimethyl fatty amines with epichlorhydrin followed by treatment of the resultant quaternary ammonium salts containing a chlorhydrin group, with salts of sulfurous acid.
  • hydroxy sulfobetaines are hereinafter referred to as hydroxy sulfobetaines.
  • the number of carbon atoms present in the fatty radical is also indicated; this fatty radical came from natural fatty acids and was, therefore, a straight-chain radical.
  • liquid detergent samples contained in detail the following quantities of sulfobetaine, referred to the total Weight of the liquid detergent:
  • Liquid detergents of corresponding composition without sulfobetaines showed a substantially poor stability of the suspensions; cellulose glycolic acid salts in general deposited within 3 weeks. Products in which the tallow oil alcohol sulfate had been replaced by the corresponding quantity of coconut oil alcohol sulfate behaved in similar manner.
  • EXAMPLE 2 The formula of the liquid detergents described in this example differed from that of Example 1 by a smaller content of amine oxide and a higher content of tallow oil alcohol sulfate; both were present in an amount of 5.5 percent by Weight of the detergent.
  • the following amounts of sulfobetaine, referred to the total weight of the liquid detergent were incorporated:
  • a liquid detergent composition consisting essentially of 40 to 70% water and 30 to 60% dissolved and suspended components as follows in percent by weight based on the total weight of the dissolved and suspended components:
  • sulfobetaine selected from the group consisting of wherein Ft is a hydrophobic radical selected from the group consisting of alkyl and cycloalkyl containing 8 to 24 carbon atoms, R and R is each an alkyl containing up to 5 carbon atoms, R and R is each a member selected from the group consisting of hydrogen and alkyl containing up to 3 carbon atoms and n is a whole positive integer of at most 2.
  • composition according to claim 1 additionally containing at least one water soluble lower alkanol.
  • composition according to claim 1 wherein said dissolved and suspended components comprise in percent by Weight based upon the total weight of the dissolved and suspended components the following:
  • composition according to claim 1 wherein said amine oxide and said ether sulfate together are present in an amount at least equivalent to the amount of said fatty alcohol sulfate.
  • composition according to claim 1 consisting essentially of:
  • alkyl dimethylamine oxide wherein said alkyl group is derived from (I -C coconut oil acid,
  • composition according to claim 1 consisting essentially of:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
US867965A 1965-03-30 1969-10-20 Liquid detergent composition Expired - Lifetime US3629126A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEH55644A DE1257339B (de) 1965-03-30 1965-03-30 Waessrige Fluessigwaschmittel mit einem Gehalt an celluloseaethercarbonsauren Salzen

Publications (1)

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US3629126A true US3629126A (en) 1971-12-21

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US867965A Expired - Lifetime US3629126A (en) 1965-03-30 1969-10-20 Liquid detergent composition

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US (1) US3629126A (enrdf_load_stackoverflow)
AT (1) AT270027B (enrdf_load_stackoverflow)
BE (1) BE678536A (enrdf_load_stackoverflow)
CH (1) CH473218A (enrdf_load_stackoverflow)
DE (1) DE1257339B (enrdf_load_stackoverflow)
DK (1) DK126126B (enrdf_load_stackoverflow)
ES (1) ES324866A1 (enrdf_load_stackoverflow)
GB (1) GB1077646A (enrdf_load_stackoverflow)
NL (1) NL6602717A (enrdf_load_stackoverflow)
SE (1) SE342254B (enrdf_load_stackoverflow)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL275490A (enrdf_load_stackoverflow) * 1961-03-04

Also Published As

Publication number Publication date
AT270027B (de) 1969-04-10
DK126126B (da) 1973-06-12
DE1257339B (de) 1967-12-28
GB1077646A (en) 1967-08-02
NL6602717A (enrdf_load_stackoverflow) 1966-10-03
SE342254B (enrdf_load_stackoverflow) 1972-01-31
CH473218A (de) 1969-05-31
BE678536A (enrdf_load_stackoverflow) 1966-09-28
ES324866A1 (es) 1967-02-16

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