EP0670834B1 - Alkylidene glyzerol-tenside und diese enthaltende waschmittelzusammensetzungen - Google Patents

Alkylidene glyzerol-tenside und diese enthaltende waschmittelzusammensetzungen Download PDF

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Publication number
EP0670834B1
EP0670834B1 EP94900806A EP94900806A EP0670834B1 EP 0670834 B1 EP0670834 B1 EP 0670834B1 EP 94900806 A EP94900806 A EP 94900806A EP 94900806 A EP94900806 A EP 94900806A EP 0670834 B1 EP0670834 B1 EP 0670834B1
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EP
European Patent Office
Prior art keywords
detergent composition
compound
cosurfactant
diglycerol
surfactant
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EP94900806A
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English (en)
French (fr)
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EP0670834A1 (de
Inventor
Robert John 134 Town Lane Crawford
Richard John 12 Ashbrook Terrace Curtis
Abid Nadin 29 Hewitt Street Khan-Lodhi
Malcolm Philip 69 Slingsby Drive Upton Nicholls
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from US07/981,737 external-priority patent/US5389279A/en
Priority claimed from GB939319462A external-priority patent/GB9319462D0/en
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Publication of EP0670834A1 publication Critical patent/EP0670834A1/de
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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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention provides novel alkylidene glycerol surfactants useful in detergent compositions.
  • Condensation products of aldehydes with glycerol are described in GB 414 772 (Johnson).
  • lauric aldehyde may be reacted with glycerol to give the monoglycerol acetal, described as having a five-membered dioxolane ring structure:
  • Such products are hydrophobic but introduction of water-solubilising groups gives products which are useful as wetting, washing, foaming and dispersing agents.
  • the compound shown above does not itself exhibit foaming properties, but may be converted by reaction with chlorosulphonic acid to give a high-foaming anionic surfactant, or ethoxylated to give a nonionic surfactant.
  • EP 12 543A discloses cyclic acetals and ketals of glycerol and other polyols, and their use as emollients in cosmetic, toilet and household cleaning compositions.
  • reaction product of an aldehyde RCHO with glycerol which comprises a mixture of a five-membered ring structure A (1,3-dioxolane) and a six-membered ring structure B (1, 3-dioxane), the proportions of which can be varied in a known manner by varying the reaction conditions:
  • These materials may optionally be alkoxylated, acylated or alkylated.
  • Monoglycerol ketals are disclosed in US 3 909 460 and US 3 948 953 (McCoy/Texaco Inc). These materials, prepared by the condensation of ketones with glycerol, have the formula where R and R' are alkyl groups containing in total 6 to 30 carbon atoms. Unlike the monoglycerol acetals, these materials can exist only in a five-membered ring form. Like the monoglycerol acetals, these materials require the introduction of a solubilising group, for example, sulphate or polyoxyethylene, to give water-soluble surfactants.
  • a solubilising group for example, sulphate or polyoxyethylene
  • the present inventors have now prepared acetals and ketals containing two or more glycerol residues. These materials, which are liquids or soft solids, behave as effective, water-soluble nonionic surfactants especially useful in detergent compositions for washing fabrics. Certain combinations with other, known surfactants have been found to display synergistic oily soil detergency.
  • the new materials behave comparably to ethoxylated alcohol nonionic surfactants, and are potential candidates for replacing them wholly or partially in detergent compositions if a reduction in the use of ethoxylated materials should become considered desirable on environmental grounds.
  • the present invention accordingly provides a compound of the formula I: wherein R 1 represents a linear or branched alkyl or alkenyl group and R 2 represents a hydrogen atom or a linear or branched alkyl or alkenyl group, the total number of carbon atoms in R 1 and R 2 being from 7 to 17; and A represents a monoglycerol or diglycerol unit.
  • a second subject of the present invention is the use of a compound as defined in the previous paragraph as a surfactant or wetting agent.
  • a third subject of the present invention is a detergent composition having a surfactant system comprising a compound as defined above.
  • a fourth subject of the present invention is a process for the preparation of a compound of the formula I, in which an aldehyde or ketone of the formula R 1 -CO-R 2 is reacted with an oligomer of glycerol.
