CN1193994A - Nonaqueous, particulate-containing detergent compositions - Google Patents
Nonaqueous, particulate-containing detergent compositions Download PDFInfo
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- CN1193994A CN1193994A CN95197939A CN95197939A CN1193994A CN 1193994 A CN1193994 A CN 1193994A CN 95197939 A CN95197939 A CN 95197939A CN 95197939 A CN95197939 A CN 95197939A CN 1193994 A CN1193994 A CN 1193994A
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3915—Sulfur-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Disclosed are nonaqueous detergent compositions which are in the form of a liquid, paste or gel. Said composition containing a bleach activator which is present as a divalent and/or trivalent metal salt.
Description
Invention field
The present invention relates to non-washing clothing Betengent product, this product is the form of liquid, gel or paste, and is the form of the stabilising dispersions of granulate material such as SYNTHETIC OPTICAL WHITNER and bleach-activating agent.
Background of invention
People usually think that the Betengent product of liquid, gel or paste form uses more convenient than dry powder or detergent granules product.Therefore described washing composition is subjected to human consumer's very big welcome.This Betengent product is easily measured, and is dissolved in fast in the washing water, can be easy to be applied to be washed with strong solution or dispersion the dirt zone of clothes, there is no dust.They also occupy less storage space than granulated product usually.In addition, this washing composition can mix it and stand in the formula materials that drying operation will degenerate, and drying operation is usually used in the manufacturing of particle or granulated detergent product.
Although described washing composition has many advantages than granulated detergent product, also there are some shortcomings inherently in they.Especially, mutual compatible detergent composition component may interact or react to each other in granulated product.Therefore, this component such as enzyme, tensio-active agent, spices, whitening agent, solvent and especially SYNTHETIC OPTICAL WHITNER and bleach-activating agent are difficult to mix in the detergent product with acceptable degree chemical stability especially.
A method that increases detergent composition component chemical stability in the Betengent product is preparation non-water (or anhydrous) detergent composition.In this non-fishery products, at least some common solid detergent composition components are tended to keep not dissolving in liquid product, and it is littler therefore such as fruit they to be dissolved in reactivity mutual in the fluid matrix.For example, the people's such as Hepworth that authorize on October 17th, 1986 US4,615,820, the people's such as Schultz that authorize May 29 nineteen ninety US4,929,380, the people's such as Schultz that on April 16th, 1991 authorized US5,008,031, June in 1981 people such as disclosed Elder on the 10th EP-A-030,096, June in 1992 people such as disclosed Hall on the 11st WO92/09678 and October in 1993 people such as disclosed Sanderson on the 13rd EP-A-565, disclose non-aqueous liquid detergent compositions in 017, comprised that those contain the non-aqueous liquid detergent compositions of reactive explosive such as peroxygen bleach.
In nonaqueous detergent, mix the observed difficulty of bleach-activating agent and comprise the chemistry and/or the physical stability of bleach-activating agent.EP339 995 has described a kind of a kind of supersalt SYNTHETIC OPTICAL WHITNER and therefore a kind of non-aqueous liquid detergent compositions of precursor of comprising, and said composition contains end capped oxyalkylated nonionogenic tenside.The bleach precursor in a kind of non-water liquid phase that is insoluble to liquid detergent composition is relatively used in EP540 090 suggestion.
The difficulty relevant with the stability of bleach-activating agent be, when dilution, this bleach-activating agent still needs to have certain sufficiently high solubleness in washings, so as in washings as bleaching species and effectively.
Given afore-mentioned, clearly continuation need discern and provide the non-water of liquid, gel or paste form to contain the detergent composition of bleach-activating agent, and said composition has the chemical stability of height and have effective bleachability in washings in enriched material.
Therefore, the purpose of this invention is to provide a kind of nonaqueous detergent composition, bleach-activating agent chemically stable in enriched material wherein, and simultaneously still effective as the SYNTHETIC OPTICAL WHITNER species in washings.
According to the present invention, the nonaqueous detergent composition of a kind of liquid, gel or paste form is provided, the bleach-activating agent that it contains SYNTHETIC OPTICAL WHITNER and exists with divalent metal salt, trivalent metal salt, mixed metal salt, thus, at least a salt is divalence or trivalent metal salt or its mixture.
Summary of the invention
The invention provides the non-water heavy-dirty liquid-detergent composition of a kind of liquid, gel or paste form, described composition comprises SYNTHETIC OPTICAL WHITNER and bleach-activating agent, it is characterized in that described bleach-activating agent exists with divalent metal salt, trivalent metal salt, mixing salt, thus, at least a salt is divalence or trivalent metal salt or its mixture.
Detailed Description Of The Invention
1. SYNTHETIC OPTICAL WHITNER and bleach-activating agent
The used SYNTHETIC OPTICAL WHITNER of the present invention can be any SYNTHETIC OPTICAL WHITNER that is useful on washing composition or textiles cleaning, hard surface cleaning or now known maybe will know other clean bleaching composition in purposes, and when being used for the present invention's processing fabric, be useful for bleaching composition.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Perborate bleach such as Sodium peroxoborate (for example one or tetrahydrate) can be used for the present invention.
Peroxygen bleach is preferred for said composition.Suitable peroxy bleaching compound comprises perborate, yellow soda ash peroxyhydrate and normal " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example by the industrial OXONE of Dupont).
Bleach-activating agent of the present invention exists with divalence and/or trivalent metal salt.Bleach-activating agent salt can add to be scattered in non-powder in water base.Also can be with bleach-activating agent salt and the non-water constituent of liquid such as nonionogenic tenside, organic solvent and/or its mixture pre-mixing.Can obtain bleach-activating agent salt by the divalent metal salt method of any known preparation anion surface activity solution.
