CN1200758A - Bleach compositions comprising oleoyl sarcosinate surfactants - Google Patents

Bleach compositions comprising oleoyl sarcosinate surfactants Download PDF

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Publication number
CN1200758A
CN1200758A CN95194432A CN95194432A CN1200758A CN 1200758 A CN1200758 A CN 1200758A CN 95194432 A CN95194432 A CN 95194432A CN 95194432 A CN95194432 A CN 95194432A CN 1200758 A CN1200758 A CN 1200758A
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composition
bleaching
acid
bleach
valerolactim
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S·包威尔
C·L·M·弗莫特
B·T·因格拉姆
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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

Abstract

Bleaching and cleaning compositions comprising a bleaching compound, oleoyl sarcosinate surfactant, and, optionally but preferably, a bleach catalyst and one or more bleach activators are provided. Thus, laundry detergent compositions which comprise perborate, percarbonate and, preferably, activators such as benzoyl caprolactam exhibit improved performance in the presence of the oleoyl sarcosinate surfactant.

Description

The bleaching composition that contains the oleoyl sarcosine salt surfactant
Technical field
The present invention relates to improve the cleaning and the bleaching composition of performance with the oleoyl sarcosine salt surfactant.Provide and have the active bleaching of improved oxygen bleaching, fabric washing, wash dish and sanitary purpose washing composition automatically.
Background of invention
The cleaning composition formulator adds SYNTHETIC OPTICAL WHITNER such as Sodium peroxoborate or SPC-D usually to play bleaching effect in these compositions.These SYNTHETIC OPTICAL WHITNER are received wide acceptance by the ability that removes various spots and dust and dirt on the fabric.Equally, automatically, wash dish composite formula Designers and find that various SYNTHETIC OPTICAL WHITNER help by removing tea stain, albumen dirt etc. on the bowl dish.Various fabric bleachings and/or preimpregnation composition also contain percarbonate or perborate bleach.
It's a pity that many SYNTHETIC OPTICAL WHITNER can not all be brought into play best efficiency under all working conditionss.As a universal law, perborate and percarbonate are more effective in hot water than in cold water.But present many human consumers carry out fabric washing and other washing operation at warm water to (being lower than about 60 ℃) between the temperature of cold water.For improving the performance of perborate and percarbonate bleach, what is called " bleach-activating agent " is sought help from by manufacturerss.The characteristics of these activators are that contain can be with perborate or percarbonate effect and discharge the organic molecule of " peracid " albic material.SYNTHETIC OPTICAL WHITNER add activator to be combined under very wide water temperature range and the working conditions usefulness good.People know that also various transition-metal cations such as manganese can play bleach-activating agent, and the chances are because they interact with the catalysis between superoxide or the peracid albic material.
It's a pity that many peracid, bleach-activating agent and transition-metal catalyst can cause that fabric damages.Bound by theory but can be sure of not, it is because activator and catalyzer precipitate on fabric that the fabric that bleaching compounds causes damages, they cause the fabric damage when forming free radical with hydrogen peroxide.Albic material is precipitable too to be formed some point spot and fabric is damaged on fabric.Fabric damages especially severe under the lesser temps, and this is that many peracid, activator and catalyst dissolution are slower, thereby are deposited in fabric face easily because at a lower temperature.
Have now found that the bleachability that the available bleaching composition that contains the oleoyl sarcosine salt surfactant provides effectively, improves.As and if these compositions can stop the fabric that is caused by peracid, catalyzer and bleach-activating agent to damage.Bound by theory but can be sure of that oleoyl creatine salt can dissolve bleaching compounds especially effectively and it is scattered in the whole washings particularly (is not lower than about 60 ℃) under colder temperature.So the precipitation of bleaching compounds in washings reduced.
Therefore, an object of the present invention is to provide the washing and the bleaching composition of the improvement of using bleaching compounds and oleoyl sarcosine salt surfactant.Another object of the present invention provides these bleach systems of a kind of the present invention of use and oleoyl sarcosinates by the method that removes dust and dirt and spot on fabric and the bowl dish.These compositions have good color protection performance and non-stimulated to skin in the hand washing operation to DYED FABRICS.By it will be appreciated that in the following discloses content, these purposes and other purpose can realize in the present invention.
Background technology
Following patent and document have been narrated oleoyl sarcosinates: U.S.2,542,385; U.S.3,402,990; U.S.3,639,568; U.S.4,772,424; U.S.5,186,855; European Patent Publication 505,129; British Patent Publication1,211,545; Japanese Patent Publication 59/232194; JapanesePatent Publication 62/295997; Japanese Patent Publication02/180811; With Chemical Abstracts Service abstracts No.s 61:3244q, 70:58865x, and 83:181020p.
Following United States Patent (USP) has been reported and has been used the manganese that has various title complex ligands to promote bleaching effect: 4,430,243; 4,728,455; 5,246,621; 5,244,594; 5,284,944; 5,194,416; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084; 5,114,606; 5,114,611.Also can be referring to EP549,271A1; EP 544,490 A1; EP 549,272 A1 and EP 544,440 A2.
U.S.Patent 4,686,063 and U.S.Patent 4,634,551 narrated the acid amides use of bleach-activating agent in laundry detergent of deriving.People such as Hodge disclosed another kind of bleach-activating agent in the U.S.Patent 4,966,723 that authorizes October 30 nineteen ninety contains benzoxazine-type activator.
Summary of the invention
The present invention relates to contain the bleaching composition of oleoyl sarcosine salt surfactant and a kind of SYNTHETIC OPTICAL WHITNER.
The invention still further relates to and contain the oleoyl sarcosine salt surfactant, a kind of SYNTHETIC OPTICAL WHITNER particularly is selected from H 2O 2, perborate, percarbonate, persulphate and peracid SYNTHETIC OPTICAL WHITNER a kind of SYNTHETIC OPTICAL WHITNER, and the bleaching composition of one or more selected bleach-activating agents.Preferred SYNTHETIC OPTICAL WHITNER comprises percarbonate or perborate bleach or their mixture.Preferred bleach-activating agent is selected from acyl lactam type activator; the acid amides activator of deriving, benzoxazine type activator, tetraacetyl ethylene-diamines (TAED); the alkyloyloxyethyl benzene sulfonate comprises nonanoyl oxygen benzene-sulfonate (NOBS) and benzoyl oxygen benzene sulfonate (BOBS) and their mixture.Also can contain peracid in the said composition.Suitable peracid comprises the acid amides peracid, positively charged ion peracid, pelargonamide of peroxide hexanodioic acid (NAPAA) and their mixture.
In addition, the invention still further relates to and contain the oleoyl sarcosine salt surfactant, a kind of SYNTHETIC OPTICAL WHITNER, the bleach-activating agent that one or more are selected and the bleaching composition of the bleaching catalyst of one or more catalytically effective amounts, particularly metal bleach catalyst.