  • the compounds of the formula I given above are believed to be novel materials.
  • the novelty resides in the presence of more than one - specifically two or three - glycerol units in the molecule.
  • These two classes of compounds will be referred to respectively as alkylidene diglycerols and alkylidene triglycerols.
  • the diglycerols (A is a monoglycerol unit) exist as a mixture of two structural isomers, of the formulae IIa and IIb: the linear isomer IIa being the predominant species.
  • the triglycerols (A is a diglycerol unit) exist as a mixture of six structural isomers, as shown in the following formulae IIIa to IIIf. Again, the linear isomer IIIa predominates.
  • the predominant linear isomers IIa and IIIa of the alkylidene di- and triglycerols may be represented by the general formula Ia: wherein n is 1 or 2.
  • the total number of carbon atoms in the groups R 1 and R 2 in the compounds of the invention may range from 7 to 17, preferably from 9 to 13. In principle the carbon atoms may be distributed in any proportions between the two groups.
  • the compounds studied by the present inventors fall into two classes: those in which R 2 is a hydrogen atom, and those in which R 2 is a methyl group.
  • R 1 in both cases is a linear or branched alkyl or alkenyl group.
  • R 2 is a hydrogen atom, derived from an aldehyde R 1 CHO
  • 1-alkylidene (di- or tri-)glycerols or (di- or tri-)glycerol acetals while compounds in which R 2 is a methyl group, derived from a methyl ketone R 1 COCH 3 , are referred to as 2-alkylidene (di- or tri-)glycerols or (di- or tri-)glycerol ketals.
  • R 2 is a hydrogen atom (1-alkylidene di- and triglycerols, or di- or triglycerol acetals) also exist in a six-membered ring isomeric form Ib:
  • HLB hydrophilic-lipophilic balance
  • alkylidene glycerols range from liquids to solids depending on the length and nature of the alkyl or alkenyl chain, the number of glycerol units in the molecule, and the particular isomer or mixture or isomers present.
  • the linear 1- and 2-decylidene diglycerols are liquids of low viscosity, and are thus especially suitable for formulation into liquid detergent compositions, more especially non-aqueous liquid detergent compositions.
  • the dodecylidene diglycerols are solids, and preferred for incorporation into particulate detergent compositions.
  • the HLB values of the diglycerols are estimated from phase behaviour to be 9.5-10.5, comparable to C 12 ethoxylated alcohol having an average degree of ethoxylation of 3-4 (hereinafter referred to for convenience as C 12 EO 3-4 ). However, their oily soil detergency is somewhat better.
  • These materials may advantageously be used in combination with cosurfactants of higher HLB (preferably >9, more preferably 9-13), such as sulphate and sulphonate-type anionic surfactants and more highly ethoxylated nonionic surfactants, for example, C 8-18 EO 5-10 .
  • cosurfactants of higher HLB preferably >9, more preferably 9-13
  • sulphate and sulphonate-type anionic surfactants and more highly ethoxylated nonionic surfactants, for example, C 8-18 EO 5-10 .
  • the linear decylidene and dodecylidene triglycerols are soft liquid-crystalline solids, suitable for incorporation into both aqueous liquid and particulate detergent compositions. They are estimated to have HLB values in the range 12-13, comparable to C 12 EO 8 nonionic surfactant.
  • the oily soil detergency is very similar. These materials may most suitably be used in combination with cosurfactants of lower HLB (preferably ⁇ 9, more preferably 7-9), for example, C 8-18 EO 2-6 . Synergistic oily soil detergency has been observed with C 12 EO 3 .
  • novel alkylidene di- and triglycerols of the invention may be prepared by condensation of the appropriate aldehyde or ketone with a glycerol oligomer or mixture of oligomers.
  • novel surfactants of the present invention may be incorporated in detergent compositions of all physical types, for example, powders, liquids, gels and solid bars.
  • compositions whatever their physical form, will generally contain detergent-active compounds and detergency builders, and may optionally contain bleaching components and other active ingredients to enhance performance and properties.
  • the detergent compositions of the invention will contain a surfactant system comprising one or more detergent-active compounds (surfactants), the surfactant system consisting at least in part of an alkylidene di- or triglycerol in accordance with the present invention.
