CN1153524A - Liquid detergent composition contg. oleoyl sarcosinates and anionic surfactants - Google Patents
Liquid detergent composition contg. oleoyl sarcosinates and anionic surfactants Download PDFInfo
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- CN1153524A CN1153524A CN 95194267 CN95194267A CN1153524A CN 1153524 A CN1153524 A CN 1153524A CN 95194267 CN95194267 CN 95194267 CN 95194267 A CN95194267 A CN 95194267A CN 1153524 A CN1153524 A CN 1153524A
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Abstract
A liquid laundry detergent composition comprising a surfactant system said surfactant system comprising an oleoyl sarcosinate and one or more of an anionic surfactant selected from the group of alkyl alkoxylated sulfates and/or alkyl sulfates.
Description
Invention field
The present invention relates to a kind of detergent composition with improved cleaning performance.More particularly, this invention is about a kind of liquid detergent composition, and it contains oleoyl sarcosinate and one or more anion surfactants, and this anion surfactant is selected from alkyl alkoxy sulfate and/or alkyl-sulphate.
Background of invention
The detergent composition that is used to clean the washing of purpose such as fabric uses various tensio-active agents usually.
Surfactant washing is various to be present in fabric dirt in the general laundry load and the ability of stain is very important for estimating the detergent washing performance.Regrettably, every kind of tensio-active agent relative capacity of satisfying various standard of performance depends on the different working conditionss of different regions.
Therefore, the washing composition producer need make preparation and the heavy balance of different surfaces promoting agent obtain best washing effect.For example, in the U.S., under American wash conditions, because the height ratio of the free hardness that exists, alkyl ethoxy sulfate is a preferred surfactants, rather than alkyl-sulphate.In Europe, alkyl-sulphate is the preferred surfactants in the high built detergent medium, and this is because their inherent degrease performances preferably under those conditions.
Therefore, for performance and handiness reason, need to obtain to provide the durable surface promoting agent system of high-performance for a long time to the different working conditionss of whole different regions.
Above-mentioned target is realized by a kind of surfactant system that this surfactant system contains oleoyl sarcosinate and one or more anion surfactants, and this anion surfactant is selected from alkyl alkoxy sulfate and/or alkyl-sulphate.
Find that surprisingly this surfactant system comprises under the situation of the different wash temperatures and the different water hardness in different working conditionss, has shown very good scourability.
In addition, people also find with the liquid detergent composition of this surfactant system preparation very effective when directly contacting with fabric, such as the pre-treatment of fabric.These compositions can also provide good color protection to painted fabric, and can keep the advantages of good skin mildness in the hand washing operation.
Oleoyl sarcosinate is existing the description in following patent with openly:
United States Patent (USP) 2,542,385; United States Patent (USP) 3,402,990; United States Patent (USP) 3,639,568; United States Patent (USP) 4,772,424; United States Patent (USP) 5,186,855; European patent discloses 505,129; English Patent discloses 1,211, and 545; Japanese Patent discloses 59/232194; Japanese Patent discloses 62/295997; Japanese Patent discloses 02/180811; And chemical abstracts portion digest number: 61:3244q, 70:58865x and 83:181020p.
Detailed Description Of The Invention
The present invention relates to contain the liquid detergent composition of surfactant system; said surfactant system contains oleoyl sarcosinate and one or more anion surfactants, and this anion surfactant is selected from alkyl alkoxy sulfate and/or alkyl-sulphate.
This liquid detergent composition preferably comprises at least 5%, and more preferably 10%～60%, the above-mentioned surfactant system of 25%～40% (weight) most preferably.
Oleoyl sarcosinate to the weight ratio of alkyl alkoxylated suifate and/or alkyl-sulphate be preferably 1: 10～10: 1, more preferably 1: 6～2: 1, most preferably 1: 3～1: 1.Oleoyl sarcosinate
The present composition contains oleoyl sarcosinate, and according to the form of the present composition and its acid of the required selection of purposes and/or salt, it has following formula:
Wherein M is hydrogen or anionicsite.The preferred hydrogen of M and an alkali metal salt, especially sodium salt and sylvite.Oleoyl sarcosinate can commerce be buied, as W.R.Grace ﹠amp; Co. Gong Ying HamposylO.Oleoyl sarcosinate be preferably composition weight about 0.1%～about 80%, more preferably from about 1%～about 40%, 2%～about 30% (weight) most preferably from about.
Except the oleoyl sarcosinate that commerce can be buied; the useful oleoyl sarcosinate of the present invention can also be preferably by oleic acid ester (preferred methyl esters) and sarcosinate (particular certain cancers) in the presence of alkaline catalysts; its basicity is equal to or greater than alkoxide catalyzer (particular methanol sodium), reacts under the anhydrous response condition.For example reaction can be represented with following formula:
This salt can randomly be neutralized into oleoylsarcosine.