The optional preferred activator that uses of the present invention comprises benzoyl caprolactam, the nonanoyl hexanolactam, the benzoyl Valerolactim, the nonanoyl Valerolactim, 3,5,5-trimethyl acetyl hexanolactam, 3,5,5-trimethyl acetyl Valerolactim, the decoyl hexanolactam, the decoyl Valerolactim, the caprinoyl hexanolactam, the caprinoyl Valerolactim, undecylene acyl hexanolactam, undecylene acyl Valerolactim, (6-decoylamide hexanoyl) oxygen benzene sulfonate, (6-pelargonamide hexanoyl) oxygen benzene sulfonate, (6-decyl amide hexanoyl) oxygen benzene sulfonate, nonanoyl oxygen-benzene sulfonate, benzoyl oxygen benzene sulfonate, tetraacetyl ethylene diamine and their mixture.The example of particularly preferred substituted benzene formyl lactan comprises the toluyl hexanolactam, the toluyl Valerolactim, the ethylbenzoyl hexanolactam, the ethylbenzoyl Valerolactim, the propyl group benzoyl caprolactam, propylbenzene carbamoyl pentyl lactan, the sec.-propyl benzoyl caprolactam, isopropyl benzene carbamoyl pentyl lactan, the butyl benzoyl caprolactam, butylbenzene carbamoyl pentyl lactan, tertiary butyl benzoyl caprolactam, tert.-butylbenzene carbamoyl pentyl lactan, the amyl group benzoyl caprolactam, amylbenzene carbamoyl pentyl lactan, the hexyl benzoyl caprolactam, hexyl benzene carbamoyl pentyl lactan, phenetole formyl hexanolactam, phenetole formyl Valerolactim, the propoxy-benzoyl caprolactam, propoxy-benzoyl Valerolactim, isopropoxy benzoyl hexanolactam, isopropoxy benzene carbamoyl pentyl lactan, the butoxy benzoyl caprolactam, butyl phenyl ether carbamoyl pentyl lactan, the tert.-butoxy benzoyl caprolactam, tert.-butoxy benzoyl Valerolactim, the pentyloxy benzoyl caprolactam, amyl phenyl ether carbamoyl pentyl lactan, the hexyloxy benzoyl caprolactam, hexyloxy benzoyl Valerolactim, 2,4,6-trichlorine benzoyl caprolactam, 2,4,6-trichlorobenzene carbamoyl pentyl lactan, penta fluoro benzene formyl hexanolactam, penta fluoro benzene carbamoyl pentyl lactan, the dichloro-benzoyl hexanolactam, dimethoxy benzoyl hexanolactam, 3-chlorobenzoyl hexanolactam, 2,4-dichloro-benzoyl hexanolactam, the terephthaloyl dicaprolactam, the dichloro-benzoyl Valerolactim, dimethoxy benzene carbamoyl pentyl lactan, 3-chlorobenzoyl Valerolactim, 2,4-dichloro-benzoyl Valerolactim, terephthaloyl two Valerolactims, 4-oil of mirbane formyl hexanolactam, 4-oil of mirbane formyl Valerolactim, the dinitrobenzene benzoyl caprolactam, dinitrobenzene carbamoyl pentyl lactan, and their mixture.
Particularly preferred bleach-activating agent is selected from following compounds: benzoyl caprolactam, the benzoyl Valerolactim, the nonanoyl hexanolactam, the nonanoyl Valerolactim, 4-oil of mirbane formyl hexanolactam, 4-oil of mirbane formyl Valerolactim, the decoyl hexanolactam, the decoyl Valerolactim, the caprinoyl hexanolactam, the caprinoyl Valerolactim, undecylene acyl hexanolactam, undecylene acyl Valerolactim, 3,5,5-trimethyl acetyl hexanolactam, 3,5,5-trimethyl acetyl Valerolactim, the dinitrobenzene benzoyl caprolactam, dinitrobenzene carbamoyl pentyl lactan, the terephthaloyl dicaprolactam, terephthaloyl two Valerolactims, (6-decoylamide hexanoyl) oxygen benzene sulfonate, (6-pelargonamide hexanoyl) oxygen benzene sulfonate, (6-decyl amide hexanoyl) oxygen benzene sulfonate, nonanoyl oxygen benzene sulfonate, benzoyl oxygen benzene sulfonate, tetraacetyl ethylene diamines, and their mixture.
Greater than about 1.0, most preferred hydrogen peroxide is about 1.5 to the ratio of bleach-activating agent to the hydrogen peroxide that peroxy bleaching compound provides at least to the preferred mol ratio of bleach-activating agent.
Preferred compositions of the present invention is the composition that its contained bleaching catalyst is a kind of metal-based catalyst.
The invention still further relates to the cleaning composition, particularly laundry detergent that contain other conventional surfactants and other cleaning ingredients.
The invention still further relates to and contain the oleoyl sarcosine salt surfactant, the washing of the water-soluble manganese salt of a kind of SYNTHETIC OPTICAL WHITNER and a kind of catalytically effective amount or bleaching composition.
The invention still further relates to a kind of method of improving oxygen or peracid bleaching composition bleachability, the manganese positively charged ion that is included in selected ligand and a kind of catalytically effective amount exists down, to wherein adding the oleoyl sarcosine salt surfactant.This just provides a kind of method by fabric removal spot, comprises allowing said fabric contact with the aqueous medium that contains said composition.
As not pointing out in addition that all percentage, ratio and mark are all calculated by weight in the literary composition.The all references document is incorporated herein by reference at this paper relevant portion.
The detailed Description Of The Invention oleoyl sarcosinates
The present composition contains oleoyl sarcosine salt, according to composition and purposes requirement, can select the form of acid and/or salt, and its structural formula is as follows:
Wherein M is hydrogen or a kind of cationic moiety.Preferred L is hydrogen and an alkali metal salt particularly sodium and potassium.Oleoyl sarcosinates can be used as commodity and has bought, for example W.R.Grace ﹠amp; Co. provide with Hamposyl O.Bleaching composition according to the present invention contains the oleoyl sarcosinates that is at least composition weight 0.1%, and typical content is about 0.1% to about 55%, and preferred content is about 1% to about 20%, and most preferred content is about 3% to about 15%.
Except the oleoyl sarcosinates that can purchase as commodity, the useful oleoyl sarcosinates of the present invention also can preferably be equal to or greater than under basic catalyst (particular methanol sodium) existence and anhydrous response condition of alkoxide catalyzer in a kind of basicity, is prepared by oleic ester (preferable methyl ester) and a kind of sarcosinate (particular certain cancers).For example, this reacts available figure below and represents:
Figure A9519443200091
This salt can randomly neutralize to form the sour form of oleoyl sarcosinates.
The preparation method of preferred oleoyl sarcosinates carries out under the temperature between about 80 ℃ to about 200 ℃, particularly at about 120 ℃ to about 200 ℃.Have at least 100 ℃ of boiling points and the alcohol of stable reaction conditions is solvent (being that glycerol is unavailable) though can use, reaction is preferably under the condition that does not have solvent to be carried out.In the reactant methyl ester reactant sarcosinate is approximately 1: 1.0 to the mol ratio of basic catalyst: during 0.05-0.2, reaction can be carried out with about 85% yield.
The methyl ester mixture that is obtained by the natural oil of high oleic acid content (at least about 60% is preferred, at least about 75% for more preferably, is most preferably at least about 90%) can particularly preferably be used as starting raw material.Example comprises high oleic sunflower oil and Semen Brassicae campestris/cannabis oil (canola oil).In addition, the high Witconol 2301 cut that is obtained by palm kernel oil or tallow also can use.Should understand, these oil generally contain some impurity, comprise some lipid acid impurity, and their available synthetic methods are converted into sarcosinate.For example, commodity hemp/rapeseed oil can contain a kind of mixture of a large amount of oleic acid and lipid acid impurity such as palmitinic acid, stearic acid, linolic acid, linolenic acid and/or eicosenoic acid, wherein some or all can be converted into sarcosinate by this reaction method.If for the needs of preparing, can before preparation is used for the oleoyl sarcosinates of the present composition, some or all impurity substances be removed from starting oil.
At last, adding maleic anhydride or aceticanhydride in mixture can be converted into a kind of acid amides with the sarkosine that remains in the reaction mixture, thereby reduces to content of sarcosine and the possibility that forms undesirable nitrogenous impurity minimum.