Bleach-activating agent salt of the present invention can comprise mixing salt, and thus, at least a salt is divalence or trivalent salt.Cocrystallization effect by bleach-activating agent salt obtains mixing salt.Mixing salt can comprise monovalent salt.The example of these salt is Na
3The amino hexylyloxy benzene sulfonate of Mg4-[N-nonanoyl-6-]
5
Preferably salt of the present invention is Ca, Mg and Al salt.Very preferably Ca and Mg salt or its mixture.
Be applicable to that bleach-activating agent of the present invention is the negatively charged ion bleach-activating agent that is described in the following document: such as English Patent GB836,988,864,798,907,356,1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522, EP-A-0174132, EP-A-0120591; And U.S. Pat 1,246,339,3,332,882,4,128,494,4,412,934 and 4,675,393.
One anionoid bleach-activating agent is at US4,751,015 and 4,397,757, EP-A-284292, EP-A-331,229 and EP-A-03520 in disclosed bleach-activating agent.The example of negatively charged ion peroxy acid bleach activator comprises 4-benzoyloxy benzene sulfonic acid sodium salt, 1-methyl-2-benzoyloxy benzene-4-sodium sulfonate, ninth of the ten Heavenly Stems acyloxy benzene sulfonic acid sodium salt, 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt.
In addition, the bleach-activating agent that is useful among the present invention is the following acid amides substitution compound of general formula or its mixture:
R wherein
1Be alkyl, aryl or the alkylaryl group that contains about 14 carbon atoms of the 1-that has an appointment, R
2Be alkylidene group, arylidene or the alkarylene group that contains about 14 carbon atoms of the 1-that has an appointment, R
5Be that H or alkyl, aryl or the alkylaryl group that contains about 10 carbon atoms of the 1-that has an appointment and L can be any basically suitable leavings groups.Leavings group is any group that breaks away from from bleach-activating agent owing to cross oxyhydroxide negatively charged ion nucleophilic attack bleach-activating agent.This hydrolysis reaction of crossing causes forming peroxycarboxylic acid.Usually, be the leavings group that suits for making group, this group must be implemented sucting electronic effect.It also should form a stable whole, thus reversed reaction speed can ignore, this helped the anionic nucleophilic attack of oxyhydroxide.
The L group must have enough reactivities to the reaction that takes place in Best Times scope (for example wash(ing)cycle).Yet if the L reactivity is too strong, this activator will be difficult to the stable bleaching composition that is used for.The pK of the general and leavings group conjugate acid of these features
aParallel, although known exception that should routine.Usually, the leavings group that shows this character is those wherein pK of its conjugate acid
aFor about 4-is about 13, preferably about 6-about 11 and the group of 8-about 11 most preferably from about.
Preferred bleach-activating agent is R in the above-mentioned general formula
1, R
2And R
5Define and L is selected from those materials of following groups and composition thereof as peroxy acid:
R wherein
1Be alkyl, aryl or the alkylaryl group that contains about 14 carbon atoms of the 1-that has an appointment, R
3Be the alkyl chain that contains about 8 carbon atoms of 1-, R
4Be H or R
3And Y is the solubilising anionic group.
Solubilizing group is-SO
3 -, CO
2 -,-SO
4 -Most preferably-SO
3 -With-CO
2 -, R wherein
3It is the alkyl chain that contains about 4 carbon atoms of the 1-that has an appointment.
The preferred anionic surfactants bleach-activating agent is those materials that L is selected from following groups in the above-mentioned general formula:
R wherein
3As defined above and Y be-SO
3 -Or-CO
2 -
The preferred embodiment of following formula bleach-activating agent comprises the amino hexylyloxy of 4-[N-capryloyl-6-] benzene sulfonate, the amino hexylyloxy of 4-[N-nonanoyl-6-] benzene sulfonate, the amino hexylyloxy of 4-[N-decanoyl-6-] benzene sulfonate and composition thereof.Described activator is described in US4, in 634,551 and US4,852,989.
Another kind of important negatively charged ion bleach-activating agent is by open loop provides organic peracid as herein described owing to cross the carbonyl carbon of oxyhydroxide negatively charged ion nucleophilic attack cyclic rings.For example, this ring-opening reaction comprises hydrogen peroxide or its negatively charged ion attack lactam nucleus carbonyl in some activator.Because hydrogen peroxide or its negatively charged ion preferably occur in the outer carbonyl of ring to the attack of acyl lactam, then obtaining significant open loop may need catalyzer.The example of another open loop bleach-activating agent can be other activator, as disclosed those activators in the people's such as Hodge that authorize in October 30 nineteen ninety the U.S. Pat 4,966,723.
Now be surprisingly found out that, opposite with monovalence bleach-activating agent salt, bleach-activating agent of the present invention chemically stable in enriched material, and simultaneously effective as the SYNTHETIC OPTICAL WHITNER material in washings.
Chemically stable more when in addition, having found bleach-activating agent and certain acid as the citric acid agglomeration.
Nonaqueous detergent composition of the present invention can comprise also and contain tensio-active agent and the liquid gel that contains weak polar solvent mutually that this liquid gel contains the bleach-activating agent salt that is dispersed in wherein mutually.Be described in more detail below detergent composition liquid phase and solid components among the present invention, and composition forms, preparation and purposes: unless otherwise indicated, all concentration and ratio are all with weight basis.Tensio-active agent
The quantity of the surfactant mixture component of detergent composition of the present invention can be with the character and the number change of other composition component, and changes with the required rheological property of the composition of final formation.Usually, the consumption of this surfactant mixture is about 10%～90% of this composition weight.More preferably this surfactant mixture accounts for about 15%～50% of this composition weight.
