CN1170428A - Stable liquid detergent compositions comprising fatty acid and silicone oil - Google Patents

Stable liquid detergent compositions comprising fatty acid and silicone oil Download PDF

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Publication number
CN1170428A
CN1170428A CN 95196870 CN95196870A CN1170428A CN 1170428 A CN1170428 A CN 1170428A CN 95196870 CN95196870 CN 95196870 CN 95196870 A CN95196870 A CN 95196870A CN 1170428 A CN1170428 A CN 1170428A
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detergent composition
alkyl
fatty acid
acid
composition according
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R·J·琼斯
P·J·M·贝兹
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/36—Organic compounds, e.g. vitamins containing silicon
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/047—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/225—Polymers
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest

Abstract

A concentrated Nil-Las containing liquid detergent comprising a silicone oil and a fatty acid mixture characterized in that said fatty acid mixture comprises: i) at least 20 % of unsaturated fatty acid; ii) at least 30 % of fatty acid having 16 or more carbon atoms.

Description

The stable liquid detergent compositions that contains lipid acid and silicone oil
Invention field
The present invention relates to the stabilized uniform liquid detergent composition.More specifically, the present invention relates to comprise a kind of liquid detergent composition of foam inhibition system, said foam inhibition system comprises a kind of siloxanes antifoams and a kind of special fatty acid mixt.
Background of invention
In liquid washing agent industry now, a kind of main tendency is to develop towards more spissated liquid washing agent direction.This transformation provides the intrinsic efficiency of producing and use liquid formulations, and for example the pumpability of liquid and easily metering property have reduced packing and transportation cost simultaneously.In consumer market product and industrial preparation, this tendency has all appearred.Tend to concentrated liquid and need reduce water-content in the obtaining liq usually.This causes the increase of ionogen and solids content in these liquid detergent formulas.Another variation is the dependency to non-aqueous solvent, and these non-aqueous solvents help the solubilising of detergent component such as tensio-active agent.These two kinds of variations make the stable more difficulty of some detergent ingredients to physical sepn and/or clustering phenomena.
One of these compositions comprise the siloxanes antifoams.Thereby said siloxanes antifoams is contained in and is controlled at the foam volume that produces in the cycles of washing in the detergent composition in washing machine.The siloxanes antifoams of having found finely divided form is special effective substance.But it is difficult especially that anti-foam preparation is dispersed in the concentrated liquid detergent.
Therefore, an object of the present invention is to provide a kind of foam inhibition system, this system can provide foam control effect (profile) for concentrated liquid detergent.
Another object of the present invention provides uniform liquid detergent composition, and it is stable that this composition will keep, particularly after storing for a long time.
Comprise the foam inhibition system that siloxanes antifoams and a kind of special fatty acid mixt make up by use, reached above purpose.
Be surprised to find the special mixture that adds lipid acid and can provide collaborative enhancement aspect the foam inhibition effectiveness of siloxanes antifoams.This discovery makes us can reduce the content of siloxanes antifoams, keeps containing the foam control effect of siloxanes washing composition simultaneously.
Summary of the invention
The present invention relates to contain the concentrated liquid detergent of Nil-Las, it comprises a kind of silicone oil and a kind of fatty acid mixt, it is characterized in that said lipid acid comprises: i) at least 20% unsaturated fatty acids; Ii) at least 30% the lipid acid that contains 16 or more a plurality of carbon atoms.
Unless stated otherwise, all herein percentage, ratio all are benchmark with weight.
Detailed Description Of The Invention
The present invention relates to concentrated liquid detergent, in this case, compare with the conventional liq washing composition, liquid detergent composition of the present invention contains the water of less amount.In concentrated liquid detergent of the present invention, in the weight of whole detergent composition, the content of water is lower than 50%, preferably is lower than 40%, more preferably less than 30%.
Concentrated liquid detergent of the present invention comprises the mixture of a kind of silicone oil and a kind of lipid acid, it is characterized in that said fatty acid mixt comprises: i) at least 20% unsaturated fatty acids; Ii) at least 30% the lipid acid that contains 16 or more a plurality of carbon atoms.