  • surfactants one or more detergent-active compounds (surfactants)
  • the surfactant system consisting at least in part of an alkylidene di- or triglycerol in accordance with the present invention.
  • one or more cosurfactants may also be present. These may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly C 12 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8- C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10- C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • the total amount of surfactant present will depend on the intended end use and may be as low as 0.5 wt%, for example, in a machine dishwashing composition, or as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate.
  • the detergent compositions of the invention will generally also contain one or detergency builders.
  • the total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt% in powders, from 5 to 25 wt% in aqueous liquids and from 10 to 40 wt% in non-aqueous liquids.
  • Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst).
  • Inorganic phosphate builders for example, sodium orthophosphate, pyrophosphate and tripolyphosphate, may also be present, but on environmental grounds those are no longer preferred.
  • Zeolite builders may suitably be present in amounts of from 5 to 60 wt%, preferably from 10 to 50 wt%. Amounts of from 10 to 45 wt% are being especially suitable for particulate (machine) fabric washing compositions.
  • the zeolite used in most commercial particulate detergent compositions is zeolite A.
  • maximum aluminium zeolite P zeolite MAP
  • Zeolite MAP is an alkali metal aluminosilicate of the P type having a silicon to aluminium ratio not exceeding 1.33, preferably not exceeding 1.15, and more preferably not exceeding 1.07.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
  • Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • Machine dishwashing compositions may suitably contain a chlorine bleach system, while fabric washing compositions may more desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • peroxy bleach compounds for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
  • organic peroxides such as urea peroxide
  • inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • sodium percarbonate having a protective coating against destabilisation by moisture Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
  • Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED).
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
  • An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate or sodium perborate monohydrate) optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
  • a peroxy bleach compound preferably sodium percarbonate or sodium perborate monohydrate
  • a bleach activator preferably sodium percarbonate or sodium perborate monohydrate
  • a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
  • Detergent compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • compositions containing little or no sodium carbonate are also within the scope of the invention.
  • powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
  • a preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
  • detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
  • alkylidene di- and triglycerols in accordance with the present invention may advantageously be incorporated into both aqueous and non-aqueous liquid detergent compositions.
  • Aqueous liquids in accordance with the invention may be isotropic. Alternatively they may be structured liquids comprising a dispersion of lamellar droplets in an aqueous continuous phase, optionally containing suspended particulate solid. Structured liquids of this type without suspended solid are disclosed, for example, in US 4 244 840, while structured liquids containing suspended solids are disclosed in US 4 244 840 and also in EP 38 101A, EP 160 342A and EP 140 452A.
  • the liquids may contain a deflocculating polymer as described and claimed in EP 346 995A (Unilever), suitably in an amount of from 0.01 to 5 wt%.
  • Non-aqueous liquids in accordance with the invention contain not more than 5 wt%, and preferably less than 3 wt%, water. They may take the form of a particulate solid phase dispersed in a non-aqueous liquid phase, the latter comprising one or more nonionic surfactants, suitably in an amount of from 1 to 90 wt%, preferably from 5 to 75 wt% and more preferably from 20 to 60 wt%.
  • the non-aqueous liquids may contain a hydrophobically modified dispersant, for example, a hydrophobic silica, to improve physical stability.
  • a deflocculant for example, an acid as described and claimed in EP 266 199A (Unilever), may also advantageously be present.
  • 1,1-Dimethoxydecane (22.0g, 0.10mol), diglycerol (86.0g, 0.52mol) and p-toluene sulphonic acid (0.25g) in dimethyl formamide (100 cm 3 ) were heated at 100°C for 7 hours.
  • the reaction mixture was allowed to cool and water (400 cm 3 ) was added and the mixture extracted with ether (2x300 cm 3 ).
  • the combined ether extracts were washed with water (2x250 cm 3 ) and brine (250 cm 3 ) and dried over anhydrous sodium sulphate.
  • the solvent was removed at reduced pressure to give the crude product.
  • Short path distillation using a Kugelrohr apparatus afforded pure 1-decylidene diglycerol (14.7g, 48%) .