The U.S. Pat 3,664,961 that licensed to Norris on May 23rd, 1972 has provided the species of the typical negatively charged ion of row, nonionic, both sexes and zwitterionics classification and these tensio-active agents.
The preferred anionic surfactants tensio-active agent comprises alkyl sulfate surfactant, and it is formula ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl preferably has C
10-C
18The alkyl of moieties or hydroxyalkyl, more preferably C
12-C
15Alkyl or hydroxyalkyl and M are H or positively charged ion, for example alkali metal cation (for example sodium, potassium, lithium), perhaps ammonium or replacement ammonium (quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion).
Anion surfactant very preferably comprises alkyl alkoxylated sulfate surfactant, and it is formula RO (A) mSO
3The water-soluble salt of M or acid, wherein R has C
10-C
24The unsubstituted C of moieties
10-C
24Alkyl or hydroxyalkyl group, 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 zero, and it is about 6 to be generally about 0.5-, and more preferably from about 0.5-about 3 and M are that H maybe can be the positively charged ion of metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement ammonium cation for example.The present invention causes and carefully considers alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The specific examples that replaces ammonium cation comprises quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion.Exemplary surfactants is C
12-C
15Alkyl polyethoxylated (1.0) vitriol (C
12-C
15E (1.0) M), C
12-C
15Alkyl polyethoxylated (2.25) vitriol (C
12-C
15E (2.25) M), C
12-C
15Alkyl polyethoxylated (3.0) vitriol (C
12-C
15And C E (3.0) M),
12-C
15Alkyl gathers b-oxide (4.0) vitriol (C
12-C
15E (4.0) M), wherein M is selected from sodium and potassium easily.
The suitable anion surfactant of used other is for comprising C
8-C
20The alkyl sulfonate surfactants of the linear ester of carboxylic acid (being lipid acid), according to " U.S. oiling association meeting will ", 52 (1975), pp323-329 uses gaseous state SO
3With described C
8-C
20The carboxylic acid sulfonation.Suitable raw material comprises the natural fat material that is derived from tallow, palm wet goods.
Preferred alkyl acid sulfonate tensio-active agent especially for the laundry purposes, comprises the alkyl sulfonate surfactants that structural formula is following:
R wherein
3Be C
8-C
20Alkyl, preferred alkyl or its combination, R
4Be C
1-C
6Alkyl, preferred alkyl or its combination and M are the positively charged ions that forms water-soluble salt with alkyl ester sulfonate.Suitable salt-forming cation comprises metal such as sodium, potassium and lithium, and replacement or unsubstituted ammonium cation.Preferably, R
3Be C
10-C
16Alkyl, and R
4Be methyl, ethyl or sec.-propyl.Especially preferred R wherein
3Be C
10-C
16The methyl ester sulfonate of alkyl.
Other anion surfactants that are useful on the washing purpose also can be included in the laundry detergent composition of the present invention.These can comprise soap salt (comprise, for example sodium, potassium, ammonium and substituted ammonium salt as one, two and triethanolamine salt), C
9-C
20This sulfonate of straight chained alkyl, C
8-C
22Uncle or secondary alkyl sulfonate, C
8-C
24The sulfonation poly carboxylic acid of the sulfonation preparation of alkene sulfonate, the pyrolysis product by alkaline earth metal citrate, for example, as british patent specification NO.1,082,179 described, C
8-C
24Alkyl polyglycol ether sulfate (comprising nearly 10 moles oxyethane), alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, isethionate such as acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (particularly saturated and unsaturation C
12-C
18Monoesters) and sulfosuccinic acid diesters (particularly saturated and unsaturation C
6-C
12Diester), sulfuric ester of the sulfuric ester of alkyl polysaccharide such as alkyl polyglycoside (compound of nonionic non-sulfuric acidization described below) and alkyl polyethoxye carboxylate salt are suc as formula RO (CH
2CH
2O)
k-CH
2COO
-M
+Those, wherein R is C
8-C
22Alkyl, k are that integer and the M of 1-10 is water-soluble salt-forming cation.Resinous acid and hydrogenated resin acid also suit, as are present in or are derived from rosin, the staybelite of oil slick, and resinous acid and hydrogenated resin acid.Further case description is in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch).The 23rd hurdle the 58th that various such tensio-active agents also are disclosed in the United States Patent (USP) 3,929,678 that licensed to people such as Laughlin on December 30th, 1975 prevailingly walks in the 29th hurdle the 23rd row (being incorporated herein by reference).
When being included in wherein, it is about 40% that detergent composition of the present invention generally comprises about 1%-, this anion surfactant of about 25% (weight) of preferably about 5%-.
The useful in the present invention nonionogenic tenside of one class is the condenses of oxyethane and hydrophobic part, is 8-17 thereby obtain average hydrophile-lyophile balance (HLB) value, preferred 9.5-14, the more preferably tensio-active agent of 12-14.Hydrophobic (oleophylic) part can be aliphatic series or aromatics in nature, and can easily regulate with arbitrarily specifically the length of the polyoxyethylene group of hydrophobic grouping condensation to obtain having the water-soluble cpds of quality of balance between required hydrophilic and hydrophobic part.
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.