The oleoyl sarcosinates of preparation oleoyl sarcosine sodium can be synthetic with following method:
The oleoyl sarcosine sodium salt synthetic-in one 2 liters three-necked round bottom flask, load onto thermometer, the Dean-Stark couch water trap of band condenser, mechanical stirrer and an inlet suction port, nitrogen is flow through by reaction mixture top by this joint.Pack in the reaction vessel sarkosine (43.3g, 0.476mol), the methanol solution of 25% sodium methylate (97.7g, 0.452mol), and methyl alcohol (400mL).Backflow 15min is with the neutralizer propylhomoserin in reaction, add then the methyl esters that obtains by the conventional high oleoyl Trisun Oil R 80 of Cargill (148.25g, 0.5mol).After removing methyl alcohol with Dean-Stark couch water trap, reaction mixture is heated to 170 ℃ keeps 1 hour to remove all water.(15.4g is 0.0714mol) with initiation reaction to add the methanol solution of 25% sodium methylate.Be reflected at 170 ℃ and keep 2.5h, methyl alcohol is collected in the Dean-Stark couch water trap during this period.To react cooling a little, add methyl alcohol (200g) then.(9.43g 0.095mol) also will react on 60 ℃ and stir 0.5h down to add maleic anhydride in methanol solution.Use rotary evaporation then, most of methyl alcohol is removed and added acetone (2L) so that product precipitation.With suction method collection product and at air drying, to obtain anhydrous solid.Show that with the GC analyze reaction mixture product mainly is an oleoyl sarcosinates, contain a small amount of following impurity: sarkosine, oleic acid and the sarcosinate that obtains by palmitinic acid, stearic acid and linolic acid.
Bleaching compounds and SYNTHETIC OPTICAL WHITNER-bleaching composition of the present invention is except containing the oleoyl sarcosine salt surfactant, also contain SYNTHETIC OPTICAL WHITNER or contain a kind of SYNTHETIC OPTICAL WHITNER and the bleaching mixture of one or more bleach-activating agents, the consumption of activator is enough to can be with one or more spot bleachings of being concerned about.The typical amounts of SYNTHETIC OPTICAL WHITNER is the about 1% to about 80%, about 5% to about 20% more typical of cleaning composition, particularly to fabric washing.Bleaching and preimpregnation composition can contain 5% to 99% SYNTHETIC OPTICAL WHITNER.If exist, the typical amounts of bleach-activating agent is to contain bleaching mixture about 0.1% to about 60%, about 0.5% to about 40% more typical that SYNTHETIC OPTICAL WHITNER adds the bleach activating thing.
The used SYNTHETIC OPTICAL WHITNER of the present invention can be any be applicable to fabric washing and at present known or be about to know other clean the SYNTHETIC OPTICAL WHITNER of the cleaning composition of purpose.They comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Perborate bleach can be used for the present invention as Sodium peroxoborate (for example one or tetrahydrate).
Peroxygen bleach is preferably used in these compositions.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate (peroxyhydrate) and suitable " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Persulphate SYNTHETIC OPTICAL WHITNER (for example Dupont is with the OXONE of commodity manufacturing) also can be used.
A kind of preferred percarbonate bleach contain mean particle size about 500 microns to about 1, the drying particulate of 000 micrometer range, less than 10% of about 200 microns no more than said particle weight of particle, greater than 10% of about 1,250 micron particle also no more than said particle weight.Randomly, percarbonate available silicon hydrochlorate, borate or water soluble surfactant active's coating.Percarbonate can be obtained by various commercial channel such as FMC, Solvay and Tokai Denka.
Composition of the present invention also can contain the mixture of bleach-activating agent.
Peroxygen bleach, perborate, percarbonate etc., best and bleach-activating agent coupling, these activators can make (promptly in washing process) on-the-spot generation peroxy acid corresponding with bleach-activating agent in the aqueous solution.
Alkyloyloxyethyl benzene sulfonate-can be used for suitable alkyloyloxyethyl benzene sulfonate structural formula of the present invention is: R wherein 1-C (O)-contain about 8 to about 12 carbon atoms, preferably about 8 to about 11, and M is the ammonium cation of for example a kind of basic metal of positively charged ion, ammonium or the replacement that suit, and sodium and potassium are the most preferred.
Particularly preferred hydrophobic alkyloyloxyethyl benzene sulfonate is to be selected from nonanoyl oxygen benzene sulfonate, 3,5,5-trimethyl acetyl oxygen benzene sulfonate, 2-ethyl hexanoyl oxygen benzene sulfonate, decoyl oxygen benzene sulfonate, caprinoyl oxygen benzene sulfonate, dodecanoyl oxygen benzene sulfonate and their mixture.
Amide group deutero-bleach-activating agent-can be used for amide group deutero-bleach-activating agent of the present invention is the substituted amide compound with following general formula:
Figure A9519443200121
Perhaps their mixture, wherein R 1Be to contain about 1 alkyl, aryl or alkaryl, R to about 14 carbon atoms 2Be to contain about 1 alkylidene group, arylidene or alkarylene, R to about 14 carbon atoms 5Be H or contain about 1 alkyl, aryl or alkaryl that L mainly is any suitable leavings group to about 10 carbon atoms.Leavings group be since the hydrogen peroxide negatively charged ion to the nucleophilic attack of bleach-activating agent and by substituted any group on the bleach-activating agent.This crosses the generation that hydrolysis reaction causes peroxycarboxylic acid.Generally, as suitable leavings group electron-withdrawing power must be arranged.It also will form a stable entity so that reversed reaction can be ignored.This helps the anionic nucleophilic attack of hydrogen peroxide.
The L group must have enough reactive behavioies reacting in Best Times scope (for example, wash(ing)cycle).If but L is too active, this activator is used in and is difficult in the bleaching composition stablize.These features are corresponding with the pKa value of leavings group conjugate acid usually, though this convention also has exception.Usually, the leavings group that shows this behavior be the pKa value of its conjugate acid at about 4 to about 13 leavings group, about 6 to about 11 is preferred, and about 8 to about 11 is the most preferred.
Preferred bleach-activating agent is to have top general formula, R in the general formula 1, R 2And R 5As above be the peroxy acid defined, and L is selected from following group:
Figure A9519443200122
Figure A9519443200131
With their mixture, wherein R 1Be to contain about 1 alkyl, aryl or alkaryl, R to about 14 carbon atoms 3Be to contain 1 alkyl chain to about 8 carbon atoms.R 4Be H or R 3, Y is H or a solubilizing group.
Preferred solubilizing group is-SO 3 -M +,-CO 2 -M +,-SO 4 -M +,-N +(R 3) 4X -And O＜--N (R 3) 3, and most preferably-SO 3 -M +With-CO 2 -M +, R wherein 3Be to contain about 1 alkyl chain to about 4 carbon atoms, M is a kind of positively charged ion, can make the bleach-activating agent dissolving, and X is a kind of negatively charged ion, can make the bleach-activating agent dissolving.M preferred as alkali, ammonium or replacement ammonium cation, and sodium and potassium are most preferably, X is a halogen.Hydroxide ion, methylsulfate or acetate anion.Should be noted that the bleach-activating agent with the leavings group that does not contain solubilizing group should fully disperse to impel its dissolving in liquid lime chloride.
Preferred bleach-activating agent have above general formula wherein L be selected from following group: R wherein 3As defined above, and Y is-SO 3 -M +Or-CO 2 -M +Wherein M as defined above.
Preferred example with bleach-activating agent of above structural formula comprises (6-decoylamide caproyl) oxygen benzene sulfonate, (6-pelargonamide caproyl) oxygen benzene sulfonate, (6-decyl amide caproyl) oxygen benzene sulfonate, and their mixture.