Preferred fatty acid mixt comprises the lipid acid that contains 16 or more a plurality of carbon atoms of at least 40% unsaturated fatty acids and at least 50%.
The example that is applicable to the lipid acid in the fatty acid mixt of the present invention comprises Zoomeric acid, Thistle oil, sunflower oil, soybean oil, oleic acid, linolic acid, linolenic acid, ricinolic acid, rape seed oil or its mixture.Saturated also can be used for the present invention with undersaturated fatty acid mixt.Preferred mixture comprises that ratio is 9: 1～1: 9, the mixture of preferred 3: 1～1: 9 palm kernel fatty acid and rape seed oil lipid acid.The suitable source of lipid acid is well-known.For example referring to " industry oil and the fatty prod " of Bailey, the third edition, Swern, international scientific press publishes, and 1964.
Recognize that lipid acid can main form with soap be present in the detergent composition.Suitable positively charged ion comprise sodium, potassium, ammonium, monoethanolamine, di-alcohol ammonium, triethanol ammonium, tetra-allkylammonium for example tetramethyl-ammonium to positively charged ions such as tetradecyl ammoniums.
The amount of lipid acid changes according to the required concrete property in the final detergent composition.
For any detergent composition that is used for automatic washing machine, form the foamy degree and should not overflow washing machine.When using froth suppressor, it preferably exists with " foam inhibition amount "." foam inhibition amount " meaning is the amount that the prescription teacher of composition can select this Foam Control, thereby the amount of this Foam Control will be enough to the low foam detergent for washing clothes that control foam obtains being used for automatic washing machine.
Preferably, the ratio of fatty acid mixt and siloxanes is 1: 1～400: 1, more preferably 10: 1～200: 1.
Have been found that the special fatty acid of selecting according to the present invention can strengthen the foam inhibition effect of siloxane foams inhibitor synergistically.Can provide satisfactorily than two kinds of significantly better foam inhibition effects of foam inhibition effect sum that composition is independent according to siloxanes/fatty acid composition of the present invention.
In industrial practice, term " siloxane foams inhibitor " has become a general term, and it comprises the various polymkeric substance that contain the relative ionic weight of siloxane unit and various types of alkyl.Usually, the siloxane foams inhibitor can be described as having the siloxanes of following general structure:
Figure A9519687000051
Wherein, n is 20～2,000 and each R can be the alkyl or aryl group individually.This substituent example is methyl, ethyl, propyl group, isobutyl-and phenyl.Preferred polydiorganosiloxane is to contain trimethyl silyl end envelope unit and have 5 * 10 at 25 ℃ -5m 2/ s～0.1m 2The viscosity of/s, promptly the n value is 40～1500 polydimethylsiloxane.Because they obtain relative low cost with them easily, these are preferred.
Other can be used for suitable silicone oil of the present invention is sense silicone oil.Preferred sense silicone oil is negatively charged ion or cationic silicone oil.
Other siloxanes comprises the composition of organopolysiloxane and silica dioxide granule, wherein this organopolysiloxane chemisorption or be molten on this silicon-dioxide.
The siloxane foams inhibitor is well-known in the art, and for example is disclosed in United States Patent (USP) 4,265,779 and February 7 nineteen ninety disclosed Starch, in the European Patent Application No. 89307851.9 of M.S..
Other siloxane foams inhibitor is disclosed in United States Patent (USP) 3,455, and in 839, it relates to by making the composition and the method for aqueous solution froth breaking to wherein mixing a spot of polydimethylsiloxane fluid.
The mixture of siloxanes and silanized silica is described in for example German patent application DOS2, in 124,526.Silicone antifoam agent in granular detergent composition and froth suppressor are disclosed in United States Patent (USP) 3,933,672 and United States Patent (USP) 4,652,392 in.