The preferred method of preparation oleoyl sarcosinate is to be about 80 ℃～about 120 ℃ in temperature, carries out under particularly about 120 ℃～about 200 ℃.Preferably carry out this reaction under solvent-free, although can use boiling point with at least 100 ℃, and under this reaction conditions stable alcoholic solvent (be glycerine cannot).At reactant mol ratio methyl esters: sarcosinate: basic catalyst=1: 1: 0.05～0.2 o'clock, this reaction yield is about 85%.
The mixtures of methyl esters that derives from the natural oil (it is about 60% that oleic acid content preferably is at least, and more preferably is at least approximately 75%, most preferably is at least about 90%) of high oleic acid content is particularly preferred raw material.Example comprises high oleic sunflower oil and rapeseed oil/canola oil.In addition, also can accept from the high oleic acid methyl cut of palm-kernel oil or Tallow, beef.Should be appreciated that this oil generally contains a certain amount of impurity, comprise some lipid acid impurity, these lipid acid impurity can be converted into the sarcosinate compound by this synthetic method.For example, commodity canola/ rapeseed oil may contain the mixture of a large amount of oleic acid and lipid acid impurity such as palmitinic acid, stearic acid, linolic acid, linolic acid and/or eicosenoic acid, and this reaction method of part or all of usefulness of these impurity is converted into sarcosinate.If the preparation purposes needs, some or all this impurity will be removed from stock oil before preparation is used for the oleoyl sarcosinate of the present composition so.
At last, the sarkosine that remains in the reaction mixture can make it to be converted into acid amides by adding maleic acid or diacetyl oxide, thereby the possibility of content of sarcosine and all undesirable nitrogenous impurity formation is reduced to minimum.
The synthetic of oleoyl sarcosinate can be undertaken by the following method for preparing oleoylsarcosine sodium.
Synthetic-one 2L of oleoyl acid amides Sodium sarcosinate, three mouthfuls of round-bottomed flasks are equipped with the dean stark trap, mechanical stirrer of thermometer, band prolong and lead to the inlet attack of nitrogen in the reaction mixture.In this reactor, pack into sarkosine (43.3g, 0.476mol), contain sodium methylate be 25% methyl alcohol (97.7g, 0.452mol) and methyl alcohol (400ml).Reaction refluxes 15 minutes with the neutralizer propylhomoserin, add then methyl esters from the common high oleoyl Trisun Oil R 80 of Cargill (148.25g, 0.5mol).Remove after the methyl alcohol with dean stark trap, reaction mixture is heated to 170 ℃ continues 1 hour to remove all water.Add the methyl alcohol (15.4g, 0.0714mol) initiation reaction that contain sodium methylate 25%.Make reaction remain on 170 ℃ and continue 2.5 hours, during this period, methyl alcohol is collected in the dean stark trap.Reactant is cooled off slightly, then add methyl alcohol (200g).(9.43g 0.095mol) joined in the methanol solution, 60 ℃ of reaction stirred 0.5 hour with MALEIC ANHYDRIDE.Remove most of methyl alcohol by rotary evaporator then, add acetone (2L) and make the product precipitation.Product is collected by suction strainer, and dry air obtains a kind of pale solid.Show that with the gas chromatographic analysis reaction mixture most of product is an oleoyl sarcosinate, and have a spot of following impurity: sarkosine, oleic acid and palmitinic acid, stearic acid and linolic acid deutero-sarcosinate.
Alkyl alkoxy sulfate and/or alkyl-sulphate
Alkyl alkoxy sulfate tensio-active agent is formula RO (A) among the present invention
mSO
3The water-soluble salt of M or acid, wherein R does not have substituted C
10-C
24Alkyl or hydroxyalkyl, it has C
10-C
24The alkyl composition, preferred C
12-C
18Alkyl or hydroxyalkyl, more preferably C
12-C
15Alkyl or hydroxyalkyl, A are 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, M is H or a positively charged ion, as metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replace ammonium cation.The present invention considers alkyl ethoxy sulfate and alkyl propoxy-vitriol simultaneously.The object lesson that replaces ammonium cation comprises methyl, dimethyl, trimethyl ammonium positively charged ion and quaternary amines positively charged ion such as tetramethyl-ammonium and dimethyl base pyridine (piperdinium) positively charged ion and those positively charged ions derived from alkylamine such as ethamine, diethylamine, triethylamine and their mixture or the like.Exemplary tensio-active agent is C
12-C
15Alkyl polyethoxye (1.0) vitriol (C
12-15E (1.0) M), C
12-C
15Alkyl polyethoxye (2.25) vitriol (C
12-15E (2.25) M), C
12-C
15Alkyl polyethoxye (3.0) vitriol (C
12-15And C E (3.0) M),
12-C
15Alkyl polyethoxye (4.0) vitriol (C
12-15E (4.0) M), wherein M is selected from sodium and potassium easily.
Alkyl sulfate surfactant among the present invention is that formula is ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-24Alkyl, preferred alkyl or hydroxyalkyl, it has C
10-C
18Alkyl composition, more preferably C
12-C
15Alkyl or hydroxyalkyl, and M is H or a positively charged ion, such as alkali metal cation (for example sodium, potassium, lithium), perhaps ammonium or replace ammonium (as methyl, dimethyl and trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethyl-ammonium and dimethyl base pyridine positively charged ion with by alkylamine such as ethamine, diethylamine, triethylamine and their deutero-quaternary ammonium cations such as mixture).