It is RO (C that another kind of ionic surfactant pack is drawn together general formula
nH
2nO)
tZ
xThe alkyl polyglycoside compound, wherein Z is the part that is derived from glucose; R is the saturated hydrophobic alkyl that contains 12-18 carbon atom; T is that 0-10 and n are 2 or 3; X is 1.3-4, and this compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the many glycosides of short-chain alkyl that are less than 50%.The compound of the type and be disclosed among the EP-B0070077,0075996 and 0094118 in detergent application.
The also suitable polyhydroxy fatty acid amide surfactant that following formula is arranged as nonionogenic tenside:
R wherein
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-31Alkyl and Z have to contain at least 3 polyhydroxy alkyls of directly linking the straight-chain alkyl chain of the hydroxyl on the chain, or its oxyalkylated derivative.Preferred R
1Be methyl, R
2It is straight chain C
11-15Alkyl or alkenyl chain such as coconut alkyl or its mixture and Z in reductive amination process derived from reducing sugar such as glucose, fructose, maltose, lactose.The on-aqueous liquid thinner.
In order to form the liquid gel of detergent composition paste phase, above-mentioned tensio-active agent (mixture) and on-aqueous liquid thinner such as liquid alcohol alcoxylates material or non-water weakly polar organic solvent can be combined.Alcohol alkoxylate
A kind of liquid diluent component that is suitable for forming the composition among the present invention comprises oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) material.This material itself also is a nonionogenic tenside.This material is corresponding to general formula:
R
1(C
mH
2mO)
nOH is R wherein
1Be C
8-C
16Alkyl group, m are that 2-4 and n are about 2-12.Preferred R
1Be to comprise about 9-15 carbon atom, the more preferably from about uncle of 10-14 carbon atom or secondary alkyl group.The Fatty Alcohol(C12-C14 and C12-C18) of preferred alkoxylated also has per molecule to comprise about 2-12 ethylene oxide moiety, and more preferably per molecule comprises the material of the ethoxylation of about 3-10 ethylene oxide moiety.
The oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) component of liquid diluent usually has hydrophile-lyophile balance (HLB) value of about 3-17.More preferably the HLB value of this material is about 6-15, most preferably is about 8-15.
Must comprise those materials that make and comprise about 7 moles of ethylene oxide by the 12-15 carbon atom alcohol by the useful fatty alcohol alkoxy compound example of component as a kind of of the on-aqueous liquid thinner in the present composition.This material by Shell Chemical Company with trade(brand)name Neodol25-7 and Neodol23-6.5 market sale.Other useful Neodol comprise that Neodol1-5-has the Fatty Alcohol(C12-C14 and C12-C18) that the ethoxylation of 11 carbon atoms is on average arranged of about 5 moles of ethylene oxide in its alkyl chain, and Neodol23-9-has the uncle C of the ethoxylation of about 9 moles of ethylene oxide
12-C
13Alcohol and Neodol91-10-have the C of the ethoxylation of about 10 moles of ethylene oxide
9-C
11Primary alconol.The alcohol ethoxylate of the type is also commercially available with trade(brand)name Dobanol by Shell ChemicalCompany.Dobanol91-5 is the C with ethoxylation of average 5 moles of ethylene oxide
9-C
11Fatty Alcohol(C12-C14 and C12-C18), and Dodanol25-7 is the C with ethoxylation of every mole of average 7 moles of ethylene oxide of Fatty Alcohol(C12-C14 and C12-C18)
12-C
15Fatty Alcohol(C12-C14 and C12-C18).
Other examples of suitable ethoxylated alcohol comprise Tergitol 15-S-7 and Tergitol 15-S-9, and the two is the linear secondary ethoxylate, and sell by Union CarbideCorporation is commercial.The former is the C with 7 moles of ethylene oxide
11-C
15The mixed ethoxylated product of linear secondary alkanol, and the latter is the analogous products with oxyethane that 9 moles of quilts react.
The alcohol ethoxylate of useful other types is higher molecular weight nonionogenic tensides in the present composition, as Neodol45-11, it is the similar oxirane condensation product of high fatty alcohol, and high fatty alcohol has 14-15 carbon atom, and every mole ethylene oxide group number is about 11.This product is sold by Shell Chemical Company is commercial.
When as the part of liquid diluent in the non-aqueous composition of the present invention, the amount that the alcohol alkoxylate component exists is generally about 1%-60% of composition weight.More preferably about 5%-40% of alcohol alkoxylate ingredients constitute present composition weight.About 10%-25% of alcohol alkoxylate ingredients constitute detergent composition weight of the present invention most preferably.Non-water weakly polar organic solvent.
Another component that can form the liquid diluent of a detergent composition part of the present invention comprises non-water weakly polar organic solvent.Term used herein " solvent " meaning is exactly the on-surface-active carrier or the thinner part of composition liquid phase.Although some of the present composition must and/or optional components in fact can contain being dissolved in " solvent " mutually in, other components will contain " solvent " particulate material in mutually to be dispersed in and exist.Therefore, term " solvent " is not meant needs to dissolve the solvent material of adding all detergent composition components wherein really.
Non-water organic materials as solvent is those low-pole fluent materials herein.Be the object of the invention, " low-pole " liquid be those if any, the particulate material that seldom dissolves used preferred type in the present composition is only arranged, i.e. the liquid of the tendency of one of peroxygen bleach, Sodium peroxoborate or SPC-D.Therefore should not use relative polarity solvent such as ethanol.The weak polar solvent of useful suitable type comprises alkylene glycol mono lower alkyl ether, low molecular poly, lower molecular weight methyl ester and acid amides etc. in non-aqueous liquid detergent compositions of the present invention.