A kind of to be used for example silicon oxyalkyl froth suppressor of the present invention be the Foam Control of certain foam inhibition amount, and it mainly is made up of following material: be about 20cs～about 1 (i) 25 ℃ of following viscosity, and the polydimethylsiloxane fluid of 500cs; (ii) corresponding to (i) about 5～50 parts of weights of per 100 parts of weights by (CH 3) 3SiO 1/2Unit and SiO 2Single
The DC resin that unit forms, (CH 3) 3SiO 1/2Unit and SiO 2Unitary ratio was had an appointment 0.6: 1～1.2: 1; (iii) corresponding to the solid silicone of (i) about 1～about 20 parts of weights of per 100 parts of weights.
In the used in this article preferred siloxane foams inhibitor, the solvent that is used for external phase is by some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably) or polypropylene glycol formation.Preferred main siloxane foams inhibitor is a side chain/crosslinked.
In order to further specify this point, contain the general liquid laundry detergent compositions of controlling foaming agent and randomly comprise about 0.001～about 1, preferred about 0.01～about 0.7, the said siloxanes inhibitor of 0.05～about 0.5% (weight) most preferably from about, this inhibitor comprises the nonaqueous emulsion of (1) main antifoams, this suds suppressor is (a) a kind of organopolysiloxane, (b) a kind of siloxanes of resin shape or a kind of silicone compounds that forms DC resin, (c) a kind of finely divided packing material and (d) a kind of component of mixture (a) that promotes, (b) thereby and (c) reaction form the mixture of catalysts of silane alkoxide; (2) at least a nonionic siloxane tensio-active agent and (3) polyoxyethylene glycol or a kind of multipolymer that at room temperature in water, has and polyethylene glycol-propylene glycol that do not have polypropylene glycol solubleness above about 2% (weight).Similarly amount can be used in granular composition, the gel etc.Referring to United States Patent (USP) 4,978,471 and 4,983,316, United States Patent (USP) 5,288,431 and United States Patent (USP) 4,639,489 and 4,749,740.
Siloxane foams inhibitor herein preferably comprises the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, and their molecular-weight average is lower than about 1,000, preferred about 100～800.Polyoxyethylene glycol herein and polyethylene/polypropylene glycol the multipolymer at room temperature solubleness in water surpass about 2% (weight), preferably surpass about 5% (weight).
Preferred herein solvent is a polyoxyethylene glycol, and it is about 1,000 that its molecular-weight average is lower than, preferably about 100-400, most preferably 200～400 and the multipolymer of polyethylene/polypropylene glycol, preferably PPG 200/PEG 300.The part by weight of preferred polyoxyethylene glycol and polyethylene glycol-propylene glycol copolymers is about 1: 1～1: 10, most preferably 1: 3～1: 6.
Preferred siloxane foams inhibitor used herein does not conform to polypropylene glycol, and particularly molecular weight is 4,000 polypropylene glycol.Preferably, they do not contain the segmented copolymer of oxyethane and propylene oxide yet, as PURONIC L101.
Though available higher amount, the general consumption of siloxane foams inhibitor are to be up to about 2.0% of detergent composition weight.This upper limit is suitable in essence, mainly is because with the maintenance low cost with for effectively the control foaming is relevant than the validity of low amount.Preferably, use about siloxane foams inhibitor of 0.01%～about 1%, more preferably from about 0.050%～about 0.5%.As used in this article, these weight percentage comprise any silicon-dioxide and the applicable any additives material that can be used in combination with organopolysiloxane.
According to working method, siloxanes/fatty acid mixt can be added in the liquid detergent composition as a kind of premixed material or as the mixture with other detergent ingredients.The additional detergent composition
Detergent composition according to the present invention comprises a surfactant system, and this system does not contain linear alkyl sulfonate surfactant (Nil-Las).Preferably, tensio-active agent is preferably selected from anion surfactant, and this anion surfactant is selected from alkyl alkoxy sulfate and alkyl-sulphate.
The United States Patent (USP) 3,664,961 that licenses to Norris on May 23rd, 1972 has provided generally enumerating of anionic, non-ionic type, amphoteric and amphoteric ion type and these surfactant materials.