Detergent ingredients:
In another embodiment of the invention, a kind of liquid detergent composition is provided, it comprises and detergent ingredients blended surfactant system of the present invention.Various tensio-active agents can be used for detergent composition of the present invention.
One row typical negatively charged ion, nonionic, both sexes and zwitterionics and these kinds of surfactants license on May 23rd, 1972 in the United States Patent (USP) 3,664,961 of Norris and are listed.
Other anion surfactant that is fit to use is an alkyl sulfonate surfactants, comprises and uses gaseous state SO
3Sulfonated C
8-C
20The linear ester of carboxylic acid (being lipid acid) is seen " U.S.'s oiling is learned association's magazine (The Journal of the American Oil ChemistsSociety) " 52 (1975), the 323rd～329 page.Suitable raw material comprises by Tallow, beef, palm wet goods deutero-natural fat material.
Preferred alkyl sulfonate surfactants, the usefulness of particularly doing washing, comprise the alkyl sulfonate surfactants of following structural formula:
R
3-CH(SO
3M)-C(O)-OR
4
R wherein
3Be a C
8-C
12Alkyl, preferred alkyl or its combination, R
4Be a C
1-C
6Alkyl, preferred alkyl, or its combination, and M is the positively charged ion that and alkyl ester sulfonate form water-soluble salt.Suitable salt-forming cation comprises metal such as sodium, potassium, lithium and replacement or unsubstituted ammonium cation, as monoethanolamine, diethanolamine and trolamine.Preferably, R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Preferred especially methyl ester sulfonate, wherein R
3Be C
10-C
16Alkyl.
Other anion surfactant that is used for the decontamination purpose also can be included in laundry detergent composition of the present invention.These can comprise the soap salt (for example comprise sodium, potassium, ammonium and substituted ammonium salt such as list, two and triethanolamine salt), C
9-C
20Linear alkylbenzene sulfonate, C
8-C
22The primary, secondary alkane sulfonate, C
8-C
24Alkene sulfonate, sulfonation poly carboxylic acid, these sulfonation poly carboxylic acid are as british patent specification No.1,082,179 described, C that the sulfonation of alkaline earth metal citrate pyrolysis product makes by making like that
8-C
24Alkyl polyglycol ether sulfate (containing oxyethane) up to 10mol; Glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate, alkyl phenol epoxy ethane ether salt, alkane sulfonate, alkylphosphonic, isethionate such as acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfo-succinic acid, sulfosuccinic acid monoesters (particularly saturated and undersaturated C
12-C
18Monoesters) and sulfosuccinic acid diesters (particularly saturated and undersaturated C
6-C
12Diester), alkyl polysaccharide vitriol such as APG vitriol (nonionic non-sulfuric acid compound hereinafter described), and alkyl polyethoxye carboxylate salt is suc as formula being RO (CH
2CH
2-O)
k-CH
2COOM
+Those, wherein R is a C
8-C
22Alkyl, k are the integers from 0～10, and M is a solubility salt-forming cation.Resinous acid and hydrogenated resin acid also suit, as rosin, staybelite, be present in the tallol or by tallol deutero-resinous acid and hydrogenated resin acid.Other example is described in " tensio-active agent and washing composition " (I, II volume, Schwartz, Perry and Berch work).Multiple such tensio-active agent also is disclosed the United States Patent (USP) 3,929,678 that licensed to people such as Laughlin on December 30th, 1975 prevailingly, and the 23rd hurdle the 58th row is to the 29th hurdle the 23rd row (being hereby incorporated by).
When being included in when interior, the weight content of this anion surfactant in laundry detergent composition of the present invention is generally about 1%～about 40%, preferred about 5%～about 25%.
A class nonionogenic tenside that is useful among the present invention is the condenses of oxyethane and hydrophobic part, and obtaining average close and distant balance (HLB) value is 8～17, and is preferred 9.5～14, more preferably 12～14 tensio-active agent.This hydrophobic (oleophylic) part can be aliphatic series or aromatic in nature, and the length of the polyoxyethylene group of any concrete hydrophobic group condensation can be regulated easily and obtained a kind of water-soluble cpds with the quality of balance between desirable wetting ability and the hydrophobicity.
Particularly preferred this class nonionogenic tenside is C
9-C
15Primary alcohol ethoxylate, every mol of alcohol contains 3～12 moles of ethylene oxide, and especially every mol of alcohol contains the C of 5～8 moles of ethylene oxide
12-C
15Primary alconol.
Another kind of ionic surfactant pack is drawn together the following alkyl polysaccharide glycoside compound of general formula:
RO(C
nH
2nO)
tZ
x
Wherein Z is the part derived from glucose; R is the saturated hydrophobic alkyl that contains 12～18 carbon atoms; T is 0～10 number, and n is 2 or 3; X is 1.3～4 number, and compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the short-chain alkyl polysaccharide glycosides that is less than 50%.This compounds and they are disclosed in Europe-B0 070 077,0 075 996 and 0 094 118 in detergent application.