A kind of non-water weak polar solvent that is used for preferred type of the present invention comprises one-, two-, three-or four-C
2-C
3Alkylene glycol mono C
2-C
6Alkyl oxide.The specific examples of this compound comprises diethylene glycol monobutyl ether, Tetraglycol 99 monobutyl ether, dipropylidene diol monoethyl ether and dipropylidene diol monobutyl ether.Preferred especially diethylene glycol monobutyl ether and dipropylidene diol monobutyl ether.The type compound is with trade(brand)name Dowanol, Carbitol and the commercial sale of Cellosolve.
The non-water weakly polar organic solvent that is useful on another preferred type of the present invention comprises low molecular poly (PEG).This material is that those molecular weight are at least about 150 material.Molecular weight ranges is most preferred for the PEG of about 200-600.
And the nonpolar non-aqueous solvent of another kind of preferred type comprises the lower molecular weight methyl ester.This material is that those general formulas are R
1-C (O)-OCH
3Material, R wherein
1Be 1-about 18.The example of suitable lower molecular weight methyl ester comprises methyl acetate, methyl propionate, methyl caprylate and methyl laurate.
Certainly, used non-water weakly polar organic solvent should with used other composition component such as SYNTHETIC OPTICAL WHITNER in the liquid detergent composition of the present invention and/or promoting agent be compatible and do not react.The consumption that this solvent composition is general is about 1%-60% of composition weight.More preferably non-water weakly polar organic solvent generally accounts for about 5%-40% of composition weight, most preferably accounts for about 10%-25% of composition weight.The liquid diluting agent concentration
As the concentration of surfactant mixture, the liquid diluent total amount is by the type of other composition component and quantity and by the decision of desired composition character in the present composition.Usually, liquid diluent accounts for about 20%-80% of present composition weight.More preferably liquid diluent accounts for about 40%-60% of composition weight.Solid phase
Nonaqueous detergent composition of the present invention also can comprise and disperse and be suspended in particulate material solid phase in the liquid phase.The size of this particulate material is generally about 0.1-1500 micron.More preferably this material is of a size of about 5-200 micron.
What the used particulate material of the present invention can comprise one or more types is insoluble to detergent composition component in the non-water liquid phase of composition basically with particle form.Details are as follows: tensio-active agent for the operable particulate material of the type
Particulate material in be suspended in the present invention non-aqueous liquid detergent compositions of another kind of possibility type comprises all or part of auxiliary anion surfactant that is insoluble in the non-water liquid phase.Anion surfactant with the most common type of this solubility properties comprises uncle or secondary alkyl sulfate anion surfactant.This tensio-active agent is that those pass through senior C
8-C
20The tensio-active agent of the sulfation preparation of Fatty Alcohol(C12-C14 and C12-C18).
Conventional primary alkyl sulphates tensio-active agent has general formula:
ROSO
3 -M
+Wherein R generally is linear C
8-C
20Hydrocarbyl group, it can be that straight or branched and M are water solubilising positively charged ions.Preferred R is C
10-C
14Alkyl and M are basic metal.Most preferably R is about C
12With M be sodium.
Conventional secondary alkyl sulfate also can be as the essential anion surfactant component of present composition solid phase.Conventional secondary alkyl sulfate surfactant is that those have along the material of the sulphate moiety of molecule alkyl " skeleton " random distribution.This material can be by following structrual description:
CH
3(CH
2)
n(CHOSO
3M
+) (CH
2)
mCH
3Wherein m and n be 2 or bigger integer and m+n sum generally be that about 9-15 and M are water solubilising positively charged ions.
If be used as all or part of of essential particulate material, auxiliary anion surfactant such as alkyl-sulphate account for about 1%-10% of composition weight usually, more preferably account for about 1%-5% of composition weight.As the alkyl-sulphate of all or part of particulate material is by the not alkoxylated alkyl sulphate material preparation that can form main alkyl ether sulfate surfactant component part as liquid phase part of the present invention, and adds in the present composition individually.The organic washing-assisting detergent material
Another may type be suspended in the present invention non-aqueous liquid detergent compositions in particulate material comprise the organic detergent washing assistant material of the water hardness that is used for offsetting calcium or other ionic effects, runs in present composition washing/bleaching application.The example of this material comprises alkali metal citrate, succinate, malonate, lipid acid, carboxymethyl succinate, carboxylate salt, multi-carboxylate and many ethanoyl carboxylate salt.Specific examples comprises sodium, potassium and the lithium salts of oxygen di-succsinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.Other organic phosphonate type sequestrant examples are material and the alkane hydroxyethylidene diphosphonic acid salt of having been sold with trade(brand)name Dequest by Monsanto such as those.Citrate trianion very preferably.
Other suitable organic washing-assisting detergents comprise known high-molecular weight polymer and multipolymer with washing assistant character.For example this material comprises suitable polyacrylic acid, polymaleic acid and poly propenoic acid maleic acid and salt thereof, such as BASF those materials with trade mark Sokalan sale.
The organic washing-assisting detergent of another kind of suitable type comprises the water-soluble salt of higher fatty acid, i.e. " soap ".These materials comprise sodium, potassium, ammonium and the alkanol ammonium salts of alkali metal soap as the higher fatty acid that contains about 24 carbon atoms of the 8-that has an appointment and about 18 carbon atoms of preferably about 12-.Soap can make by the direct saponification of fat and oil or the neutralization by free fatty acids.Useful especially is the sodium and the sylvite of the fatty acid mixt that obtained by Oleum Cocois and tallow, i.e. tallow and coconut soda soap or potash soap.