The preferred anionic surfactants tensio-active agent comprises alkyl sulfate surfactant, and its chemical formula is ROSO 3The water-soluble salt of M or acid, wherein R is preferably C 10-C 24Alkyl preferably contains C 10-C 18The alkyl of alkyl component or hydroxyalkyl, more preferably C 12-C 15Alkyl or hydroxyalkyl, with M be H or positively charged ion, for example alkali metal cation (for example sodium, potassium, lithium), or ammonium or replace ammonium (for example methyl, dimethyl and trimethyl ammonium positively charged ion and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion and from alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-quaternary ammonium cation etc.).
Anion surfactant very preferably comprises alkyl alkoxylated vitriol, and it is chemical formula RO (A) mSO 3The water-soluble salt of M or acid, wherein R is the unsubstituted C of containing 10-C 24The C of alkyl component 10-C 24Alkyl or hydroxyalkyl, preferred C 12-C 18Alkyl or hydroxyalkyl, more preferably C 12-C 15Alkyl or hydroxyalkyl, A are an oxyethyl group or propoxy-unit, and m is greater than 0, be generally about 0.5～about 6, more preferably from about 0.5～about 3 and M be hydrogen or positively charged ion, this positively charged ion can be for example metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replace ammonium cation.The propenoxylated vitriol of the vitriol of alkyl ethoxylated and alkyl is also taken into account herein.The specific examples of the ammonium cation that replaces comprise methyl, dimethyl, trimethyl ammonium positively charged ion and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion and from alkylamine for example ethamine, diethylamine, triethylamine and composition thereof deutero-those etc.Exemplary tensio-active agent is C 12-C 15Alkyl polyethoxylated (1.0) vitriol (C 12-C 15E (1.0) M), C 12-C 15Alkyl polyethoxylated (2.25) vitriol (C 12-C 15E (2.25) M), C 12-C 15Alkyl polyethoxylated (3.0) vitriol (C 12-C 15E (3.0) M) and C 12-C 15Alkyl polyethoxylated (4.0) vitriol (C 12-C 15E (4.0) M), wherein M is selected from sodium and potassium easily.
Other suitable anion surfactant that is suitable for is to comprise C 8-C 20The alkyl ester sulfonate of carboxylic acid (being lipid acid) linear ester, it is according to " U.S. oiling association magazine ", 52 (1975), pp.323-329 gas SO 3Sulfonation forms.Suitable starting material will comprise the natural fat material next as deriving from Tallow, beef, palm wet goods.
Preferred alkyl sulfonate surfactants particularly for the laundry purposes, comprises the alkyl sulfonate surfactants with following structural formula:
Figure A9519687000081
R wherein 3Be C 8-C 20Alkyl, preferred alkyl or its composition; R 4Be C 1-C 6Alkyl, preferred alkyl or its composition and M are the positively charged ions that can form water-soluble salt with alkyl ester sulfonate.Suitable salt-forming cation comprises metal for example sodium, potassium and lithium, and replacement or unsubstituted ammonium cation, for example monoethanolamine, diethanolamine and trolamine.Preferably, R 3Be C 10-C 16Alkyl, and R 4Be methyl, ethyl or sec.-propyl.Particularly preferably be methyl ester sulfonate, wherein R 3Be C 10-C 16Alkyl.
Other anion surfactant that is used for washing purposes also can be contained in laundry detergent composition of the present invention.These comprise soap salt (for example comprise sodium, potassium, ammonium and substituted ammonium salt for example single, two and triethanolamine salt), C 9-C 20Linear alkylbenzene sulfonate, C 8-C 22Uncle or secondary paraffin sulfonate, C 8-C 24The sulfonation poly carboxylic acid of the sulfonation preparation of olefin sulfonate, the pyrolysis product by alkaline earth metal citrate, for example be described in the british patent specification numbers 1,082,179 those, C 8-C 24Alkyl polyglycol ether sulfate (contain and be up to 10 moles oxyethane), alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate be acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (particularly saturated and undersaturated C for example 12-C 18Monoesters) and sulfosuccinic acid diesters (particularly saturated and undersaturated C 6-C 12Diester), alkyl polysaccharide vitriol for example alkyl polyglucoside vitriol (compound of the nonionic non-sulfuric acidization that describes below) and alkyl polyethoxye carboxylate salt for example chemical formula be RO (CH 2CH 2O) k-CH 2Those of COO-M+, wherein R is C 8-C 22Alkyl, k are that 1～10 integer and M are the positively charged ions that forms soluble salt.Resin acid and the acid of hydrogenation resin also suit, and for example are present in the tallol or by tallol deutero-resin, hydrogenation resin and resin acid and the acid of hydrogenation resin.Other case description is (I and II volume, Schwartz, Perry and Berch compile) in " tensio-active agent and washing composition ".Various such tensio-active agents also usually are disclosed in the United States Patent (USP) 3,929,678 that licensed to Laughlin etc. on December 30th, 1975, and the 23rd hurdle 58 walks to the 29th hurdle 23 row (being incorporated herein by reference).
