CN1228809A - Nonaqueous detergent compositions containing specific alkyl benzene sulfonate surfactant - Google Patents
Nonaqueous detergent compositions containing specific alkyl benzene sulfonate surfactant Download PDFInfo
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- CN1228809A CN1228809A CN97197436A CN97197436A CN1228809A CN 1228809 A CN1228809 A CN 1228809A CN 97197436 A CN97197436 A CN 97197436A CN 97197436 A CN97197436 A CN 97197436A CN 1228809 A CN1228809 A CN 1228809A
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
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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
- 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
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Abstract
This invention relates to a nonaqueous liquid detergent containing a surfactant selected from the alkali metal salts of C10-C16 alkylbenzene sulfonic acid derived from alkylbenzenes having a tetralin content lower than 5%.
Description
Invention field
The present invention relates to non-aqueous and be the liquid laundry Betengent product of the stabilising dispersions form of particulate matter such as SYNTHETIC OPTICAL WHITNER and/or other detergent composition additional adjuvants.
Background of invention
Liquid nonaqueous detergent is familiar with by those skilled in the art.The interesting especially part of this class washing composition is to have strengthened the particularly chemical compatibility of SYNTHETIC OPTICAL WHITNER of detergent composition component.
In this non-aquatic products thing, if when the common solid-state detergent composition ratio of component of small part is in being dissolved in aqueous liquid matrix, show lower reacting to each other property.
Although the chemical compatibility of component can be enhanced in non-water liquid detergent compositions, the physical stability of this composition may become problem again.This is because there is the trend that is separated in this product, because institute's dispersive insoluble solid particulate matter falls and is deposited in the container bottom of preserving described liquid detergent product in the suspensoid.As a result of this class problem, also exist relate to the tensio-active agent of suitable type and appropriate amount particularly anion surfactant fully be blended into difficulty in the non-aqueous liquid detergent product.Certainly must choose anion surfactant makes the use of its this class material when can offering the clean usefulness of the acceptable fiber of this composition can not cause viscosity to be raised to unacceptable degree.In this product, can add viscosity control agent to improve its physical stability.But this material only can increase the cost and the volume of described product, and can contribution to some extent on the laundry/cleaning performance of this detergent composition.
From the above, obviously exist identify and provide have degree of physical stability and industrial acceptable perfusion, the lasting needs that contain the liquid detergent composition of negatively charged ion of on-aqueous liquid product form.Therefore, a target of the present invention provides detergent product non-water, anion-containing, and they have the physical stability of this special needs and outstanding perfusion characteristics.
In DE 3728047, EP 484095 and WO 92/09678, the non-aqueous liquid detergent compositions that contains high-level anion surfactant has been described.The liquid nonaqueous detergent composition that these documents all can obtain having good physical properties and perfusion property less than narration, the selectivity open or alkylbenzene sulfonate of giving chapter and verse.
The present invention's general introduction
The invention provides the non-water liquid detergent compositions that comprises anion surfactant, described anion surfactant is selected from and is derived from the C of tetralin content less than 5% alkylbenzene
10-C
16An alkali metal salt of alkyl benzene sulphonate (ABS).
Detailed description of the present invention
(A) main anion surfactant
The main anion surfactant that is used as the basal component of described non-water liquid phase is selected from one of an alkali metal salt of alkyl benzene sulphonate (ABS), its alkyl is the alkyl that contains the straight or branched of 10-16 the carbon atom of having an appointment, its configuration characteristic is that the tetralin content of described alkyl benzene sulphonate (ABS) is less than 10%, preferably is less than 5%.Tetralin is the by product that a kind of linear alkyl benzene is produced.
Particularly preferably be the sodium salt and the sylvite of line style linear alkyl benzene sulphonic acid (LAS), the average carbon atom number of wherein said alkyl is about 11-14.C
11-C
14The sodium salt of LAS is preferred especially.
Described alkyl benzene sulphonate (ABS) salt anionic surfactant will be partially dissolved in the on-aqueous liquid thinner.For forming the required structure liquid phase of suitable phase stability and acceptable rheological, the amount of described alkyl benzene sulphonate (ABS) salt anionic surfactant generally is about 30-65% of described liquid phase weight.More preferably described alkyl benzene sulphonate (ABS) salt anionic surfactant accounts for about 35-50% of the non-water liquid phase weight of composition described herein.Use this anion surfactant to be equivalent to about 15-60% (weight) of anionic surfactant concentration in the whole composition, more preferably about 20-40% (weight) of described composition with this concentration.
(B) nonaqueous detergent composition of the present invention also can comprise a kind of liquid phase that contains tensio-active agent and low polar solvent that is dispersed with described alkyl benzene sulphonate (ABS) therein.The liquid phase of detergent composition described in this and solid phase and composition forms, preparation and purposes will illustrate in greater detail below:
Unless otherwise noted, all here concentration and ratio all are by weight.
Other tensio-active agent
The amount of the surfactant mixture component of detergent composition described in this can be according to the difference of the property quality and quantity of other composition component and difference, also according to the difference of the required rheological of the final composition that forms and difference.In general, the consumption of this surfactant mixture accounts for about 10-90% of described composition weight.More preferably described surfactant mixture accounts for about 15-50% of described composition weight.
The United States Patent (USP) 3664961 of the Norris that on May 23rd, 1972 authorized has been listed the type of typical negatively charged ion, nonionic, both sexes and zwitterionics and the kind of these tensio-active agents.
The preferred anionic surfactants tensio-active agent comprises the alkyl sulfuric ester tensio-active agent, in this article refers to formula ROSO
3The water-soluble salt of M or acid, R is preferably a C in the formula
10-C
24Alkyl is preferably an alkyl or has C
10-C
18The hydroxyalkyl of moieties, more preferably a C
12-C
15Alkyl or hydroxyalkyl, M are H or positively charged ion for example alkali metal cation (for example sodium, potassium, lithium) or ammonium or replace ammonium (quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion).
Anion surfactant very preferably comprises alkyl alkoxylated sulfate surfactant, in this article refers to formula RO (A)
mSO
3The water-soluble salt of M or acid, R is a unsubstituted C in the formula
10-C
24Alkyl or have C
10-C
24The hydroxyalkyl of moieties is preferably a C
10-C
18Alkyl or hydroxyalkyl, more preferably C
12-C
15Alkyl or hydroxyalkyl, A is an oxyethyl group or a propoxy-unit, m is greater than 0, generally between about 0.5-about 6, and more preferably between about 0.5-about 3, M is that H or a positively charged ion for example can be metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replace ammonium cation.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are to pay close attention in this.The example of concrete replacement ammonium cation comprises quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion.The example of this tensio-active agent has C12-C15 alkyl 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), M is selected from sodium and potassium easily in the formula.