Another kind of important bleach-activating agent can provide organic peracid, and this is owing to the carbonyl carbon of hydrogen peroxide negatively charged ion on ring started the ring opening of this paper institute appellation that nucleophilic attack causes.For example in the lactan activator, this ring-opening reaction relates to the attack to the lactan cyclocarbonyl of hydrogen peroxide or its negatively charged ion.Because hydrogen peroxide or its negatively charged ion preferably occur on the outer carbonyl of ring the attack of acyl lactam, think that obtaining more open loop may need catalyzer.For example, at the U.S.Patent that announce October 30 nineteen ninety, can find the example of another open loop bleach-activating agent among the Hodge et al. in the disclosed activator.
The disclosed activator compound of Hodge comprises the benzoxazine type activator with following structural formula:
Figure A9519443200141
The replacement benzoxazine that comprises following type:
Figure A9519443200142
R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, R 2, R 3, R 4And R 5Can be to be selected from H, halogen, alkyl, thiazolinyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, COOR 6(R wherein 6Be H or alkyl) and carbonyl functional group's identical or different substituting group.
A kind of preferred benzoxazine type activator is
Figure A9519443200143
When using these activators, between about 8.5 to about 10.5, be preferably washings between 9.5 to 10.5 promoting hydrolysis reaction, thereby obtain the best surface bleachability with the pH value.Can obtain such pH value with the material that is called buffer reagent usually, the sort buffer agent is the optional compound of bleach system of the present invention.
The preferred bleach-activating agent of a class comprises the acyl lactam activator again, particularly has the acyl caprolactam and the acyl group Valerolactim of following structural formula:
Figure A9519443200144
R wherein 6Be H, contain 1 alkyl, aryl, alkoxy aromatic yl or alkaryl, or contain about 6 substituted-phenyls to about 18 carbon atoms to about 12 carbon atoms.Referring to common unsettled U.S.applications 08/046,562 and 08/082,270, they disclose the substituted benzene formyl lactan.Also can be referring on October 8th, 1985 authorizing Sanderson, the U.S.Patent 4,545,784 that is hereby incorporated by, it discloses acyl caprolactam, comprises the benzoyl caprolactam that is adsorbed in the Sodium peroxoborate.
The various non-limitative examples of activator that can also constitute bleaching composition disclosed in this invention comprise the activator of April 10 nineteen ninety in U.S.Patent 4,915,854 that authorizes Mao et al and U.S.Patent 4,412,934.Also can be referring to U.S.4, other typically useful SYNTHETIC OPTICAL WHITNER and activator in 634,551 to the present invention.
SYNTHETIC OPTICAL WHITNER-spendable another kind of optional, also be that preferred SYNTHETIC OPTICAL WHITNER includes but not limited to percarboxylic acids SYNTHETIC OPTICAL WHITNER and its esters.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate (INTEROX), the magnesium salts of metachloroperbenzoic acid, 4-pelargonamide-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.This class SYNTHETIC OPTICAL WHITNER is disclosed in the U.S.Patent 4,483,381 of issue on November 20th, 1984, Hartman, the U.S.Pat.App.740 of application on June 3rd, 1985,446, Burns et al, the EuropeanPat.App.0 that on February 20th, 1985 delivered, 133,354, the U.S.Patent4 of Banks et al and issue on November 1 nineteen eighty-three, 412,934, Chung et al.Particularly preferred SYNTHETIC OPTICAL WHITNER also comprises respectively the U.S.Paten 4,634,551 that announces on January 6th, 1987 and on August 11st, 1987, Burns et al and 4,686,063, and 6-nonyl amine base-6-oxo of describing among the Burns et al is crossed oxy hexanoic acid.
The structural formula of suitable acid amides peroxy acid is:
Figure A9519443200151
R wherein 1, R 2And R 5Be same as above definition to acid amides derivative type bleach-activating agent.
Preferred organic peracid is selected from 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid; 6-(amino in the ninth of the ten Heavenly Stems)-6-oxo is crossed oxy hexanoic acid; The last of the ten Heavenly stems sulphonyl perpropionic acid; And heptan-, hot-, the ninth of the ten Heavenly Stems-, the last of the ten Heavenly stems-the sulphonyl perbutyric acid; With their mixture.
U.S.Pat.4,686,063 embodiment 1 has walked to the 9th hurdle the 5th line description synthesizing of NAPSA by the 8th hurdle the 40th, and has walked to the 9th hurdle the 65th line description synthesizing of NAPAA by the 9th hurdle the 15th.
This composition has excellent bleaching/scourability, and natural rubber machine parts and other natural rubber goods are comprised that the fabric that contains natural rubber and natural rubber elastomer is completely.To bleaching mechanism, particularly superficial bleaching mechanism is also not exclusively understood.But it is generally acknowledged that bleach-activating agent is subjected to the anionic attack of hydrogen peroxide that hydrogen peroxide that peroxygen bleach separates out produces, and has formed peroxycarboxylic acid.This reaction was commonly called hydrolysis (perhydrolysis).
Acid amides of the present invention is derived and the lactan bleach-activating agent also can be united use with hydrophilic activator such as the TAED to rubber and enzyme safety, and acid amides is derived or caprolactam activators: the typical weight of TAED compares between 1: 5 to 5: 1, preferably about 1: 1.
The used bleach catalyst agent material of bleaching catalyst-the present invention can comprise free acid type, salt etc.Preferably bleaching catalyst itself does not play bleaching action, but is used as catalyzer to promote the performance of market bleach agent, particularly oxygen bleaching agent such as perborate, percarbonate, persulphate, particularly when bleach-activating agent exists.
One type bleaching catalyst is to contain a kind of the have active heavy metal of certain bleach catalyst such as copper, iron or manganese positively charged ion, a kind of have very little or do not have the active assistant metal positively charged ion of bleach catalyst such as zinc or aluminium cations, with a kind of sequestrant that has certain to catalysis and assistant metal cationic stabilized constant, ethylenediamine tetraacetic acid (EDTA) particularly, the catalyst system of ethylenediamine tetraacetic (methylene phosphonic acid) and water-soluble salt thereof.This class catalyzer is disclosed in U.S.Pat.4, in 430,243.
The bleaching catalyst of other type comprises U.S.Pat.5, disclosed manganese basigamy compound in 246,621 and U.S.Pat.5,244,594.The preferred example of these catalyzer comprises Mn 2 IV(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2, Mn 2 III(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-three azepine nonanes) 2(ClO 4) 2, Mn 4 IV(u-O) 6(1,4, the 7-7-triazacyclononane) 4(ClO) 4, Mn IIIMn 4 IV(u-O) 1(u-OAc) 2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 3With their mixture.Other example is at European Pat.App Pub.No.549, narration arranged in 272.Comprise 1,5 at this other part that is suitable for, 9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and their mixture.
Be applicable to that bleaching catalyst that machine is washed dish composition and enriching powdery cleaning composition also is fit to the present invention and selects for use.The example of suitable bleaching catalyst can be referring to U.S.Pat.4, and 246,612 and U.S.Pat.5,227,084.
Also can be referring to U.S.Pat.5,194,416, wherein told about for example M of monokaryon manganese (IV) title complex n IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH 3) 3(PF 6).
At U.S.Pat.5, a disclosed class bleaching catalyst again is manganese (II), (III) and/or the water-soluble complexes (IV) with a part in 114,606, and this part is a kind of non-carboxylate salt polyols that have three serial connection C-OH at least.Preferred part comprises sorbyl alcohol, iditol, melampyrum, mannitol, arabitol, Xylitol, adonitol, meso-tetrahydroxybutane, meso-inositol, lactose and their mixture.