If be used as all or part of of essential particulate material, insoluble organic detergent washing assistant generally can account for about 2%-20% of the present composition.More preferably this washing assistant material can account for about 4%-10% of composition weight.The inorganic alkaline source
Particulate material in be suspended in the present invention non-aqueous liquid detergent compositions of another possibility type can comprise that being used to make the wash water solution that is formed by this composition is the material of alkalescence in nature usually.This material can play a part or also can not play detergent builders, promptly works to offset the material of the water hardness to the disadvantageous effect of scourability.
The example of suitable alkaline source comprises water soluble alkali metal carbonate, supercarbonate, borate, silicate (silicate) and silicate (metasilicate).Although because ecological consideration is not preferred, water-soluble phosphate also can be used as alkaline source.These materials comprise alkali metal pyrophosphate, orthophosphoric acid salt, poly-phosphate and phosphonate.In all these alkaline sources, alkaline carbonate is most preferred such as yellow soda ash.
If with the form of hydratable salt, alkaline source also can be as the siccative in the non-aqueous liquid detergent compositions of the present invention.The existence that also is the alkaline source of siccative can make those be easy to provide benefit aspect the composition component of water deactivation such as peroxygen bleach chemical stabilization.
If be used as all or part of of particulate material component, alkaline source generally accounts for about 1%-15% of present composition weight.More preferably alkaline source accounts for about 2%-10% of composition weight.Although this material is water miscible, generally be insoluble in the nonaqueous detergent composition of the present invention.Therefore, this material generally is scattered in the non-water liquid phase with the discrete particle form.Optional combination thing component
Except previously described composition liquid phase and solid components, detergent composition of the present invention can and preferably contain various optional components.This optional components or liquid form or solid form.Optional components or be dissolved in the liquid phase or with fine particle or drop form is dispersed in the liquid phase.Some can choose the material that is used for the present composition wantonly, and details are as follows: optional inorganic detergent builders
Detergent composition of the present invention can also randomly comprise the inorganic detergent builders that also plays alkaline source except that listed material above of one or more types.For example, this optional inorganic builders can comprise silico-aluminate such as zeolite.The people's United States Patent (USP) NO.4 such as Corkill that authorize on August 12nd, 1986 have more at large discussed aluminosilicate zeolite in 605,509 and as the application of detergent builders, its disclosure is hereby incorporated by.In addition, crystalline layered silicate as this ' those limits of being discussed in 509 United States Patent (USP)s are suitable in the detergent composition of the present invention.If you are using, optional inorganic detergent builders can account for about 2%-15% of present composition weight.Optional enzyme
Detergent composition of the present invention also can randomly comprise the detergent enzyme of one or more types.This kind of enzyme can comprise proteolytic enzyme, amylase, cellulase and lipase.This material is well known in the art and can commerce buys.They can be mixed in the non-aqueous liquid detergent compositions of the present invention with suspensoid, " ball (marume) " or " granule (prill) " form.The enzyme of another suitable type comprises the material of the form of those enzyme slurries in nonionogenic tenside.The enzyme of this form by Novo Nordisk for example with " LDP " commercial distribution of commercial name.
The enzyme that adds in the present composition with conventional enzyme particle shape formula is particularly preferred among the present invention.The size of this grain is generally about 100-1, and 000 micron, more preferably about 200-800 micron, and be suspended in the whole non-water liquid phase of composition.Compare with other enzyme type, found that the granule in the present composition is showing special ideal enzyme stability aspect the passing maintenance enzymic activity in time.Therefore, use the composition of enzyme grain needn't comprise conventional enzyme stable as when enzyme is added in the waterborne liquid washing composition frequent those of use.
If use the work of enzyme, its amount of mixing in the non-aqueous liquid compositions of the present invention generally is enough to provide every gram composition to be up to about 10 milligrams (weight), more generally about 0.01 milligram-Yue 5 milligrams organized enzyme.In other words, non-aqueous liquid detergent compositions of the present invention generally comprises about 0.001%-5%, the commercial enzyme preparation of preferably about 0.01%-1% (weight).For example, proteolytic enzyme is usually to be enough to the providing active amount of every gram composition 0.005-0.1Anson unit (AU) to be present in this commodity preparation.Optional sequestrant
Detergent composition of the present invention can also randomly comprise the metal ion that is used for chelating nonaqueous detergent composition of the present invention such as the sequestrant of iron and/or manganese.Therefore, this sequestrant be used for composition in otherwise can tend to make the metallic impurity of composition component such as peroxygen bleach deactivation to form title complex.Useful chelating agents can comprise aromatic chelating agent and its mixture of aminocarboxylate, phosphonate, amino phosphonates do, multifunctional replacement.
Comprise edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate, ethylenediamine disuccinate and ethanol Diglycocol as the effective aminocarboxylate of optional sequestrant.An alkali metal salt of preferred these materials.
In detergent composition, when allowing at least a small amount of total phosphorus, amino phosphonates do also is suitable as the sequestrant in this invention composition, and comprises the ethylenediamine tetraacetic (methylene phosphonic acid salt) of regarding DEQUEST as.Preferred these amino phosphonates do do not comprise alkyl or the kiki alkenyl group that has more than about 6 carbon atoms.