The anion surfactant that other available is fit to has alkyl sulfonate surfactants, comprises according to " The Journal of the American Oil Chemists Society ", and 52 (1975), use gas SO described in the 323-329 page or leaf
3The C of sulfonated line style
8-C
20The ester of carboxylic acid (being lipid acid).The raw material that is fit to will comprise that the natural fat material is as being derived from the material of tallow, palm wet goods.
Preferred alkyl sulfonate surfactants (particularly for the laundry purposes) comprises the alkyl sulfonate surfactants of following structural formula:
R in the formula
3Be a C
8-C
20Alkyl, be preferably an alkyl or its combination, R
4Be a C
1-C
6Alkyl, be preferably an alkyl or its combination, M is the positively charged ion that and described alkyl ester sulfonate form a kind of water-soluble salt.The salt-forming cation that is fit to comprises metal such as sodium, potassium and lithium and replacement or unsubstituted ammonium cation.Preferred 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 can be used for the decontamination purpose also can be included in the laundry detergent composition of the present invention.They may comprise soap salt (for example comprise sodium, potassium, ammonium and substituted ammonium salt such as one, two and triethanolamine salt), C
8-C
22Uncle or secondary sulfonated alkane, C
8-C
24Alkene sulfonate, by for example at sulfonated polycarboxylic acid, the C of the sulfonation preparation of the pyrolysis product of the alkaline earth metal citrate described in the british patent specification 1082179
8-C
24Alkyl polyglycol ether sulfate (comprising nearly 10 moles oxyethane); Monoesters (the particularly saturated and undersaturated C of alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleoyl glycerine vitriol, alkyl phenol epoxy ethane ether salt, sulfonated alkane, N-acyl taurine salt, amber alkyl amide salts and alkyl sulfo succinate, sulfosuccinate
12-C
18Monoesters) and the diester of sulfosuccinate (particularly saturated and undersaturated C
6-C
12Diester), the vitriol of the vitriol of alkyl polysaccharide such as alkyl polyglucoside (the not Sulfated compound of nonionic is narrated below) and all suc as formula RO (CH
2CH
2O)
K-CH
3COO-M
+The many ethoxy carboxylates of alkyl (R is a C in the formula
8-C
22Alkyl, k are the integers of a 1-10, and M is the salt-forming cation of a solubility).Resinous acid and hydrogenated resin acid also are suitable for, such as rosin, staybelite be present in or be derived from the resinous acid and the hydrogenated resin acid of tallol.In " Surface Active Agents and Detergents " (Vol. I and II by Schwartz, Perry and Berch), narrated other example.23 hurdles, 58 row of United States Patent (USP) 3929678 that license to Laughlin etc. on December 30th, 1975 also generally disclose various these class tensio-active agents (document is incorporated this paper by reference into) to 29 hurdles, 23 row.
When described anion surfactant was included in the detergent composition of the present invention, it is about 40% that its amount is generally about 1-, about 25% (weight) of preferably about 5-.
One class can be used for the condenses that nonionogenic tenside of the present invention is the oxyethane of tool one hydrophobic part, and it provides, and to have scope be 8-17, preferred 9.5-14, the more preferably tensio-active agent of the average hydrophile-lyophile balance (HLB) of 12-14.Described hydrophobic (oleophylic) part can be aliphatic series or aromaticity, and the length of the polyethylene oxide base of any concrete hydrophobic group condensation can easily be regulated and produced equilibrated water-soluble cpds between the hydrophilic and hydrophobic units with required degree.
Particularly preferred this class nonionogenic tenside is the C that every mol of alcohol contains the 3-12 moles of ethylene oxide
9-C
15Primary alcohol ethoxylate, particularly 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 alkyl polyglucoside compound of following general formula:
RO (C
nH
2nO)
tZ
xZ is the part that is derived from glucose in the formula; R is the saturated hydrophobic alkyl that contains 12-18 carbon atom; T is 0-10, and n is 2 or 3; X is 1.3-4, and described compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) and the 50% following short-chain alkyl polyglucoside below 10%.Such compound and its purposes aspect washing composition are disclosed in EP-B 0070077,0075996 and 0094118.
The same nonionogenic tenside that is suitable for is the polyhydroxy fatty acid amide surfactants with following formula:
R in the formula
1Be H or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-31Alkyl, Z are to have a linear hydrocarbyl chain and at least 3 many hydroxyl alkyls or its alkoxy derivatives that hydroxyl directly links to each other with described chain.Preferred R
1Be methyl, R
2Be a straight C
11-15Alkyl chain or alkenyl chain such as coconut alkyl or its mixture, Z are derived from a kind of reducing sugar in reductive amination process such as glucose, fructose, maltose and lactose.
The on-aqueous liquid thinner
In order to form the liquid phase of described detergent composition, the low polar organic solvent of previously described tensio-active agent (mixture) with a kind of on-aqueous liquid thinner such as liquid alcohol alkoxide or a kind of non-water can be mixed.
The alcohol alkoxide
Be applicable to that a kind of component that forms the liquid diluent of composition described in this comprises the alkoxy fatty alcohols material.This class material itself also is a nonionogenic tenside.This class material has following general formula:
R
1(C
mH
2mO)
nR in the OH formula
1Be C
8-16Alkyl, m are 2-4, and the n scope is about 2-12.Preferred R
1Be one and contain 9-15 the carbon atom of having an appointment, more preferably contain the primary alkyl or the secondary alkyl of 10-14 the carbon atom of having an appointment.Also preferred described alkoxy fatty alcohols is that per molecule contains 2-12 the ethylene oxide moiety of having an appointment, and more preferably per molecule contains the ethoxylation material of 3-10 the ethylene oxide moiety of having an appointment.
The alkoxy fatty alcohols component of described liquid diluent has the hydrophile-lyophile balance (HLB) of scope for about 3-17 usually.More preferably the HLB scope of this material is about 6-15, most preferably is about 8-15.