U.S.Pat 5,114, and 611 have told about a kind of bleaching catalyst that a kind of transition metal comprises the title complex of Mn, Co, Fe or Cu and non--(greatly)-ring part that contains.The structural formula of said part is:
Figure A9519443200171
Each R wherein 1, R 2, R 3And R 4Can be selected from H, substituted alkyl and aryl make each R 1-N=C-R 2And R 3-C=NR 4Form one five yuan or six-ring.Said ring also can further be substituted.B is selected from O, S, CR 5R 6, NR 7With the abutment of C=O, wherein each R 5, R 6And R 7Can be H, replacement or unsubstituted alkyl or aryl.Preferred part comprises: pyridine, pyridazine, pyrimidine, imidazoles, pyrazoles, and triazole ring.Randomly, substituting groups such as the available for example alkyl of said ring, aryl, alkoxyl group, halogen and nitro replace.Particularly preferably be part 2,2 '-two pyridine amine.Preferred bleaching catalyst comprises Co, Cu, Mn, Fe-two pyridine methane and-two pyridine amine complexes.Highly preferred catalyzer comprises Co (2,2 '-two pyridine amine) Cl 2, two (isothiocyanato) two pyridine amine-cobalts (II), three or two pyridine amine-cobalt (II) perchlorate, Co (2,2-two pyridine amine) 2-O 2ClO 4, two-(2,2 '-two pyridine amine) copper (II) perchlorate, three (two-2-pyridine amine) iron (II) perchlorate and their mixture.
Other example comprises managanese gluconate, Mn (CF 3SO 3) 2, Co (NH 3) 5Cl and comprise N with four-N-coordination and two-N-ligand 4Mn III(u-o) 2Mn IVN 4) +(Bipy 2Mn III(u-o) 2Mn IVBipy 2)-(ClO 4) 3The double-core Mn that cooperates.
Prepare the also available way of water soluble ligand being mixed in aqueous media with water-soluble manganese salt and concentrating the gained mixture with method of evaporation of bleaching catalyst of the present invention.Here available any water-soluble manganese salt easily.Mn (II), Mn (III), Mn (IV) and/or (V) be easy to obtain with commercial size.Under some situation, may there be enough manganese in the washings, exists with catalytically effective amount to guarantee it but generally tend in composition, add the Mn positively charged ion.For example, with the sodium salt of part be selected from MnSO 4, Mn (ClO 4) 2Or MnCl 2A kind of salt of (least preferred) is under neutrality or subacidity pH value condition, with about 1: 4 to 4: 1 part: manganese salt mol ratio is dissolved in the water.With method for boiling earlier with water deoxygenation and be blown into nitrogen and cool off.The gained solution evaporation (can be led to N in case of necessity, 2), the gained solid can need not to be further purified and be used for bleaching of the present invention and cleaning composition.
In another embodiment, with water-soluble manganese source such as MnSO 4Add in the bleaching/cleaning composition or contain in the water bleaching/rinse bath of part.Obviously, the scene has formed certain title complex, is guaranteed thereby bleachability is improved.In this field process, using the part to a large amount of molar excess of manganese is easily, and the typical mol ratio of part: Mn is 3: 1 to 15: 1.Superfluous part also can be used for removing buoyant metal ion such as iron and copper, thereby has prevented the decomposition of SYNTHETIC OPTICAL WHITNER.European Pat.App.Pub.No.549 has narrated a possible this system in 271.
Though the structure of bleaching of the present invention-catalysis manganese complex is not illustrated as yet, can suppose that they contain inner complex or other hydration coordination compound of the generation because the carbonyl of part and nitrogen-atoms and manganese positively charged ion interact.Equally, the oxidation state of manganese positively charged ion in catalytic process is also imprecise to be known, may be (+II), (+III), (+IV) or (+V) valence state.Because part may be six with the manganese positively charged ion and combine, and can have reason to suppose may have multinuclear species and/or " cage shape " structure in water bleaching medium.No matter active Mn-part species are with which kind of form physical presence, and it obviously is to have improved bleachability to stain such as tea, tomato-sauce, coffee, blood etc. in catalytic mode.
Other bleaching catalyst is at for example European Pat. App. Pub. Nos.408,131 (cobalt complex catalyzer), 384,503 and 306,089 (metal-porphyrin catalysts), U.S.4,728,455 (manganese/polygamy position ligand catalyst), U.S.4,711,748 and EuropeanPat.App.Pub.No.224,952 (silico-aluminate suction Mn catalysts), U.S.4,601,845 (aluminosilicate carrier supports manganese and zinc or magnesium salts), U.S.4,626,373 (manganese/ligand catalysts), U.S.4,119,557 (high price iron complex catalyzer), German Pat.Specification 2,054,019 (cobalt sequestrant catalyzer), Canadian 866,191 (salt that contain transition metal), U.S.4,430,243 (sequestrant and manganese positively charged ion and on-catalytic metallic cations), and U.S.4, be described in 728,455 (the managanese gluconate catalyzer).
If use bleaching catalyst in the present composition and method, its consumption should reach the catalysis effective level.So-called " catalysis effective level " is meant an amount, and it all is being enough to strengthen by target matrix the ability that removes one or more spots of being concerned about under used any comparison test condition.For example, in fabric washing operation, the typical fabrics that target matrix will be made dirty by for example various food stains.To washing dish automatically, target matrix may be porcelain cup or a porcelain dish or polyethylene pan of being made dirty by tomato soup that the tea stain is arranged for example.Change test conditions according to the type of used washing implement and user's custom.For example, the anterior loading type washing machine of Europe use generally uses less water and denseer washing composition than top loading American version washing machine.The wash(ing)cycle of some machine is long more a lot of than other machine.The certain user selects awfully hot water for use; And other user uses warm water even cold water to carry out the fabric washing operation.Certainly, the catalytic performance of bleaching catalyst will be subjected to these condition effect, and the consumption of bleaching catalyst can suitably be adjusted in fill a prescription fully washing and the bleaching composition.In fact be not in a limitative way ground, the present composition and method can be regulated to provide and be contained the approximately water washings of ten million/active bleaching catalyst species at least, be preferably about 0.1ppm to about 700ppm, more preferably about 1ppm is to about 500ppm.For further specifying this point, under the European condition of using perborate and a kind of bleach-activating agent (for example benzoyl caprolactam), at 40 ℃, during pH10, about 3 micromolar Mn catalysts can be effectively.Under U.S.'s condition, to obtain equifinality and concentration need be improved 3 to 5 times.On the contrary, use a kind of bleach-activating agent and Mn catalyst can make formulator be issued to same bleaching effect with perborate at the perborate consumption lower than the product that does not have Mn catalyst.
Additive component
The present composition also can randomly contain one or more detergent additive materials or other material, in order to auxiliary or enhancing scourability, handles being cleaned matrix or improving cleaning composition aesthetic properties (as fragrance, color, tint permanence etc.).Below be these illustrative examples of adding material.