Preferred sequestrant comprises hydroxyethyl di 2 ethylhexyl phosphonic acid (HEDP), diethylene triaminepentaacetic acid(DTPA) (DTPA), ethylenediamine disuccinic acid (EDDS) and pyridine dicarboxylic acid (DPA) and salt thereof.Certainly, sequestrant also can be used for fabric washing/bleaching process at the present composition and plays detergent builders.If the use sequestrant, it can account for about 0.1%-4% of present composition weight.More preferably sequestrant accounts for about 0.2%-2% of detergent composition weight of the present invention.Optional thickening, viscosity controller and/or dispersion agent.
Detergent composition of the present invention can also randomly comprise and is used for enhancing composition and keeps the polymeric material of the ability that its solid particulate components suspends.This material thereby can play thickening material, viscosity control agent and/or dispersion agent.This material often is the multi-carboxylate polymer, but can comprise other polymeric materials such as polyvinylpyrrolidone (PVP) and polymeric amine derivative such as quaternised ethoxylation hexamethylene-diamine.
The polymeric polycarboxylic acid salt material can be by making suitable unsaturated monomer, preferred its sour form, the incompatible preparation of polymerization or copolymerization.The unsaturated monomer acid that can polymerization 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.Have in multi-carboxylate polymer of the present invention not that the monomer fragment of carboxylate-containing group is to suit as vinyl methyl ether, vinylbenzene, ethene etc., if this fragment do not constitute polymer weight more than about 40%.
Shi Yi multi-carboxylate polymer can be obtained by vinylformic acid especially.Thisly be useful on the water-soluble salt that acrylic acid based polymer of the present invention is a polymeric acrylic acid.It is about 2 that the molecular-weight average of this polymkeric substance of acid form is preferably, 000-10,000, more preferably from about 4,000-7,000 and most preferably from about 4,000-5,000.The water-soluble salt of this acrylate copolymer can comprise for example an alkali metal salt.The water-soluble polymers of the type is known material.The application of the type polyacrylate in detergent composition has been disclosed in the United States Patent (USP) 3,308,067 of the Diehl that for example authorized on March 7th, 1967.This material also can work to help washing composition.
If use optional thickening material, viscosity control agent and/or dispersion agent, its amount in the present composition should be about 0.1%-4% (weight).More preferably this material can account for about 0.5%-2% of detergent composition weight of the present invention.Optional whitening agent, suds suppressor and/or spices
Detergent composition of the present invention can also randomly comprise conventional whitening agent, suds suppressor, silicone oil, bleaching catalyst and/or fragrance material.Certainly, this whitening agent, suds suppressor, silicone oil, bleaching catalyst and spices must be compatible with other composition component in the non-water surrounding and not be reacted.If present, whitening agent, suds suppressor and/or spices generally account for about 0.1%-2% of present composition weight.
Suitable bleaching catalyst is included in US5, disclosed manganese basigamy compound in 246,621, US5,244,594, US5,114,006 and US5,114,611.Composition forms
The particle-liquid detergent composition that contains of the present invention is non-water (or anhydrous) in nature basically.Although the water of minute quantity can mix in this composition as the impurity in essential or the optional components, the amount of water never should be above about 5% of present composition weight.The water-content of nonaqueous detergent composition more preferably of the present invention accounts for and is less than about 1% (weight).
It is the form of liquid, gel or paste that the present invention contains particle nonaqueous detergent composition.Preparation of compositions and application
Nonaqueous detergent composition of the present invention can by with any order easily with bleach-activating agent salt and its optional components in conjunction with and by the obtained component mixture is mixed for example stir with formation the present invention mutually stable composition prepare.
Zhi Bei composition of the present invention can be used for being formed for the wash water solution of fabric washing and bleaching as mentioned before.Usually this composition with significant quantity adds in the entry, preferably uses conventional fabric washing automatic washing machine, to form this washing/aqueous bleaching solution.Washing/the aqueous bleaching solution that will so form preferably under agitation contacts with the fabric that is washed with bleaching immediately then.
The adding in the entry can to account for the liquid detergent composition of the present invention that forms washing/aqueous bleaching solution of significant quantity, be enough to form about 500-7, the amount of 000ppm composition solution.More preferably detergent composition of the present invention is about 1 in washing/aqueous bleaching solution, 000-3,000ppm.
Embodiment
The following example illustrates composition of the present invention, but do not mean that the restriction or in other words, limit scope of the present invention.
Preparation has and contains the non-washing clothing of SYNTHETIC OPTICAL WHITNER washing composition as the described composition of Table I.
Table I component wt% liquid-based C
12-15Alkyl oxide (EO=3) sodium sulfate salt 17C
12-14N-methyl glucose amide 9C
12-14EO=5 alcohol ethoxylate 17N-butoxy propoxyl group propyl alcohol (BPP) 24 spices 0.7 solid topping palm kernel fatty acid sodium salt 5.7 trisodium citrates 1.9 SODIUM PERCARBONATEs 9.4 sodium carbonate 7.5 ethoxy di 2 ethylhexyl phosphonic acid sodium (HEDP), the amino hexanoyl oxygen of Na salt 1.7[4-[N-pelargonyl group-6-4.7 bases] benzene sulfonate]2, Ca salt whitening agent 0.2 silicone oil DB-100 0.5 enzyme and a small amount of component are up to 100%
Said composition is stable anhydrous liq detergent for washing clothes, and wherein bleach-activating agent is stable in enriched material, and wherein bleach-activating agent is effective in washings.
Claims (9)
1. the nonaqueous detergent composition of a liquid, paste or gel form, described nonaqueous detergent composition comprises SYNTHETIC OPTICAL WHITNER and bleach-activating agent, it is characterized in that described bleach-activating agent exists with divalent metal salt, trivalent metal salt, mixed metal salt, one of described at least salt is divalence or trivalent metal salt or its mixture thus.