The example of fatty alcohol alkoxy compound of one of main ingredient that can be used as the on-aqueous liquid thinner of composition described herein comprises by the alcohol preparation of 12-15 carbon atom and comprises the alcoxylates of those Fatty Alcohol(C12-C14 and C12-C18) of about 7 moles oxyethane.This class material is sold with commodity Neodol 25-7 by name and Neodol 23-6.5 by Shell Chemical Company.Other useful Neodols comprises Neodol 1-5 (be a kind of have about 5 moles of ethylene oxide and the ethoxylized fatty alcohol of average 11 carbon atoms on its alkyl chain); Neodol 23-9 (a kind of ethoxylation C with about 9 moles of ethylene oxide
12-C
13Primary alconol) and Neodol 91-10 (a kind of ethoxylation C with about 10 moles of ethylene oxide
9-C
11Primary alconol).Such alcohol ethoxylate is also sold with the trade(brand)name of Dobanol by Shell Chemical Company.Dobanol 91-5 is a kind of ethoxylation C with average 5 moles of ethylene oxide
9-C
11Fatty Alcohol(C12-C14 and C12-C18), Dobanol 25-7 are the ethoxylation C that a kind of every mole of Fatty Alcohol(C12-C14 and C12-C18) has average 7 moles of ethylene oxide
12-C
15Fatty Alcohol(C12-C14 and C12-C18).
The example of the ethoxylated alcohol that other is suitable for comprises Tergitol 15-S-7 and Tergitol 15-S-9, and both all are linear secondary alcohol ethoxyl compounds of being sold by Union Carbide Corporation.The former is the C of tool 7 moles of ethylene oxide
11-C
15The mixed ethoxylated product of linear secondary alcohol, the latter is a kind of similar product, but has 9 moles of oxyethane for reaction.
The alcohol ethoxylate in the composition of the present invention of can be used for of other type is that the nonionogenic tenside of higher molecular weight is such as Neodol 45-11, they are oxirane condensation products of similar more senior Fatty Alcohol(C12-C14 and C12-C18), described more senior Fatty Alcohol(C12-C14 and C12-C18) has 14-15 carbon atom, and the quantity of every moles of ethylene oxide base is about 11.This class product is also sold by Shell ChemicalCompany.
The alcohol alkoxylate component that is used as the part of liquid diluent in the non-aqueous composition hereinto is generally about 1-60% of described composition weight.Described alcohol alkoxylate component more preferably constitutes about 5-40% of composition weight described in this.Most preferably described alcohol alkoxylate component constitutes about 10-25% of the weight of detergent composition described in this.
Non-water hangs down polar organic solvent
The another kind of component that can constitute the liquid diluent of the part of detergent composition described in this comprises non-water, low polar organic solvent.Used term " solvent " is meant the on-surface-active carrier or the thinner part of described composition liquid phase in this.Although some basal components of composition described in this and/or optional components can be dissolved in really contain " solvent " mutually in, the form that other component will contain " solvent " particulate matter in mutually to be scattered in exists.Therefore used term " solvent " and do not mean that and require vehicle substance really can dissolve adding all detergent composition components wherein.
Be used as that non-water organic substance of solvent is those low polar liquid in this.For purpose of the present invention, " low polarity " liquid is the liquid of one of particulate matter (being peroxygen bleach, Sodium peroxoborate or SPC-D) of those little preferred types that may (if possibleization) dissolving be used for composition described in this.Therefore should not use the solvent such as the ethanol of high polarity.Can be used for the actual alkylene glycol list that comprises of the low polar solvent of the suitable type in the non-aqueous liquid detergent compositions described in this than the methyl ester of lower alkyl ether, low molecular poly, lower molecular weight and acid amides etc.
For the non-water low polar solvent of a kind of preferred type used in this comprise one-, two-, three-or four-C
2-C
3Alkylene glycol list C
2-C
6Alkyl oxide.The object lesson of this compounds comprises diglycol monotertiary butyl ether, Tetraglycol 99 single-butyl ether, the single ethyl ether of dipropylene glycol and dipropylene glycol single-butyl ether.The single ethyl ether of diglycol monotertiary butyl ether and dipropylene glycol is particularly preferred.Such compound becomes commercialized, and its commodity are called Dowanol, Carbitol and Cellosolve.
Non-water of useful other preferred type, low polar organic solvent comprise lower molecular weight polyoxyethylene glycol (PEGs) in this.This material has the molecular weight at least about 150.Molecular weight ranges is most preferred for the PEGs of about 200-600.
Another preferred type nonpolar, non-aqueous solvent comprises the methyl esters of lower molecular weight.This class material has general formula R
1-C (O)-OCH
3, R in the formula
1Scope is 1 to about 18.The example of the lower molecular weight methyl esters that is suitable for comprises methyl acetate, methyl propionate, methyl caprylate and methyl dodecanoate.
Used non-water, low polar organic solvent yes should be able to other component such as SYNTHETIC OPTICAL WHITNER and/or promoting agent compatibility and the Fails To Respond in the liquid detergent composition that is used for this.The conventional amount used of this solvent composition is about 1-60% of described composition weight.More preferably non-water, low polar organic solvent account for about 5-40% of composition weight, most preferably account for about 10-25% of composition weight.
The liquid diluting agent concentration
The same with the concentration of surfactant mixture, the liquid diluent total amount will depend on the type and the consumption of other component of composition and depend on required composition character in the described composition hereinto.In general, liquid diluent will account for about 20-95% of composition weight described in this.More preferably liquid diluent accounts for about 50-70% of described composition weight.
Solid phase
Nonaqueous detergent composition in this can further comprise a solid phase of disperseing and being suspended in the particulate matter in the liquid phase.In general, the particle diameter of this particulate matter is about 0.1-1500 micron.More preferably the particle diameter of this particulate matter is about 5-500 micron.
Used particulate matter comprises one or more granular detergent composition components in this, its actual non-water liquid phase that is insoluble to described composition.The particulate matter of available types is described in detail as follows:
The peroxygen bleach of the optional bleach activator of tool
The particulate matter that is used to form the most preferred type of the detergent composition solid phase described in this comprises the peroxygen bleach particle.This in nature peroxygen bleach can be organic or inorganic.The inorganic peroxy SYNTHETIC OPTICAL WHITNER is used with bleach activator usually.