Very suitable as nonionogenic tenside be polyhydroxy fatty acid amide surfactant, it has following formula:
R
2-C(O)-N(R
1)-Z
R wherein
1Be H or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R
2Be C
5-31Alkyl, Z are polyhydroxy alkyls, and it has a straight-chain alkyl chain, and have at least 3 hydroxyls directly to link to each other with this chain, or its alkoxy derivative.R
1Preferable methyl, R
2Preferred straight chain C
11-15Alkyl or alkenyl chain such as coconut alkyl or its mixture, Z in reductive amination process by reducing sugar such as glucose, fructose, maltose, lactose-derived.
When being included in when interior, laundry detergent composition of the present invention generally comprises anion surfactant, and the weight ratio of contained anion surfactant and nonionogenic tenside is 3: 1～1: 3, preferred 2.5: 1～1.5: 1.
The cationic detersive surfactants that is applicable to laundry detergent composition of the present invention is those compounds with a long chain hydrocarbon groups.The example of this cationoid tensio-active agent comprises ammonium surfactant such as alkyl dimethyl amine halogenide, and these tensio-active agents have following formula:
[R
2(OR
3)
y][R
4(OR
3)
y]
2R
5N
+X
-
R wherein
2Be alkyl or the alkyl benzyl that has about 18 carbon atoms of about 8-in the alkyl chain, each R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-or their mixture; Each R
4Be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, by two R
4The benzyl ring structure that group is connected to form ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH, wherein R
6Be any hexose or molecular weight less than about 1000 hexose polymkeric substance with when y is not equal to 0, R
4Be H; R
5With R
4Identical or work as R
2And R
5No more than about 18 o'clock of carbonatoms sum, R
5It is an alkyl chain; Each y value is 0～about 10, and the summation of y value is 0～about 15; X is any compatible negatively charged ion.
Preferred cationic surfactants is the water-soluble quaternary ammonium compounds that is useful in the present composition, has following formula:
R
1R
2R
3R
4N
+X
-(i)
R wherein
1Be C
8-C
16Alkyl, each R
2, R
3And R
4Be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
4O)
xH, wherein the x value be 1～5 and X be a negatively charged ion.R
2, R
3Or R
4In maximum one be benzyl.
R
1Alkyl chain length is C preferably
12-C
15, especially wherein alkyl be by the mixture of coconut or palm-kernel fat deutero-chain length or by alkene pure synthetic and synthetic the obtaining of synthetic or OXO.R
2, R
3And R
4Group preferable methyl and hydroxyethyl, and negatively charged ion X is selected from halogenide, Methylsulfate (methosulphate), acetate moiety and phosphate anion.
The example that is applicable to formula of the present invention (i) quaternary ammonium compound is as follows:
Coconut trimethyl ammonium chloride or coconut trimethylammonium bromide;
Coconut methyl dihydroxy ethyl ammonium chloride or coconut methyl dihydroxy ethyl brometo de amonio;
The decyl triethyl ammonium chloride;
Decyl dimethyl trihydroxyethyl ammonium chloride or decyl dimethyl trihydroxyethyl brometo de amonio;
C
12-15Dimethyl hydroxyethyl ammonium chloride or C
12-15Dimethyl hydroxyethyl brometo de amonio;
Coconut dimethyl hydroxyethyl ammonium chloride or coconut dimethyl hydroxyethyl brometo de amonio;
Tetradecyl trimethyl ammonium Methylsulfate;
Dodecyl benzyl dimethyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide;
Dodecyl dimethyl (oxyethylene group)
4Ammonium chloride or dodecyl dimethyl (oxyethylene group)
4Brometo de amonio;
Cholinesterase (formula (i) compound, wherein R
1Be-CH
2-O-C (O)-C
12-14Alkyl and R
2R
3R
4Be methyl);
Being useful on other cats product of the present invention also has been described in the United States Patent (USP) 4,228,044 of the Cambre of mandate on October 14th, 1980.
When being included in when interior, this cats product weight content is generally 0.5%～about 5%, preferred about 1%～about 3% in the laundry detergent composition of the present invention.
Also contain a kind of builder system according to composition of the present invention.The builder system of any routine all is applicable to the present invention, comprise alumino-silicate materials, silicate, polycarboxylate and fatty acid material such as ethylenediamine tetraacetic acid (EDTA), metal ion chelation agent such as amino polyphosphonate, specifically ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Although since tangible environment reason, more less preferred phosphate builders, and the present invention still can use.
Be applicable to that polycarboxylate washing assistant of the present invention comprises citric acid, preferably water dissolubility salt form, formula is R-CH (COOH) CH
2(COOH) succinic acid derivative, wherein R is C
10-20Alkyl or alkenyl, preferred C
12-16Or wherein R can be replaced by hydroxyl, sulfo group sulfoxylic acid base (sulfo sulfoxyl) or sulfone substituting group.Concrete example comprises dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate, 2-tetradecene base succinate.The succinate washing assistant preferably comprises the form use of sodium salt, sylvite, ammonium salt and alkanol ammonium salts with its water-soluble salt.