2. nonaqueous detergent composition according to claim 1, wherein said divalent salts is selected from Ca and/or Mg.
3. nonaqueous detergent composition according to claim 1, wherein mixed metal salt comprises the monovalence metal.
4. nonaqueous detergent composition according to claim 1-3, wherein bleach-activating agent is 4-benzoyloxy benzene sulfonate, 1-methyl-2-benzoyloxy benzene-4-sulfonate, nonanoly acyloxy benzene sulfonate, 3,5,5-trimethyl acetyl oxygen base benzene sulfonate.
5. nonaqueous detergent composition according to claim 1-3, wherein bleach-activating agent is the amino hexylyloxy of 4-[N-capryloyl-6-] benzene sulfonate, the amino hexylyloxy of 4-[N-nonanoyl-6-] benzene sulfonate, the amino hexylyloxy of 4-[N-decanoyl-6-] benzene sulfonate and composition thereof.
6. nonaqueous detergent composition according to claim 1-5, wherein SYNTHETIC OPTICAL WHITNER is a percarbonate.
7. nonaqueous detergent composition according to claim 1-6, it also comprises polyol surfactant.
8. nonaqueous detergent composition according to claim 7, wherein polyol surfactant is selected from polyhydroxy fatty acid amide.
9. nonaqueous detergent composition according to claim 1-8, it also comprises the anion surfactant of 5-25% (weight).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95924005A EP0833887B1 (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
| CN95197939A CN1193994A (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
| PCT/US1995/007823 WO1997000937A1 (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
| CA002225596A CA2225596A1 (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95197939A CN1193994A (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
| PCT/US1995/007823 WO1997000937A1 (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
| CA002225596A CA2225596A1 (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1193994A true CN1193994A (en) | 1998-09-23 |
Family
ID=27170586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95197939A Pending CN1193994A (en) | 1995-06-20 | 1995-06-20 | Nonaqueous, particulate-containing detergent compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0833887B1 (en) |
| CN (1) | CN1193994A (en) |
| CA (1) | CA2225596A1 (en) |
| WO (1) | WO1997000937A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2258668A1 (en) * | 1996-06-28 | 1998-01-08 | Jean Wevers | Nonaqueous detergent compositions containing bleach precursors |
| JP2000500806A (en) † | 1996-06-28 | 2000-01-25 | ザ、プロクター、エンド、ギャンブル、カンパニー | Non-aqueous liquid detergent composition containing bleach precursor |
| BR9810490A (en) * | 1997-06-27 | 2001-11-27 | Procter & Gamble | Non-aqueous detergent compositions containing bleach |
| WO1999000482A1 (en) * | 1997-06-27 | 1999-01-07 | The Procter & Gamble Company | Non-aqueous, particulate-containing detergent compositions containing bleach |
| ATE241003T1 (en) * | 1997-11-10 | 2003-06-15 | Procter & Gamble | MULTI-LAYER DETERGENT TABLET WITH BOTH COMPRESSED AND NON-COMPRESSED PARTS |
| ATE244296T1 (en) * | 1997-11-10 | 2003-07-15 | Procter & Gamble | METHOD FOR PRODUCING A DETERGENT TABLET |
| MXPA02001521A (en) * | 1999-08-10 | 2002-07-02 | Procter & Gamble | Non-aqueous liquid detergents with water-soluble low-density particles. |
| US6770615B1 (en) | 1999-08-10 | 2004-08-03 | The Procter & Gamble Company | Non-aqueous liquid detergents with water-soluble low-density particles |
| US20110166370A1 (en) | 2010-01-12 | 2011-07-07 | Charles Winston Saunders | Scattered Branched-Chain Fatty Acids And Biological Production Thereof |
| EP2675784B1 (en) | 2011-02-17 | 2017-09-13 | The Procter and Gamble Company | Bio-based linear alkylphenyl sulfonates |
| CA2827627C (en) | 2011-02-17 | 2016-10-11 | The Procter & Gamble Company | Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates |
| US9228158B2 (en) | 2012-02-01 | 2016-01-05 | Gurtler Industries, Inc. | Composition and method for removing stains derived from chlorhexidine gluconate |
| DE102014218951A1 (en) * | 2014-09-19 | 2016-03-24 | Henkel Ag & Co. Kgaa | Solid composition for textile treatment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4634551A (en) * | 1985-06-03 | 1987-01-06 | Procter & Gamble Company | Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain |
| PH25878A (en) * | 1987-01-27 | 1991-12-02 | Colgate Palmolive Co | Built liquid laundry detergent composition containing an alkaline earth metal or zinc salt of higher fatty acid liquifying agent |
| GB9123220D0 (en) * | 1991-11-01 | 1991-12-18 | Unilever Plc | Liquid cleaning compositions |
-
1995
- 1995-06-20 WO PCT/US1995/007823 patent/WO1997000937A1/en not_active Application Discontinuation
- 1995-06-20 EP EP95924005A patent/EP0833887B1/en not_active Revoked
- 1995-06-20 CA CA002225596A patent/CA2225596A1/en not_active Abandoned
- 1995-06-20 CN CN95197939A patent/CN1193994A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0833887A1 (en) | 1998-04-08 |
| EP0833887B1 (en) | 2000-01-19 |
| WO1997000937A1 (en) | 1997-01-09 |
| CA2225596A1 (en) | 1997-01-09 |
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