Detergent surfactant-be applicable to that the optional detergent surfactant non-limitative example of cleaning composition of the present invention comprises: common C 11-C 18Alkylbenzene sulfonate (" LAS ") and side chain and random C 10-C 20Primary alkyl sulphates (" AS "), molecular formula is CH 3(CH 2) x(CHOSO 3 -M +) CH 3And CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3C 10-C 18Secondary (2,3) alkyl-sulphate, x and (y+1) be about 7 integer at least wherein preferably is about 9 at least, M is a water-soluble cationic, sodium particularly, unsaturated vitriol such as oleyl vitriol, C 10-C 18Alkyl alkoxy sulfate (" AExS "; Particularly x is until the ethoxy sulfate of EO about 7), C 10-C 18Alkyl alkoxy carboxylate salt (the particularly ethoxy carboxylate salt of EO 1-5), C 10-C 18Glyceryl ether, C 10-C 18Alkyl polyglycoside and the corresponding many glycosides of sulfation thereof, and C 12-C 18α-sulfonated fatty acid ester, their typical amounts about by weight 1% to about 55%.If desired, also can be with common nonionic and amphoterics such as C 12-C 18Alkyl ethoxy compound (" AE ") comprises so-called narrow peak alkyl ethoxy compound and C 6-C 12Alkylphenol alkoxy compound (particularly ethoxy compound and mixing ethoxy/propoxylation compound), C 12-C 18Trimethyl-glycine and sulfonation trimethyl-glycine (" Sultaines "), C 10-C 18Amine oxides etc. are included in the whole composition.Also can use C 10-C 18N-alkyl polyhydroxy fatty acid amide.Typical example comprises C 12-C 18The N-methyl glucose amide.Referring to WO-9,206,154.Other sugar-deriving surface promoting agent comprises fluorine-based polyhydroxy fatty acid amide of N-alkane such as C 10-C 18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C 12-C 18Glucamide can be used for having hanged down alveolitoid.C 10-C 20Common soap also can use.If it is many to wish to bubble, can use side chain C 10-C 16Soap.Negatively charged ion and nonionogenic tenside are particularly useful, and other common appropriate table surface-active agent is listed in the standard textbook.
Washing assistant-detergent builder compound can randomly be contained in the composition of the present invention to help the control hardness of minerals.Except that organic washing-assisting detergent, also can use inorganic builders.Washing assistant typically is used for fabric cleaning composition to help to remove the particle dust and dirt.
The washing assistant consumption can change significantly, depends on the application target of composition and the physical form of hope.If washing assistant is arranged in the composition, its typical content is about 1% at least.Contain about 5% detergent builder compound in the typical liquid formulations to about 50% weight, more typical with about 5% to about 30%.Contain about 10% detergent builder compound in the exemplary particles prescription to about 80% weight, more typical with about 15% to about 50%.But and do not mean that the lower or more high-load washing assistant of eliminating.
Inorganic or contain the polyphosphate (for example three polyphosphate, pyrophosphate salt and transparent polymetaphosphate) that the P detergent builder compound includes but not limited to basic metal, ammonium and pure ammonium, salts such as phosphoric acid salt, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.But need nonphosphate builders in some occasion.Importantly, though at so-called " weak " washing assistant (comparing) with phosphoric acid salt as Citrate trianion down or when using zeolite or layered silicate washing assistant under contingent " help and wash deficiency " situation, the effect of the present composition must be surprising.
The example of silicate-like builder is an alkalimetal silicate, particularly SiO 2: Na 2O is than alkalimetal silicate and layered silicate between 1.0: 1 to 3.2: 1, for example layered silicate of describing in the U.S.Patent 4,664,839 that H.H.Rieck authorizes on May 12nd, 1987.NaSKS-6 is the trade mark (among the present invention " SKS-6 ") usually slightly of a kind of crystalline layered silicate of selling of Hoechst.Different with zeolite builders, this NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has the δ-Na of layered silicate 2SiO 5Configuration.Its available for example German DE-A-3, the method for describing in 417,649 and DE-A-3,742,043 prepares.SKS-6 is the highly preferred layered silicate that the present invention uses, but other this layered silicate, as have general formula NaMSi xO 2x+1YH 2The layered silicate of O also can be used for the present invention, and wherein M is sodium or hydrogen, and x is the number between 1.9 to 4, and is preferred 2, and y is the number between 0 to 20, and preferred 0.Various other layered silicates that Hoechst provides comprise NaSKS-5, NaSKS-7 and NaSKS-11, and they are with α, and β and γ configuration exist.As above said, δ-Na 2SiO 5(NaSKS-6 type) uses the most preferred to the present invention.Other silicate such as Magnesium Silicate q-agent also can be suitable for, and it can be used as in the granular recipe crisp dose, a kind of composition in the stablizer of oxygen bleaching agent and the foaming hierarchy of control.
The example of carbonate builders is the German PatentApplication No.2 that delivered on November 15th, 1973, disclosed alkaline-earth metal and alkaline carbonate in 321,001.
The silico-aluminate washing assistant is useful in the present invention.In the powerful particle cleaning composition of last sale, the silico-aluminate washing assistant is very important, and it also is a kind of important washing assistant composition in the liquid scrubbing prescription.The silico-aluminate washing assistant comprises the silico-aluminate with following empirical formula:
M Z/n[(AlO 2) z(SiO 2) y] xH 2O is z and y at least 6 integer normally wherein, and between 1.0 to 0, x is by 0 to about 264 integer to z to the mol ratio of y, and M is that valency is the IA of n or IIA family element such as Na, K, Mg, Ca.
Silico-aluminate-the ion-exchange material that is suitable for can be used as commodity and has bought.Can be crystallization or amorphous on these aluminosilicate structures, can naturally occurringly or synthetic obtain.The U.S.Patent 3,985,669 of issue on October 12nd, 1976 discloses a kind of method of producing aluminosilicate ion exchange material among the Krummel et al.The preferred synthetic crystallization aluminosilicate ion exchange material that the present invention is suitable for can be with name of an article Zeolite A, Zeolite P (B), and Zeolite MAP and Zeolite X buy.In a particularly preferred embodiment, the crystal aluminosilicate ion-exchange material has structural formula:
Na 12[(AlO 2) 12(SiO 2) 12] xH 2O wherein x by about 20 to about 30, particularly about 27.This material is called zeolite A.Dehydration zeolite (x=0-10) also can be used for the present invention.The preferred granularity of silico-aluminate is that diameter is approximately the 0.1-10 micron.
Be suitable for the organic detergent builder compound of the object of the invention and include, but not limited to miscellaneous multi-carboxylic acid's compound.Here used " multi-carboxylic acid " is meant the compound that contains a plurality of hydroxy-acid groups, preferably at least 3.Multi-carboxylic acid's washing assistant generally can be added in the composition with the form of acid, but also can add with the form of neutralized salt.When using with the form of salt, basic metal such as sodium, potassium and lithium, or pure ammonium salt is preferred.
Multi-carboxylic acid's washing assistant comprises many kinds of useful materials.The important multi-carboxylic acid's washing assistant of one class comprises poly carboxylic acid ether, is included in the Berg that announced on April 7th, 1964, U.S.Patent3, the Lamberti et al that on January 18th, 128,287 and 1972 announced, U.S.Patent3, disclosed oxygen connects two Succinic Acid in 635,830.Also can be referring on the May 5th, 1987 of " TMS/TDS " washing assistant in the U.S.Patent 4,663,071 of Bush et al promulgation.The ether carboxylic acid that is suitable for also comprises ring compound, particularly for example in U.S.Patent 3,923,679; 3,835,163; 4,158,635; The alicyclic compound of describing in 4,120,874 and 4,102,903.
Other detergent builder compound that is suitable for comprises hydroxypolycarboxylic acid's ether, the multipolymer of maleic anhydride and ethene or methoxy ethylene, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carbonyl methyl oxygen connect Succinic Acid, the polyacetic acid salt of various basic metal, ammonium and replacement ammonium such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and multi-carboxylic acid such as mellitic acid, Succinic Acid, oxygen connect two Succinic Acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carbonyl methyl oxygen connect Succinic Acid, and their soluble salt.