When comprising such anion surfactant, laundry detergent composition of the present invention generally comprise have an appointment 1%～about 40%, preferred about 5%～about 25% (weight).
Being used for a class nonionogenic tenside of the present invention is the condenses of oxyethane and hydrophobic part, is 8～17 thereby average hydrophilic-lipophilic balance (HLB) value is provided, preferred 9.5～14, more preferably 12～14 tensio-active agent.Hydrophobic (oleophylic) part can be aliphatic or aromatic in nature, thereby and and the length of the polyoxyethylene groups of any concrete hydrophobic grouping condensation can easily regulate the water-soluble cpds that obtains having required balance degree between wetting ability and hydrophobic parts.
Particularly preferred such nonionogenic tenside is that every mol of alcohol contains 3-12 moles of ethylene oxide, C 9-C 15Primary alcohol ethoxylate, particularly every mol of alcohol contains the C of 5-8 moles of ethylene oxide 12-C 15Primary alcohol ethoxylate.
Another kind of ionic surfactant pack is drawn together the alkyl polyglucoside compound with following general formula
RO(C nH 2nO) tZ x
Wherein Z is from glucose deutero-part; R is the saturated hydrophobic alkyl group that comprises 12～18 carbon atoms; T be 0～10 and n be 2 or 3; X is 1.3～4, and this compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the short-chain alkyl poly glucoside that is less than 50%.Such compound and they are disclosed in EP-B 0 070 077,0 075 996 and 0 094 118 in detergent application.
Also suitable is the polyhydroxy fatty acid amide with following chemical formula as the non-ionic surface agent R wherein 1Be H or R 1Be C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-31Alkyl and Z have at least three polyhydroxy alkyl or its oxyalkylated derivatives that directly are connected the straight-chain alkyl chain of the hydroxyl on the chain.Preferably, R 1Be methyl, R 2It is straight chain C 11-C 15Alkyl or alkenyl chain for example coconut alkyl or its mixture and Z be in reductive amination process from reducing sugar, for example glucose, fructose, maltose, lactose-derivedly come.
Detergent composition herein also can comprise additional froth suppressor.These for example comprise high-molecular-weight hydrocarbons for example paraffin, fatty acid ester (for example fatty acid glyceryl ester), the fatty acid ester of monovalent alcohol, aliphatics C 18-C 40Ketone (for example stearone) etc.Other froth suppressor comprises the alkylating aminotriazine of N-for example three-six-alkyl melamine or two-four-alkyl diamine chlorination triazine, it is melamine chlorination thing and two or three moles the uncle of containing 1～24 carbon atom or product, 1,2 epoxy prapane and for example single Stearyl alcohol phosphoric acid ester of single octadecyl phosphoric acid salt and single octadecyl two basic metal (for example K, Na and Li) phosphoric acid salt and the phosphoric acid ester of secondary amine formation.Hydro carbons for example paraffin and halo paraffin also can use with liquid form.Liquid hydrocarbon is liquid under room temperature and normal pressure, and pour point for-40 ℃ approximately～about 50 ℃ and minimum boiling point be not less than about 110 ℃ (normal pressures).It also is known utilizing napalite, and preferred fusing point is lower than about 100 ℃ napalite.Hydro carbons has constituted the froth suppressor that a class preferably is used for detergent composition.The hydro carbons froth suppressor for example is described in the United States Patent (USP) 4,265,779.Like this, hydro carbons comprises the saturated and unsaturated hydro carbons of aliphatic, alicyclic, aromatic and heterocyclic that contains about 12～about 70 carbon atoms.Be meant the mixture that comprises true paraffin and cyclic hydrocarbon as used term " paraffin " in the discussion of this froth suppressor.