Useful organic peroxy SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises magnesium salts, 4-nonyl amino-4-oxo Perbutyric Acid and the diperoxy dodecanedioic acid of Magnesium monoperoxyphthalate hexahydrate, metachloroperbenzoic acid.This class SYNTHETIC OPTICAL WHITNER is disclosed in United States Patent (USP) people's such as disclosed Banks on the 20th February in 4483781,1985 the European patent application EP-A-133354 of the Hartman that authorized on November 20th, 1984 and the people's such as Chung that authorize November 1 nineteen eighty-three the United States Patent (USP) 4412934.SYNTHETIC OPTICAL WHITNER very preferably comprises that also the 6-nonyl amino-6-oxo described in the United States Patent (USP) 4634551 that licenses to people such as Burns on January 6th, 1987 crosses oxy hexanoic acid (NAPAA).
The inorganic peroxy SYNTHETIC OPTICAL WHITNER also can be used in this detergent composition with the particulate matter form.In fact inorganic SYNTHETIC OPTICAL WHITNER is that institute is preferred.This class inorganic peroxy compounds comprises alkali metal perborate and percarbonate material, most preferably percarbonate.For example can use Sodium peroxoborate (for example one or tetrahydrate).The inorganic SYNTHETIC OPTICAL WHITNER that is suitable for also can comprise the carbonate peroxidation hydrate and " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxidation hydrate, urea peroxidation hydrate and the sodium peroxide of equal value of sodium or potassium.Persulphate SYNTHETIC OPTICAL WHITNER (as the OXONE by the DuPont suitability for industrialized production) also can be used.Usually applying silicate, borate, vitriol or water soluble surfactant active on the inorganic peroxy SYNTHETIC OPTICAL WHITNER.For example, the percarbonate particles thing of coating can be bought from different suppliers such as FMC, Solvay Interox, Tokai Denka and Degussa.
Inorganic peroxy SYNTHETIC OPTICAL WHITNER such as perborate and percarbonate etc. are preferred to mix uses with bleach activator, promptly on the spot with the corresponding peroxy acid aqueous solution of bleach activator in preparation (promptly using the composition in this to carry out fabric washing and/or bleach central the preparation).The various non-limiting examples of promoting agent are disclosed in the United States Patent (USP) 4915854 that licenses to people such as Mao April 10 nineteen ninety and license to November 1 nineteen eighty-three in people's such as Chung the United States Patent (USP) 4412934.Nonanoly acyloxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) promoting agent are typical cases wherein.Also can use its mixture.Also can be for other typical SYNTHETIC OPTICAL WHITNER of available in this and promoting agent referring to previously described US 4634551.
The bleach activator that other available is derived from amido is the material with following formula:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2R in C (O) the L formula
1Be an alkyl that contains about 12 carbon atoms of the 6-that has an appointment, R
2Be an alkylidene group that contains about 6 carbon atoms of 1-, R
5Be H or alkyl, aryl or the alkaryl that contains about 10 carbon atoms of the 1-that has an appointment, L is any suitable leavings group.Leavings group is as all-hydrolytic (perhydrolysis) negatively charged ion substituted any group in the result of the nucleophilic reaction on the bleach activator and from the bleach activator.
The example of the bleach activator of preferred following formula comprises as at (6-decoyl amino-caproyl) the oxo benzene sulfonate described in the previously described United States Patent (USP) 4634551, (6-nonanoyl amino-caproyl) oxo benzene sulfonate, (6-caprinoyl amino-caproyl) oxo benzene sulfonate and its mixture.This class mixture is characterized as being (6-C in this
8-C
10Alkyl amido-caproyl) oxo benzene sulfonate.
Another kind of useful bleach activator comprises the promoting agent of disclosed benzoxazine type in the people's such as Hodge that authorize on October 30 nineteen ninety of incorporating this paper by reference into the United States Patent (USP) 4966723.A kind of promoting agent of benzoxazine type very preferably is:
Another kind of useful bleach activator comprises the acyl caprolactam and the acyl group Valerolactim promoting agent of acyl lactam promoting agent, particularly following formula;
R in the formula
6Be H or alkyl, aryl, alkoxy aromatic yl or an alkaryl that contains about 12 carbon atoms of 1-.Lactan promoting agent very preferably comprises benzoyl caprolactam, decoyl hexanolactam, 3,5,5-trimethyl acetyl hexanolactam, nonanoyl hexanolactam, caprinoyl hexanolactam, undecylene acyl hexanolactam, benzoyl Valerolactim, decoyl Valerolactim, caprinoyl Valerolactim, undecylene acyl Valerolactim, 3,5,5-trimethyl acetyl Valerolactim and its mixture.Also referring to the United States Patent (USP) 4545784 that licenses to Sanderson on October in 1985 8 of incorporating this paper by reference into, it discloses and has comprised the acyl caprolactam that is adsorbed onto the benzoyl caprolactam on the Sodium peroxoborate.
If peroxygen bleach is used as all or part of of particulate matter of main existence and uses, they generally account for about 1-30% of described composition weight so.More preferably peroxygen bleach accounts for about 1-20% of composition weight.Most preferably the peroxygen bleach amount is about 3-15% of composition weight.If the use bleach activator, it will account for about 0.5-20% of composition weight so, more preferably account for the 1-10% of composition weight.When using promoting agent, the molar ratio scope of SYNTHETIC OPTICAL WHITNER and promoting agent is about 1 usually: 1-10: 1, more preferably from about 1.5: 1-5: 1.
In addition, found that its chemical stability is better when bleach activator and some acid during as the citric acid agglomeration.
Tensio-active agent
The another kind of possible particulate matter type that can be suspended in the non-water described in this, the liquid detergent composition comprises the auxiliary anion surfactant that is insoluble to non-water liquid phase wholly or in part.The general type of this deliquescent anion surfactant of tool comprises uncle or secondary alkyl sulfate anion surfactant.This tensio-active agent is that those pass through higher C
8-C
20The tensio-active agent that the sulfation of Fatty Alcohol(C12-C14 and C12-C18) is produced.
Conventional uncle's a heatable brick bed base sulfate surfactant has following general formula:
ROSO
3 -M
+Wherein R generally is the linear C of straight or branched
8-C
20Alkyl, M are that water adds dissolved cation.Preferred R is a C
10-C
14Alkyl and M are basic metal.Most preferably R is about C
12And M is a sodium.
Conventional secondary alkyl sulfate also can be used as the main anion surfactant component of the solid phase of composition described in this.Conventional secondary alkyl sulfate surfactant is those materials with sulphate moiety of alkyl " main chain " stochastic distribution along described molecule.This class material can be represented by following structural formula:
CH
3(CH
2)
n(CHOSO
3 -M
+) (CH
2)
mCH
3In the formula m and n be 2 or bigger integer and m+n sum be generally about 9-15, M is that water adds dissolved cation.