  • the compound was characterised by nuclear magnetic resonance (NMR) spectroscopy: delta H (360 MHz, CDCl 3 , TMS) 0.89 (3H, t, CH 3 -), 1.3-1.4 (14H, m, -(CH 2 ) 7 -), 1.65 (2H, m, C 8 H 17 -CH 2 -), 3.5-4.4 (10H, m, -O-CH 2 -CH(O)-CH 2 -O-), 4.88,4.98 (1H, t, C 9 H 19 -CH-).
  • NMR nuclear magnetic resonance
  • 1,1-Dimethoxydodecane (11.5g, 0.05mol), triglycerol (240g, 1.0mol) and p-toluene sulphonic acid (0.5g) in dimethyl formamide (250 cm 3 ) was heated at 100°C for 5 hours.
  • the reaction mixture was allowed to cool and water (400 cm 3 ) was added and the mixture extracted with ether (2x300 cm 3 ).
  • the combined ether extracts were washed with water (2x250 cm 3 ) and brine (250 cm 3 ) and dried over anhydrous sodium sulphate.
  • the solvent was removed at reduced pressure to give the crude product.
  • Short path distillation using a Kugelrohr apparatus was used to remove low boiling impurities to leave near-pure 1-dodecylidene triglycerol ( 14.2g, 70%).
  • the compound was characterised by nuclear magnetic resonance (NMR) spectroscopy: delta H (360 MHz, CDCl 3 , TMS) 0.88 (3H, t, CH3-), 1.3-1.4 (18H, m, -(CH 2 ) 9 -), 1.64 (2H, m, C 10 H 21 -CH 2 -), 3.5-4.4 (15H, m, -O-CH 2 -CH(O)-CH 2 -O-), 4.88,4.97 (1H, t, C 11 H 23 -CH-).
  • NMR nuclear magnetic resonance
  • 3 H-radiolabelled triolein was used to assess soil removal. Knitted polyester test cloths carrying this soil (level about 1.9%) were washed in the Tergotometer UR 7227 for 20 minutes, the agitation being 70 rpm, the wash liquor volume being 500 ml, and the wash temperature being 40°C. The surfactants were used at a concentration of 1 g/litre in distilled water in the presence of sodium metaborate buffer (0.05M). Subsequent to the wash, 4 x 1 ml samples of wash liquor were removed from each tergotometer pot and the activity determined using a liquid scintillation counter.
  • decylidene and dodecylidene diglycerols all showed synergistic detergency behaviour when used in combination with the high-HLB cosurfactants, primary alcohol sulphate (cocoPAS) and C 12 EO 8 ethoxylated alcohol.
  • Triolein removal (%) 2-decylidene diglycerol cocoPAS 100 0 30 80 20 68 60 40 52 40 60 48 20 80 46 0 100 44
  • Triolein removal (%) 2-dodecylidene diglycerol cocoPAS 100 0 8 80 20 60 60 40 68 40 60 66 20 80 58 0 100 44
  • detergencies were measured by a method similar to that used in Examples 5 to 8, but the tergotometer wash liquors contained the following ingredients in 24° (French) hard water: g/litre surfactant (total) 1.00 zeolite 2.42 sodium carbonate 1.82 acrylic/maleic copolymer 0.592
  • Triolein removal (%) 1-decylidene diglycerol cocoPAS 100 0 2.5 80 20 58.6 60 40 58.2 40 60 52.8 20 80 44.7 0 100 40.1
  • Triolein removal (%) 1-dodecylidene diglycerol C 10-12 EO 7 nonionic 100 0 1.5 80 20 4.9 60 40 62.0 40 60 65.9 20 80 65.0 0 100 60.7
  • Detergent powders incorporating the compounds of the invention may be prepared to the following formulations (weight %): 13 14 Decylidene or dodecylidene diglycerol 17 - Decylidene or dodecylidene triglycerol - 8.5 C 12-15 EO(av) 7 ethoxylate 8.5 zeolite 32 32 sodium carbonate 12 12 alkaline sodium silicate 0.5 0.5 fatty acid soap 2 2 sodium carboxymethylcellulose 0.6 0.6 sodium perborate monohydrate 15 15 TAED 6.5 6.5 bleach stabiliser (EDTMP) 0.4 0.4 silicone suds suppressor 0.4 0.4 enzymes 1.0 1.0 fluorescer 0.2 0.2 perfume 0.6 0.6 moisture and salts to 100%
  • Example 15 non-aqueous liquid detergent

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Claims (18)

  1. Verbindung der Formel I:
    Figure imgb0019
        worin R1 eine lineare oder verzweigte Alkyl- oder Alkenylgruppe wiedergibt und R2 ein Wasserstoffatom oder eine lineare oder verzweigte Alkyl- oder Alkenylgruppe wiedergibt. wobei die Gesamtzahl, an Kohlenstoffatomen in R1 und R2 7 bis 17 ist und
       A eine Monoglycerin- oder Diglycerineinheit wiedergibt.