Other suitable polycarboxylate is the mixture of oxygenate disuccinate and tartrate monosuccinic acid and tartrate disuccinic acid, as United States Patent (USP) 4,663, described in 071.In particular for liquid washing agent of the present invention, be applicable to that lipid acid washing assistant of the present invention is saturated or unsaturated C
10-18Lipid acid, and corresponding soap.On the preferred saturated kind alkyl chain 12～16 carbon atoms are arranged.Preferred unsaturated fatty acids is an oleic acid.The builder system of other preferred liquid composition is based on dodecenyl succinic succsinic acid and citric acid.
Decontamination lotion promoter salt is 3%～50% of composition weight usually with the amount, preferred 5%～30%, the most frequently used 5%～25%.
Can randomly contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching component of one or more bleach-activating agents according to detergent composition of the present invention.When SYNTHETIC OPTICAL WHITNER existed, its amount was generally detergent composition, in particular for the composition of fabric washing about 1%～about 30%, typically be about 5%～about 20%.If there is bleach-activating agent, its amount be generally SYNTHETIC OPTICAL WHITNER+bleach-activating agent bleaching composition about 0.1%～about 60%, be more typically about 0.5%～about 40%.
The used SYNTHETIC OPTICAL WHITNER of the present invention can be that arbitrarily fabric cleans or other cleans the effective SYNTHETIC OPTICAL WHITNER of detergent composition of purpose to being used for, and comprises now knownly maybe will knowing.
Being fit to SYNTHETIC OPTICAL WHITNER of the present invention can be activatory or non-activated SYNTHETIC OPTICAL WHITNER.
Be fit to SYNTHETIC OPTICAL WHITNER of the present invention and comprise peroxygen bleach.The example of suitable water-soluble solid peroxygen bleach comprises hydrogen peroxide releasing agent such as hydrogen peroxide, and perborate is as perborate monohydrate, peroxyboric acid tetrahydrate, persulphate, percarbonate, peroxosulphuric hydrogen salt, superphosphate and peroxyhydrate.Preferred SYNTHETIC OPTICAL WHITNER is percarbonate and perborate.
Hydrogen peroxide also can obtain by adding enzyme catalysis system (being a kind of enzyme and matrix), and this enzyme catalysis system can produce hydrogen peroxide in beginning or during washing and/or rinse cycle.This enzyme catalysis system is disclosed in the european patent application 91202655.6 of application on October 9th, 1991.
Other is applicable to that peroxygen bleach of the present invention comprises organic peroxide acid such as percarboxylic acids.
The suitable example of this class reagent has magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and two peroxide dodecandioic acid of six hydration monoperphthalic acid magnesium, metachloroperbenzoic acid.These SYNTHETIC OPTICAL WHITNER are disclosed the United States Patent (USP) 4 of the Hartman that authorized on November 20th, 1984,483,781, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740,466, February in 1985 people such as disclosed Banks on the 20th european patent application 0,133,354, in the people's such as Chung that authorize November 1 nineteen eighty-three the United States Patent (USP) 4,412,934.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxo crosses oxy hexanoic acid, and the United States Patent (USP) 4,634,551 that licenses to people such as Bums as on January 6th, 1987 is described.
It is about 500 microns～about 1000 microns dried particle that preferred percarbonate bleach comprises median size, is no more than the about 10% of said particle weight less than about 200 microns particle, is no more than about 10% of said particle weight greater than about 1,250 micron particle.Percarbonate can randomly use silicate, borate or water soluble surfactant active to coat.Percarbonate can obtain by various commercial source, as FMC, Solvay and Tokai Denka.
Also can use the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate or the like preferably combine with bleach-activating agent, and this produces the peroxy acid aqueous solution (promptly in washing process) corresponding to bleach-activating agent on the spot.The non-limiting example of various activators is disclosed in the United States Patent (USP) 4,915,854 and United States Patent (USP) 4,412,934 that licenses to people such as Mao April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activator are typical, and their mixture also can use.Be useful on other typical SYNTHETIC OPTICAL WHITNER of the present invention and activator and see United States Patent (USP) 4,634,551.
Amido deutero-bleach-activating agent very preferably is those of following formula:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L
R wherein
1Be an alkyl that contains 6～about 12 carbon atoms of having an appointment, R
2Be an alkylidene group that contains 1～about 6 carbon atoms, R
5Be H or alkyl, aryl or the alkaryl that contains 1～about 10 carbon atoms of having an appointment, L is the leavings group of any appropriate.Leavings group is meant any group that is replaced from activator of bleaching agent owing to the result of hydrolysis negatively charged ion nucleophilic attack bleach-activating agent.Preferred leavings group is a benzene sulfonate.