If auxiliary anion surfactant such as alkyl-sulphate is used as all or part of that institute must particulate matter, it will account for about 1-10% of composition weight so, more preferably account for about 1-5% of composition weight.Preparation is added in the composition described in this as all or part of alkyl-sulphate of described particulate matter and with it, described composition with the not alkoxylated alkyl sulphate separating substances of the part that can constitute main alkyl ether sulfate surfactant component as the described liquid phase of part in this.
The organic synergistic auxiliary agent
The shadow that the another kind of possible type that can be suspended in the particulate matter in non-water, the liquid detergent composition described in this comprises calcium that the composition that is used for offseting this runs in the middle of being used to do washing/bleach or other ion and the water hardness to organic washing builder.This class examples of substances comprises basic metal, Citrate trianion, succinate, malonate, lipid acid, carboxymethyl succinate, carboxylate salt, polycarboxylate and poly-acetyl carboxylate salt.Object lesson comprises sodium, potassium, the lithium salts of oxo disuccinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.Other example comprises material and the alkane hydroxy phosphonate of the commodity Dequest by name that organic phosphate type multivalence integrated agent such as Monsanto sells.Citrate trianion is very preferred.
Other organic synergistic auxiliary agent that is fit to comprises known polymkeric substance and multipolymer with higher molecular weight of builder character.For example, this material comprises that the trade mark that suitable polyacrylic acid, polymaleic acid and poly propenoic acid maleic acid and its salt such as BASF sell is the material of Sokalan.
The suitable type of other organic synergistic auxiliary agent comprises that the water-soluble salt of more senior lipid acid is " soap ".They comprise that alkali metal soap such as containing about 24 carbon atoms of the 8-that has an appointment, preferably contains sodium, potassium, ammonium and the alkanol ammonium salts of the more senior lipid acid of about 18 carbon atoms of the 12-that has an appointment.Soap can prepare by the direct saponification of fat and oil, maybe can prepare by the neutralization of free fatty acids.Useful especially is that the sodium salt and the sylvite of mixture that is derived from the lipid acid of Oleum Cocois and tallow is sodium tallowate soap or tallow potash soap and Oleum Cocois soda soap or Oleum Cocois potash soap.
If insoluble organic detergent builder as institute must particulate matter all or part of, they generally account for about 1-20% of composition weight described in this so.More preferably this builder accounts for about 4-10% of composition weight.
The inorganic alkaline material
Can be suspended in the another kind of possible particulate matter type in non-water, the liquid detergent composition described in this may comprise and be used to make the rinsing solution that is formed by this composition to be generally the material of alkalescence.This class material also can be used as washing builder (promptly as being used to offset the material of the water hardness to the negative impact of washing effect), or also can be not as the washing builder.
The example of the alkaline material that is fit to comprises water soluble alkali metal carbonate, supercarbonate, borate, silicate (silicate) and silicate (metasilicate).Although owing to the reason of ecological aspect is not preferably used water-soluble phosphate, it still can be used as alkaline material.They comprise alkali metal pyrophosphate, orthophosphoric acid salt, polyphosphate and phosphonate.In all these alkaline materials, alkaline carbonate such as yellow soda ash is most preferred.
But described alkaline material is if the form of the salt of hydration, and they also can be used as siccative in the non-aqueous liquid detergent compositions hereinto so.Also can provide and make easily by the chemically stable benefit of those composition component such as peroxygen bleach of water inactivation as the existence of the alkaline material of siccative.
If described alkaline material is used as all or part of particulate matter component, it generally accounts for about 1-15% of composition weight in this so.More preferably described alkaline material can account for about 2-10% of composition weight.Although this class material is water miscible, it generally is insoluble in the nonaqueous detergent composition in this.Therefore this class material generally is scattered in the non-water liquid phase with the form of independent particulate.
Optional composition component
Except previously described composition liquid phase and solid components, the detergent composition in this also can and preferably contain various optional components.This optional components both can be that liquid form also can be a solid form.Described optional components both can be dissolved in the liquid phase and also can be scattered in the liquid phase with the form of particulate or droplet.Some materials that can choose wantonly in the composition that is used for this illustrate in greater detail as follows:
Optional inorganic washing auxiliary detergent
Detergent composition in this also can be chosen the inorganic washing auxiliary detergent that comprises the listed auxiliary agent of preamble one or more types in addition that also are used as alkaline material wantonly.This optional inorganic assistant agent can comprise that for example aluminosilicate is such as zeolite.Aluminosilicate zeolites and its purposes as detergent builder have more fully in the people's such as Corkill of mandate on August 12nd, 1986 United States Patent (USP) 4605509 to be discussed, and the content of this patent disclosure is incorporated this paper by reference into.Same crystalline multilayer silicate such as the crystalline multilayer silicate of discussing in this ' 509 United States Patent (USP) also is suitable in the detergent composition in this.If use optional inorganic detergent builder, it can account for about 2-15% of composition weight in this.
Optional enzyme
Detergent composition in this also can randomly comprise the enzyme for detergent of one or more types.This kind of enzyme can comprise proteolytic enzyme, amylase, cellulase and lipase.This class material is known and commercialization in this area.They can be blended into the form of suspension, " marumes " or " particle " in the non-aqueous liquid detergent compositions in this.The another kind of enzyme type that is fit to comprises the enzyme type of the slurry form of the enzyme of enzyme in nonionogenic tenside.The enzyme of this form is for example by the trade(brand)name commercialization of Novo Nordisk with " LDP ".
Join enzyme in the composition in this particularly preferably in using here with the enzyme particle shape formula of routine.The particle size range that this kind of enzyme grain is general is about 100-1000 micron, more preferably from about 200-800 micron and being suspended in the non-water liquid phase of whole composition.Compare with other enzyme form, have been found that according to the enzymic activity retention time enzyme grain in composition of the present invention demonstrates the enzyme stability of special needs.Therefore use the composition of enzyme grain needn't contain conventional enzyme stabilizers such as the enzyme stabilizers that when enzyme is blended into aqueous liquid detergent, must often use.
If the use enzyme, so its generally to be enough to providing every gram composition up to about 10mg, more the level of the about 5mg organized enzyme of Chang Weiyue 0.01-is blended in the said non-aqueous liquid compositions.In other words, the non-aqueous liquid detergent compositions in this generally contains the 0.001-5% that has an appointment, the commercial enzyme preparation of preferably about 0.01-1% (weight).For example the proteolytic enzyme level in this commodity preparation is enough to reach usually provides every gram composition 0.005-0.1Anson unit (AU) active level.