Other useful froth suppressor comprises the mixture of secondary alcohol (for example 2-alkyl chain triacontanol) and this kind alcohol and silicone oil among the present invention, for example is disclosed in United States Patent (USP) 4,798,679,4,075,118 and European patent 150872 in siloxanes.Secondary alcohol comprises having C 1-C 16The C of chain 6-C 16Alkyl alcohol.A kind of preferred alcohol is 2-butyl octanol, and it can obtain with trade name ISOFOL 12 from Condea.The secondary alcohol mixture can obtain with trade mark ISALCHEM123 from Enichem.It is 1: 5～20: 1 the alcohol and the mixture of siloxanes that the blended froth suppressor generally comprises weight ratio.
When mono carboxylic lipid acid and its salt used mainly as froth suppressor, its general consumption was up to about 15% of detergent composition weight.Preferably use about 5%～about 15% fatty monocarboxylate froth suppressor.In addition, composition herein generally includes 0%～about 5% froth suppressor.
The common amount ranges of single stearyl phosphoric acid salt froth suppressor is about 0.1%～about 2% (weight) of composition.Though can use higher amount, the general consumption of hydro carbons froth suppressor is about 0.01%～about 5.0%.The general consumption of alcohols froth suppressor is 0.2%～3% of a composition finished weight.
Also can comprise builder system according to composition of the present invention.Any conventional builder system here all is suitable for, it comprises alumino-silicate materials, silicate, polycarboxylate and lipid acid, material such as edetate, metal ion chelation agent for example amino polyphosphonate, particularly ethylenediamine tetramethylene phosphonic acid and diethylidene three ammonia pentamethylene phosphonic acids.Though because significantly environment reason is and not too preferred, phosphate builders also can be used in this article.
The polycarboxylate washing assistant of Shi Yonging comprises citric acid herein, the form of preferred water-soluble salt, and chemical formula is the succinic acid derivative of RCH (COOH) CH2 (COOH), wherein R is C 10-20Alkyl or alkenyl, preferred C 12-16, or wherein R can be replaced by hydroxyl, sulfo group sulfoxylic acid base or sulfone substituting group.Concrete example comprises lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate, 2-tetradecene base succinate.The succinate washing assistant comprises that preferably with its water-soluble salt the form of sodium, potassium, ammonium and alkanol ammonium salts is used.
Other suitable polycarboxylate is the oxo disuccinate and as is described in United States Patent (USP) 4,663, the tartrate monosuccinic acid in 071 and the mixture of tartrate disuccinic acid.
Be used in particular for the preparation of liquid herein, the lipid acid washing assistant of Shi Yonging is saturated or unsaturated C herein 10-18Lipid acid and corresponding soap class.Preferred saturate contains 12-16 carbon atom in alkyl chain.The another kind of preferred builder system that is used for liquid composition is based on dodecenyl succinic succsinic acid and citric acid.
The content that the detergency builder salt is general is the 10-80% of composition weight, preferred 20%～70% and most preferably be generally 30%～60%.
Can use other component that is used for detergent composition, for example enzyme and stablizer or activator, soil-suspending agent, abrasive, sterilant, the dark inhibitor of enzyme, tinting material and corrosion inhibitor and spices.Particularly preferably be and the zymotechnic combination that a kind of color protection benefit can be provided.Being used for color maintenance/regenerated example is cellulase.Other example is the polymkeric substance and the oxydasis thing scavenging agent that is disclosed in the european patent application of applying on January 31st, 1,992 92870018.6 that is disclosed in the european patent application of applying on January 31st, 1,992 92870017.8.
The amido catalyst stabilizer that is disclosed in the european patent application of applying on January 31st, 1,992 92870019.4 also is suitable especially.