Lemon acids washing assistant such as citric acid and soluble salt thereof (particularly sodium salt) are the multi-carboxylic acid's washing assistants to powerful liquid washing agent particularly important, and this is because they can and biological degradation can take place available from renewable resources.The lemon acids also can be used for particulate composition, particularly with zeolite and/or the coupling of layered silicate washing assistant.Oxygen connects two Succinic Acid classes at this composition and unite in the use particularly useful.
Disclosed 3 in the U.S.Patent 4,566,984 of the Bush of on January 28th, 1986 promulgation, 3-dicarbapentaborane-4-oxa--1,6-hexane two acids and related compound also are applicable to cleaning composition of the present invention.The Succinic Acid washing assistant that is suitable for comprises C 5-C 20Alkyl and alkenyl succinic acid and its esters.This compounds particularly preferably is the dodecenyl succinic Succinic Acid.The object lesson of Succinic Acid class washing assistant comprises: dodecyl Succinic Acid class, tetradecyl Succinic Acid class, hexadecyl Succinic Acid class, 2-dodecenyl succinic Succinic Acid class (preferably), 2-15 carbene base Succinic Acid classes etc.Dodecyl Succinic Acid class is the preferred person in this group, among the European Patent Application 86200690.5/0,200,263 that on November 5th, 1986 delivered it is described.
Other multi-carboxylic acid who is suitable for is disclosed in the U.S.Patent4 of promulgation on March 13rd, 1979, and 144,226, the U.S.Patent3 of Crutchfield et al and promulgation on March 7th, 1967,308,067, among the Diehl.Also can be referring to the U.S.Patent 3,723,322 of Diehl.
Lipid acid is C for example 12-C 18Monocarboxylic acid such as oleic acid and/or its esters also can be added in the composition separately, or add together so that the washing assistant activity further to be provided with above-mentioned washing assistant, particularly citric acid and/or Succinic Acid washing assistant.So use lipid acid generally can cause bubbling and lack, this point formulator should take in.
Under the situation that can use phosphorus base washing assistant, particularly at the block preparation that is used for hand-washing operation, available various alkali metal phosphates such as famous three sodium polyphosphates, trisodium phosphate and sodium orthophosphate.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1, and 1-diphosphonate and other known phosphonate (can be referring to for example, U.S.Patents 3,159, and 581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).
Enzyme-enzyme can be included in the preparation that the present invention is used for various fabrics washing purpose, and these purposes comprise for example removes protein-based, glycosyl or tri-glyceride base spot, and dye transfer and fabric is restored prevents to come off.The enzyme that adds comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and their mixture.Other kind fermentoid also can be included.They can be from any suitable source such as vegetables, animal, bacterium, fungi and yeast source.But, select any will decision by Several Factors, as pH-active and/or the most suitable stable condition, thermostability, to the stability of activated detergent, washing assistant etc.In this respect, for example bacterial amylase and proteolytic enzyme and fungal cellulase are preferred for bacterium or fungal enzyme.
Usually the enzyme content that adds should be enough to provide the organized enzyme that contains 5mg weight in high extremely every gram composition, and more typical is extremely approximately 3mg of about 0.001mg.In other words, typically contain about 0.001% in the present composition, preferably contain the commercial enzyme preparation of 0.01%-2% weight to about 5%.Proteolytic enzyme is present in usually can be provided in active those commodity preparations of 0.005 to 0.1 Anson unit (AU) to every gram composition.
The suitable example of proteolytic enzyme is the subtilysin that obtains in the bacterial strain by B. withered grass and the special rhzomorph of B. lichenoid form.Another kind of suitable proteolytic enzyme is to derive from a kind of Bacillus strain, and it all has high reactivity in the whole pH scope of 8-12, by Novo Industries A/S exploitation, sells with registrar name of an article ESPERASE.The preparation of this kind of enzyme and similar enzyme is at the BritishPatent of Novo Specification No.1, is described in 243,784.The protease that being suitable for of can be used as that commodity have bought removed the protein-based spot comprise that Novo Industries A/S (Denmark) sells with trade name ALCALASE and SAVINASE with International Bio-Synthetics, the MAXATASE protease of Inc. (Holland).Other proteolytic enzyme comprises that protease A (sees the European Patent Application130 that on January 9th, 1985 delivered, 756) and proteolytic enzyme B (see the European PatentApplication Serial No.87303761.8 of on April 28th, 1987 application and the EuropeanPatent Application 130 that delivered on January 9th, 1985,756, Bott et al).Most preferably this paper is called " proteolytic enzyme C ", it is by genus bacillus, a kind of alkali serine protease variants that obtains by the bacillus Lentinus Edodes fungus particularly, in the bacillus Lentinus Edodes fungus, arginine replaces Methionin at 27, tyrosine replaces Xie Ansuan at 104, and Serine replaces aspartic acid at 123, and L-Ala replaces Threonine at 274.Proteolytic enzyme C is at EP 90915958:4; U.S.PatentNo.5 is described in 185,250 and U.S.Patent No.5,204,015.Be entitled as the common pending application U.S.Serial No.08/136 that contains the proteolytic enzyme cleaning combination, 797 and be entitled as the common pending application U.S.Serial No 08/136 that contains the proteolytic enzyme bleaching composition, the proteolytic enzyme of describing in 626 also is preferred, and these two parts of patent applications are hereby incorporated by.The genetically altered variant of genetically altered variant, particularly proteolytic enzyme C is also included among the present invention.
Amylase for example comprises at British Patent Specification No.1, the α-Dian Fenmei of describing among 296,839 (Novo), the RAPIDASE of International Bio-Synthetics Inc. and the TERMAMYL of Novo Industrios.
Can be used for cellulase of the present invention and comprise bacterial fibers enzyme and fungal cellulase.Best pH is preferred between 5 to 9.5.The U.S.Patent 4 of promulgation on March 6th, 1984,435,307, Barbesgoard et al, in suitable cellulase is disclosed, this patent disclosure produce fungal cellulase that moulds obtain and by the cellulase that extracts in a kind of extra large mollush liver pancreas of (extra large axe belongs to Holothuroidea car shellfish) by the cellulase 212 of Humicola insolens and Humicola strain DSM 1800 or Aeromonas.Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.CAREZYME (Novo) is particularly useful.
The lipase that washing composition is suitable for comprises by the pseudomonas microorganism belonging to genus, British Patent1 for example, the lipase that the unicellular Si Tacerui bacterium of disclosed vacation ATCC 19.154 produces in 372,034.Also can be referring to the Japanese Patent Application53 that announced on February 24th, 1978 for public's examination, the lipase in 20487.This lipase can be by Amano Pharmaceutical Co.Ltd., Nagoya, and Japan buys with trade(brand)name Lipase P " Amano ", hereinafter will be called " Amano-P ".Other commodity lipase comprises Amano-CES, and by the pigment bacillus mucus Pseudomonas lipase that obtains of pigment bacillus slime-fungi variant steatolysis bacterium NRRLB 3673 for example, it can be by Toyo Jozo Co., Tagata, and Japan has bought with commodity; And U.S.BiochemicalCorp., U.S.A. and Disoynth Co., pigment bacillus slime-fungi lipase that The Netherlands provides and the lipase that obtains by the gladiolus pseudomonas.By drawing the corruption of slave's yarn to plant (also can referring to EPO 341,947) LIPOLASE enzyme that bacterium obtains and that can be bought with commodity by Novo is a kind of preferred fat enzyme that the present invention uses.