Optional sequestrant
Detergent composition in this also can be chosen the metal ion that comprises in the nonaqueous detergent composition that is used to be sequestered in described in this such as the sequestrant of iron and/or manganese wantonly.Therefore this sequestrant is used for forming title complex with the metallic impurity of composition, otherwise these metallic impurity easily make composition component such as the peroxygen bleach inactivation.Useful chelating agents can comprise fragrant chelating agent and its mixture of aminocarboxylate, phosphonate, amino phosphonates do, multifunctional replacement.
The aminocarboxylate that can be used as optional sequestrant comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate, ethylenediamine disuccinate and ethanol Diglycocol.An alkali metal salt of preferred these materials.
When allowing that in detergent composition when having low-level total phosphorus at least, amino phosphonates do also is adapted at being used as sequestrant in the composition of the present invention and comprises the ethylenediamine tetraacetic (methylene phosphonic acid salt) that is called DEQUEST.These amino phosphonates do preferably do not contain have an appointment 6 carbon atoms above alkyl or alkenyl.
Preferred sequestrant comprises hydroxyethyl di 2 ethylhexyl phosphonic acid (HEDP), diethylene triaminepentaacetic acid(DTPA) (DTPA), ethylenediamine disuccinic acid (EDDS) and two pyridine carboxylic acids (DPA) and its salt.When described sequestrant can certainly composition hereinto be used for fabric washing/bleaching as washing auxiliary detergent.If use described sequestrant, they can account for about 0.1-4% of composition weight described in this.More preferably described sequestrant accounts for about 0.2-2% of the weight of detergent composition described in this.
Optional thickening material, viscosity control agent and/or dispersion agent
Detergent composition described in this also can randomly comprise and a kind ofly be used for strengthening described composition and keep the polymkeric substance of its solid particulate components in the ability of suspension.Therefore this class material can be used as thickening material, viscosity control agent and/or dispersion agent.This class material normally the polymeric multi-carboxylate but can comprise other polymkeric substance such as polyvinylpyrrolidone (PVP) and polyamine derivatives such as quaternized, ethoxylation hexamethylene-diamine.
Polymeric multi-carboxylate material can prepare by the polymerization or the copolymerization of suitable unsaturated monomer (preferably with its sour form).The unsaturated monomer acid that polymerizable forms suitable multi-carboxylate polymer comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.The existence in the multi-carboxylate polymer such as monomer segment such as vinyl methyl ether, vinylbenzene and ethene of carboxylate-containing base do not suit, as long as this class segment is no more than about 40% of described polymer weight.
The multi-carboxylate polymer of particularly suitable can make with vinylformic acid.This class in this available be polyacrylic water-soluble salt based on the polymerizing acrylic acid thing.The molecular-weight average of this sour form polymkeric substance is preferably about 2000-10000, and more preferably about 4000-7000 most preferably is about 4000-5000.The water-soluble salt of this acrylate copolymer can comprise for example an alkali metal salt.Such soluble polymer is a known substances.The purposes of such polyacrylate in detergent composition has been disclosed in the United States Patent (USP) 3308067 of the Deihl that authorizes as on March 7th, 1967.This class material also can be fulfiled the function of auxiliary agent.
During use, the amount in the described optional described hereinto composition of thickening material, viscosity control agent and/or dispersion agent should be about 0.1-4% of its weight.More preferably this class material accounts for about 0.5-2% of the weight of detergent composition described in this.
Optional whitening agent, suds suppressor and/or spices
Detergent composition in this also can randomly comprise conventional whitening agent, suds suppressor, silicone oil, bleaching catalyst and/or fragrance material.This class whitening agent, suds suppressor, silicone oil, bleaching catalyst and spices certainly must with the compatible and Fails To Respond of other composition component in non-water surrounding.When whitening agent, suds suppressor and/or spices existed, it generally accounted for about 0.01-2% of composition weight described in this.
The bleaching catalyst that is suitable for comprises the manganese basigamy compound that is disclosed among US 5246621, US 5244594, US5114606 and the US 5114611.
Composition forms
Of the present invention contain the particulate matter liquid detergent composition actual in nature be non-water (or anhydrous).Although seldom water gaging may be blended into as the impurity of major constituent or optional components in this composition, water content at any time all should not surpass about 5% of composition weight described in this.More preferably the water content in the composition of nonaqueous detergent described in this is less than about 1% (weight).
The particulate matter nonaqueous detergent composition that contains described in this is a kind of liquid form.
Preparation of compositions and use
Non-aqueous liquid detergent compositions in this can prepare by following method: at first form the non-water liquid phase that contains described tensio-active agent, then by will other particulate matter component join with any order easily this mutually in, and by the phase stable composition that forms described in this is for example stirred in resulting component mixture mixing.In this method for compositions of a typical preparation, the component of main ingredient and some priority option is with a particular order and mixing under given conditions.
In the first step of a preferred preparation method, what preparation earlier was used to form the liquid phase that contains described tensio-active agent contains the anion surfactant powder.This preparation process comprises one or more line styles C that contains 40-50%
10-C
16The formation of the aqueous slurry of the nonsurfactant salt of one or more dilution usefulness of an alkali metal salt of alkyl benzene sulphonate (ABS) and 3-15%.In the step of following, this slurry is dried to required degree and forms contain the solids that is less than 5% (weight) residuary water.
After being prepared into the material that contains this solid anion surfactant, this material can being mixed with one or more non-aqueous organic solvents and form the liquid phase that contains described tensio-active agent of detergent composition described in this.This can be reduced into powder-form and finish by this powder material is under agitation mixed with a kind of liquid medium that contains one or more non-aqueous organic solvents (tensio-active agent or nonsurfactant or both all have) as previously described by the anion surfactant material that contains that will make in aforementioned pre-preparation step.This being blended in is enough to carry out under whole non-water organic liquid forms the agitation condition of dispersion of the described LAS/ salt of complete blended material.
In the processing step of following, the non-water liquid dispersion that makes is like this ground under the condition of the liquid phase structural, that contain tensio-active agent that is enough to provide detergent composition described in this or the high-shear stirring.This grinding or high-shear agitation condition generally comprise temperature maintenance between 20-50 ℃.The grinding of this mixture and high-shear are stirred the yield value of described structural liquid phase will be brought up in the 1-5Pa scope.