The preferred embodiment of following formula SYNTHETIC OPTICAL WHITNER comprises (6-caprylamide caproyl) oxygen base benzene sulfonate, (6-nonanoyl ammonia caproyl) oxygen base benzene sulfonate, (6-caprinoyl ammonia caproyl) oxygen base benzene sulfonate; with their mixture, as United States Patent (USP) 4,634; 551 is described, is hereby incorporated by.
Another kind of bleach-activating agent comprises the benzo oxazinyl activator, is disclosed in the United States Patent (USP) 4,966,723 that licenses to people such as Hodge October 30 nineteen ninety, is hereby incorporated by.Benzo oxazinyl activator very preferably is:
Also have, another kind of preferred bleach-activating agent comprises the acyl caprolactam and the acyl group Valerolactim of acyl lactam activator, particularly following formula:
R wherein
6Be H or alkyl, aryl, alkoxy aromatic yl or an alkylaryl group that contains 1～about 12 carbon atoms.Lactan activator very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl hexanolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and their mixture.On October 8th, also visible licensed to the United States Patent (USP) 4,545,784 of Sanderson, be hereby incorporated by, this patent disclosure be adsorbed the into acyl caprolactam of Sodium peroxoborate, comprise benzoyl caprolactam.
SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also is known in the art and can be used to the present invention.One class has the non-oxygen bleaching agent of privilege to comprise photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonation phthalocyanine phthalocyanine zinc and/or aluminum phthalocyanine.See the United States Patent (USP) 4,033,718 that licensed to people such as Holcombe on July 5th, 1977.If you are using, the general content of this SYNTHETIC OPTICAL WHITNER, especially sulfonation phthalocyanine phthalocyanine zinc is about 0.025%～about 1.25% (weight) in the detergent composition.
If necessary, this bleaching compounds can be by manganic compound catalysis.These compounds are well-known in the art, comprise, the disclosed manganese-based catalyst of for example following patent: United States Patent (USP) 5,246,621, United States Patent (USP) 5,244,594, United States Patent (USP) 5,194,416; United States Patent (USP) 5,114,606; And European patent application publication No. 549,271A1,549,272A1,544,440A2 and 544,490A1; These catalyzer preferred examples comprise Mn
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(ClO
4)
2, Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV 4(u-O)
1-(u-OAc)
2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
3, Mn
IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH
3)
3(PF
6), and their mixture.Other metal matrix bleaching catalyst comprises that those are disclosed in United States Patent (USP) 4,430,243 and United States Patent (USP) 5,114,611 in catalyzer.In order to strengthen bleaching, manganese has various cooperation ligands; It is applied in report in the following United States Patent (USP): 4,728,455; 5,284,944; 5,246,6 12; 5,256,779; 5,280,117; 5,274,147; 5,153,161; With 5,227,084.
In fact, and it is unrestricted, the compositions and methods of the invention can be conditioned, thereby obtain in wash water solution at least about millionth active bleaching catalyst species, the concentration of catalyst species is about 0.1ppm～about 700ppm in the preferred washing liquid, more preferably from about 1ppm～about 500ppm.
Can contain amine according to detergent composition of the present invention.The general corresponding following formula of this amine:
R wherein
1Be C
6-C
22Alkyl, alkenyl, cyclic aliphatic or many cyclic groups, they can be reached, and three hydroxyls or phenyl replace and can be reached 12 ethylene oxide moieties is interrupted.
R wherein
2And R
3Be respectively H or C
1-C
18Straight or branched alkyl or alkenyl, they can be by nearly 12 ethylene oxide moieties replacements; With
R wherein
1And R
2Can form the imidazoline group of following structure jointly:
R wherein
4Be C
8-C
18Alkyl.
R in the following formula
1Preferred C
6-C
18Alkyl; R
2And R
3The preferred C of difference
1-C
4Alkyl is randomly by 1 or 2 ethylene oxide moieties interruptions; And R
4Be C
10-C
16Alkyl.
As implied above, the amine in the following formula is commonly referred to as tensio-active agent amine.This material is at Kirk-Othmer, chemical technology encyclopedia (Encyclopedia of Chemical Technology), and the 4th edition, second volume, " aliphatic amide " has more detailed description in the 405th～425 page (1992).Be incorporated herein this piece article as a reference.
Suitable primary amine, i.e. R in the following formula
2And R
3All be those of H, comprise 1-hexylamine, 1-octylame, lauryl amine, palmitamide, stearylamide, oleylamide, coconut alkylamine, Tallow, beef alkylamine, 6-amino-1-hexanol, 3-isopropoxy propylamine, 3-(2-methoxy ethoxy)-propylamine, 2-(2-amino ethoxy)-ethanol and hexahydroaniline.
Suitable secondary amine, i.e. R in the following formula
2And R
3In have only one to be those of H, comprise two coconut alkylamines, two inferior lauryl amine, two n-hexadecyl amine, two Octadecane base amine and two Tallow, beef alkylamine.
Suitable tertiary amine, i.e. R in the following formula
2And R
3Not those of H, comprise coconut alkyl dimethyl amine, dimethyl oleyl amine, two positive decyl methylamines, two coconut alkyl methylamines, tri-n-octyl amine, three dodecyl amine, hexadecyl three (vinyloxy group) dimethyl amine, two (2-hydroxyethyl) amine of Tallow, beef alkyl, two (2-hydroxyethyl) amine of stearyl and two (2-hydroxyethyl) amine of oleoyl.