  2. Verbindung nach Anspruch 1. der Formel Ia:
    Figure imgb0020
        worin n 1 oder 2 ist.
  3. Verbindung nach Anspruch 1, worin R1 eine C9- oder C11-Alkylgruppe wiedergibt und R2 ein Wasserstoffatom wiedergibt.
  4. Verbindung nach Anspruch 1, worin R1 eine C8- oder C10-Alkylgruppe wiedergibt und R2 eine Methylgruppe wiedergibt.
  5. Verwendung einer Verbindung nach Anspruch 1 als Tensid oder Netzmittel.
  6. Waschmittel, enthaltend ein Tensidsystem, umfassend ein oder mehrere grenzflächenaktive Verbindungen, dadurch gekennzeichnet, daß das Tensidsystem eine Verbindung nach Anspruch 1 umfaßt.
  7. Waschmittel nach Anspruch 6, umfassend als Tensidsystem eine Verbindung der Formel I, worin A eine Monoglyccrineinheit ist, in Kombination mit einem Cotensid mit einem HLB-Wert von mindestens 9.
  8. Waschmittel nach Anspruch 7, worin das Cotensid einen HLB-Wert von 9 bis 13 aufweist.
  9. Waschmittel nach Anspruch 7, worin das Cotensid aus anionischen Sulfat- und Sulfonattensiden und ethoxylierten nichtionischen Tensiden ausgewählt ist.
  10. Waschmittel nach Anspruch 7, worin das Cotensid ein primäres Alkoholsulfat darstellt.
  11. Waschmittel nach Anspruch 7, worin das Cotensid einen C8-18-Alkohol darstellt, der mit durchschnittlich 5 bis 10 Mol Ethylenoxid pro Mol Alkohol ethoxyliert ist.
  12. Waschmittel nach Anspruch 6, umfassend als Tensidsystem eine verbindung der Formel I, worin A eine Diglycerineinheit wiedergibt, in Kombination mit einem Cotensid, das einen HLB-Wert von nicht mehr als 9 aufweist.
  13. Waschmittel nach Anspruch 12, worin das Cotensid einen HLB-Wert im Bereich von 7 bis 9 aufweist.
  14. Waschmittel nach Anspruch 12, worin das Cotensid ein ethoxyliertes, nichtionisches Tensid darstellt.
  15. Waschmittel nach Anspruch 12, worin das Cotensid einen C8-18-Alkohol darstellt, der mit durchschnittlich 2 bis 6 Mol Ethylenoxid pro Mol Alkohol ethoxyliert ist.
  16. Waschmittel nach Anspruch 6 in flüssiger Form.
  17. Waschmittel nach Anspruch 6 in nichtwässeriger, flüssiger Form.
  18. Verfahren zur Herstellung einer verbindung nach Anspruch 1, umfassend Umsetzen eines Aldehyds oder Ketons der Formel R1-CO-R2 mit einem Oligomer von Glycerin.