At LAS/ salt after altogether the dispersion of dry thing in on-aqueous liquid forms, this dispersion ground or stirred improve its yield value before or after, can add the other particulate matter that is used for detergent composition described in this.This class component that can add under high-shear is stirred comprises any optional surfactant granules thing, can add all basically organic synergistic builder granule thing such as Citrate trianions and/or lipid acid and/or alkaline material such as yellow soda ash, continue to keep the mixture of this composition component simultaneously under shear agitation.Continue to stir described mixture, if desired, can increase this stirring and make it form the homogeneous dispersion of insoluble solid phase particles thing in described liquid phase.
In second treatment step, the bleach precursor particulate matter is mixed with the levigated suspensoid that obtains in first mixing step.Then with this mixture wet-milling, thus the median size that makes bleach precursor less than 600 microns, preferred 50-500 micron, most preferably 100-400 micron.Then other compound such as bleaching compounds is joined in the resulting mixture.
After part or all of aforesaid solid matter all joins in this stirred mixture, the particulate matter of very preferably peroxygen bleach can be added in the said composition, keep the shear agitation of mixture simultaneously.Add peroxygen bleach to the end, or after all or most of other component add, particularly after the alkaline material particle adds, can really reach the stable benefit of required peroxide bleaching.If add the enzyme grain, so preferably they joined in the on-aqueous liquid matrix at last.
As last step, after adding all particulate matters, the stirring of mixture lasts till for some time that is enough to form the composition with necessary viscosity, yield value and phase stability.Usually this comprises stir about 1-30 minute.
According to preceding method solid ingredient is being joined in the process of on-aqueous liquid, free, the unconjugated moisture content of keeping these solid matters are useful under certain limit.Free water content in these solidss reach usually 0.8% or more than.By reducing free water content, for example, the stability of the composition that makes is significantly improved by with being 0.5% or following level by fluidised bed drying to free water content before solid particulate matter is in being mixed into detergent composition matrix.
The rinsing solution that can be used for being formed for the washing and the bleaching of fabric by the described composition of the present invention that makes of preamble.In general, this composition of significant quantity is added in the water (preferably in the fabric automatic washing machine of routine) and forms described washing/aqueous bleaching solution.Washing/the aqueous bleaching solution that will form like this (preferably under agitation) contacts with waiting to wash with fabric to be bleached then.
The significant quantity that forms liquid detergent composition described in this of washing/aqueous bleaching solution that is added to the water can comprise the amount that is enough to the about 500-7000ppm composition of formation in the aqueous solution.Detergent composition described in this of about 800-5000ppm more preferably is provided in washing/aqueous bleaching solution.
The following example illustrates the preparation of non-aqueous liquid detergent compositions of the present invention and the advantage on the performance.But this embodiment does not also mean that formation limitation of the scope of the invention or qualification.
The embodiment I
The preparation of non-aqueous liquid detergent compositions
1) with butoxy-propoxy--propyl alcohol (BPP) and a kind of C
12-16EO (5) ethoxylated alcohol nonionic surfactant (Genapol 24/50) short period of time (1-5 minute) mixing in the mixing tank of band slurry formula homogenizer makes it to become single-phase.
2) NaLAS is joined in the BPP/Genapol solution in the mixing tank NaLAS is partly dissolved.Mixing time is about one hour.Described jar is covered in order to avoid absorb airborne moisture with nitrogen.
3) liquid base material (LAS/BPP/NI) is pumped in the drum if desired.Add the molecular sieve (3A type, 4-8 order) that is equivalent to liquid base material net weight 10% in each drum.With single blade wheel mixing tank and rotary drum technology molecular sieve is sneaked in the liquid base material.To be blended under the nitrogen covering and carry out in order to avoid from absorption of air moisture.Total mixing time is 2 hours, and the moisture of 0.1-0.4% is removed in the liquid base material afterwards.Make liquid base material pass through a 20-30 mesh sieve filtering molecular sieve.And liquid base material sent back in the mixing tank.
4) preparation joins the other solid ingredient in the described composition, and this class solid ingredient comprises following material:
Yellow soda ash (100 microns of particle diameters)
Citric Acid, usp, Anhydrous Powder sodium
Maleic acid-acrylic acid copolymer (BASF Sokolan)
Whitening agent (Tinopal PLC)
Hydroxyl ethylidene diphosphonic acid tetra-na salt (HEDP)
Diethylenetriamine pentamethylenophosphonic acid(DTPP) sodium.
But with these all levigated solidss join in the mixing tank and to mix with liquid base material up to evenly.The last powder of its time interval is incorporated as about 1 hour.After adding these powder, described jar is covered with nitrogen.The order that these powder add is unimportant.
6) this batch materials disposable pump is crossed a Fryma colloidal mill, described colloidal mill is a simple rotor-stator structure, and one of them high speed rotor rotates in a stator, produces a high shear zone.This has reduced the particle diameter of all solids thing.Caused the raising of yield value (promptly structural).After the cooling this batch materials is reloaded in the mixing tank.
7) in second mixing step, the bleach precursor particulate matter is mixed with levigate suspensoid from first mixing step.The median size of then this mixture being carried out wet-milling and making described bleach precursor is less than 600 microns, preferred 50-500 micron, most preferably 100-400 micron.
8) behind first treatment step, can add other solids, described solids comprises following material:
SPC-D (400-600 micron)
Proteolytic enzyme, cellulase and amylase enzyme grain (400-800 micron)
Titanium dioxide granule (5 microns)
Then these non-solid matters that grind are joined in the mixing tank, then add liquid ingredient (suds suppressor of spices and siloxanes).Then this batch materials is mixed one hour (under nitrogen covers).The composition that obtains has the listed prescription of table I.
The table I
The non-aqueous liquid detergent compositions that contains SYNTHETIC OPTICAL WHITNER
The amino hexanoyl oxygen of composition activity thing % (weight) * LAS sodium salt 21.7C12-16E O=5 alcohol ethoxylate 18.98BPP 18.98 natrium citricum 1.42[4-[N-pelargonyl groups-6-] benzene sulfonic acid] 0.95 chloride salt sodium carbonate, 3 maleic acid-acrylic acid copolymer 3.32HEDP sodium salts, 0.90 protease grain, 0.40 amylase grain, 0.84 cellulase grain, 0.5 SODIUM PERCARBONATE, 18.89 foam inhibitors, 0.35 spices, 0.46 titanium dioxide, 0.5 brightening agent, 0.14 all the other materials to 100.00% of the quaternized many ethoxylations hexamethylene diamine of sodium salt 7.34 diethylenetriamines, 0.90 pentamethylene sodium ascorbyl phosphate methyl
The table I composition that obtains is a kind of stable, pourable non-water efficient liquid laundry washing-agent, and when being used for the laundry operation of fabrics in general, it can provide good decontamination stain and dirt usefulness.