Be applicable to those that tetrahydroglyoxaline of the present invention is a following formula:
R wherein
4Be C
9-C
13Alkyl.This material is sold with trade(brand)name VARINE market.
Suitable polycyclic amines comprises based on those of sylvic acid.The example of this amine is those of following formula:
Wherein x and y are 1～3.This class amine is commercially available with trade(brand)name POLYRAD.
Preferable material has the tertiary amine of selling with trade(brand)name ADOGEN in above-mentioned all amine, with the long chain alkyl dimethyl amine of trade(brand)name ARMEEN sale and the ethoxylated amine of selling with trade(brand)name ETHOMEEN.Being used for the most preferred amine of the present composition is 1-hexylamine, 1-octylame, dodecyl dimethylamine (ARMEEN DM12D) and double hydroxyethyl coconut alkylamine (ETHOMEEN C/12).
Bound by theory not, think the amine of the above-mentioned type under the use pH of detergent composition of the present invention condition by protonated.Protonated amine of gained positively charged ion and oleoylsarcosine and may the reaction of other anion surfactant then, it is right to generate a kind of lipophilic surfactant, and this will cause bigger surface absorption and to the superior washing effect of grease dirt.The pKa of the alkylamine that the present invention is useful generally is 9-11, also can play shock absorption for detergent composition in use.
Preferably, be " conc forms " according to liquid composition of the present invention, in this case, liquid detergent composition of the present invention is compared with the conventional liq washing composition, and water content is lower.Water-content is less than 50% of composition weight, preferably is less than 30%, the water more preferably less than 20%.
The advantage that this concentrated product provides is, for consumers, but the product that the human consumer has a kind of less amount to use, for the producer, the producer has lower transportation cost.
Other various components that are applied in the liquid detergent composition can be used, as enzyme and its stablizer, soil-suspending agent, soil release polymer, abrasive, sterilant, tarnish inhibitor, tinting material, foam control agent, sanitas and spices.
The following example is an exemplary composition of the present invention, and does not mean that and limit the scope of the invention.
Example I
Doing following washing test illustrates with AS or AES surfactant system and compares the weather resistance of OS/AS or OS/AES surfactant system:
Test conditions:
-in washing machine, test
-1 circulation
40 ℃ of-temperature
-ballast weight load composition: 2.5kg HEAVY FLANNELETTE felt
-town water (2.5mmol/l hardness)
-product consumption 100ml
Process of the test:
The design of this test is in order to estimate tested composition and the reference group compound removal performance to fat dirt on the fabric.Test is that a series of fat stains that are applied on the calico are carried out.Stain is divided into two parts, a directly contrast to be arranged with object of reference.In 4 total circulations, reciprocally carry out, consider the difference of washing machine simultaneously and exchange washing machine.
Each circulation comprises 1 replicate(determination) of each comparison.
Under the optical condition of control, carry out classification by expert classification person.
With scoring unit of group (PSU) record difference, "+" expression performance is better than with reference to product.
Grade scale (PSU classification)
0=is identical
I think this better 1=
I think this good slightly 2=
This a kind of majority of 3=is better
This is a kind of all better for 4=
The PSU ranked data is statistical computation result repeatedly, gets the mean value of 4 replicate(determination)s.
Prepared the liquid detergent composition that contains following ingredients:
The weight percent % of detergent composition
C
12-C
14N-methyl glucose amide 6.5
C
12-C
14Fatty alcohol ethoxylate 6.5
C
12-C
16Lipid acid 7
Citric Acid, usp, Anhydrous Powder 6.0
Diethylenetriamine pentamethylenophosphonic acid(DTPP) 1.0
Monoethanolamine 13.2
Propylene glycol 12.7
Ethanol 1.8
Amylase (300 KNU/g) 0.1
Lipase (100 KNU/g) 0.15
Proteolytic enzyme (34g/l) 0.5
Endo-A(500?CEVU/G)???????????????????????0.05
Carezyme(5000?CEVU/g)????????????????????0.09
Terephthalate based polyalcohol 0.5
Boric acid 2.4
Micro substance and water
Table I (reference)
The liquid detergent composition of supplementary table I, (composition AI/AII) as follows: composition AI
-do not contain oleoyl sarcosinate
Contain 22% AS (C
12-C
15Alkyl-sulphate)/4%AES (C
12-C
15Alkyl ethoxy sulfate)
Composition AII-does not contain oleoyl sarcosinate and contains 0% AS/26% AES result:
*Notable difference, 95% fiducial interval (LSD)
| Stain | Reference | ????AI | ????AII |
| Hydrophobicity fat stain (repairing/automotive oil) | ????0 | ???+0.1 | ???-1.7 * |
| Wetting ability fat stain (beef/cream) | ????0 | ???-0.2 | ???-1.7 * |
Conclusion is not containing under the oleoyl sarcosinate situation, and the AES tensio-active agent is poorer than the AS system.Liquid detergent composition among the supplementary table I, (composition BI/BII) as follows: composition BI-contains oleoyl sarcosinate (9% OS) and contains 9%AS composition BII-and contain oleoyl sarcosinate (9% OS) and contain 9% AES result:
*Notable difference, 95% fiducial interval (LSD)
| Stain | Reference | ????AI | ????AII |
| Hydrophobicity fat stain (repairing/automotive oil) | ????0 | ????0.9 * | ????1.1 * |
| Wetting ability fat stain (beef/cream) | ????0 | ????1 * | ????0.7 * |
Conclusion:
When preparing with oleoyl sarcosinate, the AES tensio-active agent has identical washing effect with AS.