EP94900806A 1992-11-25 1993-11-17 Alkylidene glyzerol-tenside und diese enthaltende waschmittelzusammensetzungen Expired - Lifetime EP0670834B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US981737 1992-11-25
US07/981,737 US5389279A (en) 1991-12-31 1992-11-25 Compositions comprising nonionic glycolipid surfactants
GB939319462A GB9319462D0 (en) 1992-11-25 1993-09-21 Alkylidene glycerol surfactants and detergent compositions containing them
GB9319462 1993-09-21
PCT/EP1993/003170 WO1994012489A1 (en) 1992-11-25 1993-11-17 Alkylidene glycerol surfactants and detergent compositions containing them

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EP0670834A1 EP0670834A1 (de) 1995-09-13
EP0670834B1 true EP0670834B1 (de) 1997-03-12

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AU (1) AU682835B2 (de)
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WO (1) WO1994012489A1 (de)

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DE10042514A1 (de) * 2000-08-30 2002-03-14 Clariant Gmbh Wässerige Flüssigkeiten enthaltend ein Tensid und ein Acetal
DE10232780A1 (de) * 2002-07-18 2004-02-12 Basf Ag Co-Tenside auf Basis von Aldehyden
PL1954140T3 (pl) 2005-11-22 2013-08-30 Segetis Inc Ketale lewulinianu glicerolu i ich zastosowanie
CN101896474B (zh) 2007-10-09 2016-02-03 希凯迪斯股份有限公司 制备缩酮和乙缩醛的方法
CN102239156B (zh) 2008-09-25 2014-10-15 塞格提斯有限公司 缩酮酯衍生物
BRPI1013943B1 (pt) 2009-06-22 2020-03-17 Segetis, Inc. Composto, método para sintetizar o mesmo, composição e composição lubrificante
WO2011143242A2 (en) 2010-05-10 2011-11-17 Segetis, Inc. Fragrant formulations, methods of manufacture thereof and articles comprising the same
MX336783B (es) 2010-08-03 2016-02-02 Segetis Inc Metodos para la fabricacion de acetales y cetales, y los acetales y cetales producidos mediante dicho metodo.
US8828917B2 (en) 2010-08-12 2014-09-09 Segetis, Inc. Carboxy ester ketal removal compositions, methods of manufacture, and uses thereof
EP2603565B1 (de) 2010-08-12 2015-10-07 Segetis, Inc. Latexbeschichtungszusammensetzungen mit carboxy-ester-ketal-koaleszenten, verfahren zur herstellung und verwendungen davon
US8632612B2 (en) 2010-09-07 2014-01-21 Segetis, Inc. Compositions for dyeing keratin fibers
WO2012037122A2 (en) 2010-09-13 2012-03-22 Segetis, Inc. Fabric softener compositions and methods of manufacture thereof
US8728625B2 (en) 2010-10-18 2014-05-20 Segetis, Inc. Water reducible coating compositions including carboxy ester ketals, methods of manufacture, and uses thereof
JP5832930B2 (ja) * 2012-02-20 2015-12-16 三洋化成工業株式会社 外用組成物
US9458414B2 (en) 2012-09-21 2016-10-04 Gfbiochemicals Limited Cleaning, surfactant, and personal care compositions
US9156809B2 (en) 2012-11-29 2015-10-13 Segetis, Inc. Carboxy ester ketals, methods of manufacture, and uses thereof
CN106946840B (zh) * 2017-04-11 2019-05-24 太原理工大学 一种二甘油单缩醛及其制备方法和应用
US20230174895A1 (en) * 2021-12-08 2023-06-08 The Procter & Gamble Company Glycerol acetal sulfate and sulfonate surfactants

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JP2541226B2 (ja) * 1987-07-06 1996-10-09 日本油脂株式会社 ポリオキシアルキレン誘導体からなるカルボニル化合物の修飾剤
JP2870119B2 (ja) * 1990-05-08 1999-03-10 日本油脂株式会社 アルケニルポリグリセロールエーテルおよびアルケニルイソプロピリデンポリグリセロールエーテル
WO1992008685A1 (fr) * 1990-11-14 1992-05-29 L'oreal Composes amphiphiles non-ioniques derives du glycerol, leur procede de preparation, composes intermediaires correspondants et compositions contenant lesdits composes

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AU5562394A (en) 1994-06-22
DE69308883T2 (de) 1997-07-24
JPH08503476A (ja) 1996-04-16
DE69308883D1 (de) 1997-04-17
AU682835B2 (en) 1997-10-23
EP0670834A1 (de) 1995-09-13
JP2848706B2 (ja) 1999-01-20
BR9307517A (pt) 1999-08-24
ES2100664T3 (es) 1997-06-16
WO1994012489A1 (en) 1994-06-09

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