Detergent composition of the present invention also can be used as the detergent additives product.The purpose of such additive product is the performance that remedies or improve conventional detergent composition.
Detergent composition according to the present invention comprises and is used for substrate, for example the component of the cleaning of fabric, fiber, crust etc., for example laundry detergent composition and automatic and non-automatic dishwashing compositions, hard surface cleaner.
The following examples are used for illustrating the present composition, but the scope that is not intended to limit the present invention.
Liquid detergent composition below the preparation;
I II III IV C 12-C 15Alkyl-sulphate 7 15 7 15 C 12-C 15Vitriol 19 3 19 3 C of alkyl ethoxylated 12-C 14N-methyl grape acid amides 6666 C 12-C 14Alcohol ethoxylate 5555 anhydrous citric acids 3.5 3.5 3.5 3.5 diethylenetriamine pentamethylenophosphonic acids 22 2.0 2.0 MEAs 12.8 11.0 12.8 11.0 propane diols 13.1 10.0 13.1 10.0 ethanol, 4.7 5.4 4.7 5.4 amylase (300KNU/g) 0.1 0.1 0.1 0.1 lipase (100KNU/g) 0.15 0.15 0.15 0.15 FNA-alkali (34g/L), 0.5 0.5 0.5 0.5 Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05 Carezyme (5000 CEVU/g) 0.09 0.09 0.09 0.09 terephthalate based polyalcohol 0.5 0.5 0.5 0.5 brightening agents 0.15 0.15 0.15 0.15 boric acid Aerosil 200 0.01 0.01 0.01 0.01 side chain siloxanes 0.15 0.15 0.15 0.15 vegetable seeds aliphatic acid 3453 senior palm-kernel oil aliphatic acid 7657 water and a small amount of component ... reach 100%
Liquid detergent composition (I-IV) above finding is very effective aspect control foam, still can keep stable after the prolonged preservation simultaneously.

Claims (10)

1) a kind of concentrated liquid detergent that contains Nil-Las comprises silicone oil and fatty acid mixt, it is characterized in that said fatty acid mixt comprises:
I) at least 20% unsaturated fatty acids;
Ii) at least 30% the lipid acid that contains 16 or more a plurality of carbon atoms.
2) a kind of liquid detergent composition according to claim 1, wherein the weight ratio of fatty acid mixt and siloxanes is 1: 1～400: 1, more preferably 10: 1～200: 1.
3) a kind of liquid detergent composition according to claim 1, wherein fatty acid mixt comprises the lipid acid that contains 16 or more a plurality of carbon atoms of at least 40% unsaturated fatty acids and at least 50%.
4) a kind of detergent composition according to claim 1, also comprises surfactant, washing assistant, enzyme and other conventional detergent component.
5) a kind of detergent composition according to claim 1 also comprises the vitriol that is selected from alkyl ethoxylated and/or the anion surfactant of alkyl sulfate surfactant.
6) a kind of detergent composition according to claim 5 also comprises a kind of nonionogenic tenside that is selected from polyhydroxy fatty acid amide.
7) a kind of detergent composition according to claim 6, wherein nonionogenic tenside is C 12-C 14N-methyl grape acid amides.
8) a kind of detergent composition according to claim 1, it is the form of additive.
9) be used for the purposes of cleaning fabric, bowl dish and crust according to the detergent composition of claim 1.
10) be used for the pretreated purposes of fabric, bowl dish and crust according to the detergent composition of claim 1.
CN 95196870 1994-10-28 1995-10-13 Stable liquid detergent compositions comprising fatty acid and silicone oil Pending CN1170428A (en)

Applications Claiming Priority (2)

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EP94307979.8 1994-10-28
EP94307979A EP0709451A1 (en) 1994-10-28 1994-10-28 Stable liquid detergent compositions

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JP5396707B2 (en) * 2007-11-07 2014-01-22 ライオンハイジーン株式会社 Cleaning composition
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JPH10508060A (en) 1998-08-04
EP0709451A1 (en) 1996-05-01
MX9703106A (en) 1997-07-31
WO1996013566A1 (en) 1996-05-09

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