Example II
Prepared following liquid detergent composition:
The weight percent % of detergent composition:
A???????B???????C???????D
C
12-C
15Alkyl ethoxy sulfate-11.0 6.0 16.0
Oleoyl sarcosinate 63 12 9
Linear alkylbenzene sulfonate 14-6-
C
12-C
15Alkyl-sulphate 4 16.0--
C
12-C
14N-methyl glucose amide-7.0 9.0 6
C
12-C
14Fatty alcohol ethoxylate 12.0 5.0 3.0 4
C
12-C
16Lipid acid 7777
Citric Acid, usp, Anhydrous Powder 6.0 4.5 3.5 3.5
Diethylenetriamine pentamethylenophosphonic acid(DTPP) 1.0 1.0 2.0 2.0
Monoethanolamine 13.2 12.7 12.8 11.0
Propylene glycol 12.7 14.5 13.1 10.0
Ethanol 1.8 1.8 4.7 5.4
Amylase (300 KNU/g) 0.1 0.1 0.1 0.1
Lipase (100 KNU/g) 0.15 0.15 0.15 0.15
Proteolytic enzyme (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
Boric acid 2.4 2.4 2.8 2.8
DC?3225C????????????????????????0.03??0.04?????0.03???0.04
High dispersing silica gel 200 0.03 0.04 0.04 0.03
Side chain polysiloxane 0.3 0.3 0.3 0.3
Water and micro substance are added to 100%
Find that the aforesaid liquid detergent composition is very effective for removing the grease dirt under different working conditionss.
Claims (10)
1. liquid laundry detergent compositions that contains surfactant system; said surfactant system comprises a kind of oleoyl sarcosinate and one or more anion surfactants, and this anion surfactant is selected from alkyl alkoxy sulfate and/or alkyl-sulphate.
2. liquid laundry detergent compositions according to the conc forms of claim 1, it comprises and is less than 30% water.
3. liquid laundry detergent compositions according to claim 1 or 2, wherein anion surfactant is selected from alkyl alkoxy sulfate.
4. one kind according to any one liquid laundry detergent compositions in the claim 1～3, and wherein anion surfactant is selected from a kind of alkyl ethoxy sulfate.
5. one kind according to any one liquid laundry detergent compositions in the claim 1～4, and wherein anion surfactant is C
12-C
15Alkyl ethoxy sulfate.
6. liquid laundry detergent compositions according to claim 1 or 2, wherein anion surfactant is C
12-C
15Alkyl-sulphate.
7. one kind according to any one liquid laundry detergent compositions in the claim 1～6, and it also comprises the nonionogenic tenside that is selected from polyhydroxy fatty acid amide.
8. liquid laundry detergent compositions according to claim 7, wherein nonionogenic tenside is C
12-C
14The N-methyl glucose amide.
9. one kind according to any one liquid laundry detergent compositions in the claim 1～8, its also comprises surfactant, washing assistant, enzyme and other conventional detergent ingredients.
10. purposes according to the liquid laundry detergent compositions of any one in the claim 1～9, it is used for the pre-treatment of fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95194267 CN1153524A (en) | 1994-06-01 | 1995-05-18 | Liquid detergent composition contg. oleoyl sarcosinates and anionic surfactants |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/252,037 | 1994-06-01 | ||
| CN 95194267 CN1153524A (en) | 1994-06-01 | 1995-05-18 | Liquid detergent composition contg. oleoyl sarcosinates and anionic surfactants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1153524A true CN1153524A (en) | 1997-07-02 |
Family
ID=5082644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95194267 Pending CN1153524A (en) | 1994-06-01 | 1995-05-18 | Liquid detergent composition contg. oleoyl sarcosinates and anionic surfactants |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1153524A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935054A (en) * | 2018-09-21 | 2020-03-31 | 理研香料控股株式会社 | Stabilizer for sulfite aqueous solution and deodorant |
-
1995
- 1995-05-18 CN CN 95194267 patent/CN1153524A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935054A (en) * | 2018-09-21 | 2020-03-31 | 理研香料控股株式会社 | Stabilizer for sulfite aqueous solution and deodorant |
| CN110935054B (en) * | 2018-09-21 | 2023-03-28 | 理研香料控股株式会社 | Stabilizer for sulfite aqueous solution and deodorant |
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