* LAS: be derived from the alkyl benzene sulphonate (ABS) sodium salt that tetralin content is lower than 5% alkylbenzene.
Claims (5)
1. non-aqueous liquid detergent that contains tensio-active agent, described tensio-active agent are selected from and are derived from the C that tetralin content is lower than 5% alkylbenzene
10-C
16An alkali metal salt of alkyl benzene sulphonate (ABS).
2. according to the non-aqueous liquid detergent compositions of claim 1, wherein said tensio-active agent is the sodium salt or the sylvite of linear straight chain alkyl benzene sulphonate (ABS), and the average carbon atom number of wherein said alkyl is 10-16.
3. according to the non-aqueous liquid detergent compositions of claim 2, wherein the average carbon atom number in described alkyl is 11-14.
4. according to the non-aqueous liquid detergent compositions of claim 1-3, wherein said tensio-active agent is C
11-C
14The LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium salt.
5. according to the non-aqueous liquid detergent compositions of claim 1-4, the 10-60% of the described composition weight of wherein said surfactant comprise.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2082696P | 1996-06-28 | 1996-06-28 | |
| US60/020,826 | 1996-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1228809A true CN1228809A (en) | 1999-09-15 |
Family
ID=21800808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97197436A Pending CN1228809A (en) | 1996-06-28 | 1997-06-24 | Nonaqueous detergent compositions containing specific alkyl benzene sulfonate surfactant |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0907708A2 (en) |
| JP (1) | JPH11513069A (en) |
| CN (1) | CN1228809A (en) |
| AR (1) | AR008052A1 (en) |
| AU (1) | AU3387197A (en) |
| BR (1) | BR9710004A (en) |
| CA (1) | CA2258667A1 (en) |
| CZ (1) | CZ417398A3 (en) |
| MA (1) | MA24228A1 (en) |
| NO (1) | NO986142L (en) |
| WO (1) | WO1998000508A2 (en) |
| ZA (1) | ZA975690B (en) |
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|---|---|---|---|---|
| CN1145690C (en) | 1997-06-27 | 2004-04-14 | 普罗格特-甘布尔公司 | Non-aqueous particulate-containing detergent compositions containing bleach |
| US7297354B2 (en) | 2000-04-26 | 2007-11-20 | Land O'lakes, Inc. | Protein material |
| US7037883B2 (en) | 2003-09-17 | 2006-05-02 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Process of making a liquid laundry detergent with polyanionic ammonium surfactant |
| US7018968B2 (en) | 2003-09-17 | 2006-03-28 | Unilever Home & Personal Care Usa | Liquid laundry detergent with polyanionic ammonium surfactant |
| US6969700B2 (en) * | 2004-02-12 | 2005-11-29 | Unilever Home & Personal Care, Usa Division Of Conopco, Inc | Liquid detergent with polyanionic ammonium surfactant and a high pKa solid inorganic base |
| FR3010074B1 (en) | 2013-09-05 | 2019-08-02 | Saint-Gobain Glass France | METHOD FOR MANUFACTURING A MATERIAL COMPRISING A SUBSTRATE HAVING A FUNCTIONAL LAYER BASED ON TIN OXIDE AND INDIUM |
| JP7449125B2 (en) * | 2020-03-09 | 2024-03-13 | 花王株式会社 | Cleaning composition for textile products |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2010893B (en) * | 1977-12-22 | 1982-11-17 | Unilever Ltd | Liquid detergent composition |
| NZ206213A (en) * | 1982-11-16 | 1985-12-13 | Unilever Plc | Foaming liquid detergent compositions containing alkylbenzenesulphonates and alkyl ether sulphates |
| US4923635A (en) * | 1987-07-06 | 1990-05-08 | Colgate-Palmolive Company | Liquid detergent composition containing alkylbenzene sulfonate, alkyl ethanol ether sulfate, alkanolamide foam booster and magnesium and triethanolammonium ions |
| ATE135739T1 (en) * | 1990-11-02 | 1996-04-15 | Clorox Co | A STABLE, DISSOLVED PERACID CONTAINING LIQUID, NON-AQUEOUS DETERGENT |
| GB9025624D0 (en) * | 1990-11-26 | 1991-01-09 | S B Chemicals Limited | Liquid built detergent concentrates |
-
1997
- 1997-06-24 CZ CZ984173A patent/CZ417398A3/en unknown
- 1997-06-24 CN CN97197436A patent/CN1228809A/en active Pending
- 1997-06-24 AU AU33871/97A patent/AU3387197A/en not_active Abandoned
- 1997-06-24 JP JP10504141A patent/JPH11513069A/en not_active Ceased
- 1997-06-24 EP EP97929923A patent/EP0907708A2/en not_active Ceased
- 1997-06-24 WO PCT/US1997/010114 patent/WO1998000508A2/en not_active Application Discontinuation
- 1997-06-24 CA CA002258667A patent/CA2258667A1/en not_active Abandoned
- 1997-06-24 BR BR9710004A patent/BR9710004A/en unknown
- 1997-06-26 ZA ZA9705690A patent/ZA975690B/en unknown
- 1997-06-27 MA MA24683A patent/MA24228A1/en unknown
- 1997-06-27 AR ARP970102892A patent/AR008052A1/en unknown
-
1998
- 1998-12-28 NO NO986142A patent/NO986142L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2258667A1 (en) | 1998-01-08 |
| NO986142L (en) | 1999-02-24 |
| WO1998000508A3 (en) | 1998-06-11 |
| AU3387197A (en) | 1998-01-21 |
| AR008052A1 (en) | 1999-12-09 |
| BR9710004A (en) | 1999-08-10 |
| EP0907708A2 (en) | 1999-04-14 |
| NO986142D0 (en) | 1998-12-28 |
| MA24228A1 (en) | 1997-12-31 |
| JPH11513069A (en) | 1999-11-09 |
| WO1998000508A2 (en) | 1998-01-08 |
| ZA975690B (en) | 1998-01-23 |
| CZ417398A3 (en) | 1999-08-11 |
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