Couplings such as peroxidase and oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide.They are used to carry out " solution bleaching ", promptly avoid in washing operation being transferred on other matrix in the washings by dyestuff of taking off on the matrix or pigment.Peroxidase is ripe in the present technique field, and it comprises for example horseradish peroxidase, ligninase and haloperoxidase such as chloro peroxidase and bromoperoxidase.The cleaning composition that contains peroxidase is disclosed in for example to be announced on October 19th, 1989, was transferred by O.Kirk among the PCT International Application WO 89/099813 of Novo Industries A/S.Wish that material that those are regarded as the peroxidase accelerator such as phenolsulfonate and/or thiodiphenylamine and these peroxidase unite use.
In the U.S.Patent 3,553,139 of people such as Mc Carty promulgation, also disclosed the plurality of enzymes material on January 5th, 1971 and they have been mixed method in the synthesis of detergent composition.Enzyme also is disclosed in the U.S.Patent4 that Place et al is given in promulgation on July 18th, 1978, and on March 26th, 101,457 and 1985, promulgation was given among the U.S.Patent 4,507,219 of Hughes.The method that is applicable to the enzyme material of liquid washing agent and mixes this preparation is disclosed in promulgation on April 14th, 1981 and gives among the U.S.Patent 4,261,868 of Hora et al.The enzyme that is used for washing composition can be stablized with various technology.The enzyme stabilization technique discloses and is illustrated in the U.S.Patent 3 of promulgation on August 17th, 1971 to people such as Gedge, 600, the European Patent Application Publication No.0 that delivered on October 29th, 319 and 1986,199,405, Venegas is among the Application No.68200586.5.At for example U.S.Patent3, the enzyme stabilising system has also been described in 519,570.
The used enzyme of enzyme stabilizers-the present invention is stablized by the water-soluble calcium source and/or the magnesium ion source that exist in the final product composition having, these ion sources provide these ions to enzyme, and (calcium ion is more effective than magnesium ion usually, if only use a kind of positively charged ion, the preferred calcium of the present invention).If the particularly borate species existence of the disclosed stablizer of various other technology is arranged, stability is increased, referring to Severson, U.S.4,537,706.Typical washing composition, particularly liquid should contain every liter of final product composition having about 1 to about 30, the calcium ions that preferably approximately 2 to about 20, more preferably about 5 to about 15, most preferably about 8 rubs to about 12 millis.This content can suitably change, and depends on the enzyme content and its reaction to calcium and magnesium ion of existence.When selecting calcium or magnesium ion content, should with composition in washing assistant, after lipid acid etc. cooperate, still can provide calcium, the magnesium ion of minimum level for enzyme.Any water-soluble calcium or magnesium salts all can be used as calcium or magnesium ion source, include but not limited to calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formiate and calcium acetate, and corresponding magnesium salts.The small amount of calcium ion generally by every liter about 0.05 to about 0.4 little rubbing, usually also is present in the composition, and this is owing in enzyme slurries and the prescription water calcium is arranged.In solid detergent composition, can contain the water-soluble calcium ion source of q.s in the prescription so that make and reach above-mentioned content in the washing liquid.In work-around solution, natural water hardness is just enough.
Should understand, the above-mentioned content of calcium and/or magnesium ion just is enough to make enzyme stable.Can add more calcium and/or magnesium ion so that the addition thereto of degrease performance to be provided to composition.Therefore the suggestion present composition typically should contain about 0.05% water-soluble calcium or magnesium ion source to about 2% weight usually, or the both has.Certainly, this content can change with the amount and the type of used enzyme in the composition.
The present composition also can be randomly, but preferably contain various additional stability agent, particularly borate type stablizer.Typically, the consumption of these stablizers in composition is about 0.25% to about 10% of boric acid or other boric acid compound weight that can form boric acid in composition, preferably about 0.5% to about 5%, is more preferably about 0.75% to about 3% (is that benchmark calculates with boric acid).Boric acid is preferred person, though other compound such as boron oxide, borax and other alkali metal borate (as sodium former-, partially-and pyroborate and sodium pentaborate) also be suitable for.Substituted boracic acid (as benzene for boric acid, butane boric acid and right-bromophenyl boric acid) also can be used to replace boric acid.Should be understood that these materials also can be used as unique stablizer and are used in the preparation, also can unite use with the calcium and/or the magnesium ion that add.
At last, wish to add chlorine scavenger, particularly in the composition that contains proteolytic enzyme, avoid the destruction of the chlorine that the city typically exists in supplying water with protective enzyme.This class material is described among 810, the 413 to Pancheri et al at for example U.S.Patent4.
Polymerization soil releasing agent-any polymerization soil releasing agent well known to those skilled in the art all can randomly be used for composition of the present invention and method.The feature of polymerization soil releasing agent is the existing hydrophilic radical that makes hydrophobic fabric such as polyester and nylon surface hydrophilic, the hydrophobic group is also arranged, it can be deposited on the hydrophobic fabric and in whole washing and rinse cycle attached to top, thereby as the attachment point of hydrophilic radical.Like this can be so that handle easier washing off in the back spot washing step afterwards that occurs with soil releasing agent.
The useful polymerization soil releasing agent of the present invention particularly including: (a) have the soil releasing agent of the one or more nonionic hydrophilic components that mainly contain following group: (i) polymerization degree is at least 2 polyoxyethylene group, or (ii) propylene oxide or the polymerization degree are 2 to 10 polyoxypropylene group, wherein said hydrophilic radical does not contain any propylene oxide unit, unless it with ehter bond at two ends and group keyed jointing on every side, or (iii) by ethylene oxide and 1 to a kind of olefin oxide unit mixture that about 30 propylene oxide units are formed, wherein said mixture contains the ethylene oxide unit of q.s, so that can make hydrophilic compounds have enough big wetting ability, thereby increase conventional polyester synthon surface in the wetting ability of soil releasing agent when it deposits, said hydrophilic radical preferably contains about at least 25% ethylene oxide unit, more preferably, particularly those contain the composition of about 20-30% propylene oxide unit, contain about at least 50% ethylene oxide unit; Or (b) has a soil releasing agent of the one or more hydrophobic compositions that contain following group: (i) oxidation C 3The alkene terephthalate is if wherein said hydrophobic composition also contains the ethylene oxide terephthalate, the ethylene oxide terephthalate: oxidation C 3The ratio of alkene terephthalate units is about 2: 1 or lower, (ii) C 4-C 6Alkene or oxidation C 4-C 6Olefin group or their mixture, (iii) poly-(vinyl acetate) group, preferred degree of polymerization is at least 2 Vinyl Acetate Copolymer, or (iv) C 1-C 4Alkyl oxide or C 4Hydroxyalkyl ether substituting group or their mixture, wherein said substituting group is with C 1-C 4Alkyl oxide or C 4Hydroxyalkyl ether derivatived cellulose or its form of mixtures exist, and these derivatived celluloses are hydrophilic, thereby make them have the C of q.s 1-C 4Alkyl oxide and/or C 4The hydroxyalkyl ether unit deposition is to conventional polyester synthon surfaces and keep the hydroxyl of q.s, in case be adhered to these common synthon surfaces, can increase the wetting ability of fiber surface, or (a) and associating (b).
Typically, (a) polyoxyethylene group of (i) has 2 to about 200 the polymerization degree, though also can use the higher polymerization degree, preferably 3 to about 150, is more preferably 6 to about 100.Suitable oxidation C 4-C 6Alkene hydrophobic group includes but not limited to, the end-blocking of polymerization soil releasing agent such as MO 3S (CH 2) nOCH 2CH 2O-, wherein M is a sodium, and n is the integer of 4-6, and it discloses on January 26th, 1988 in the U.S.Patent 4,721,580 of Gosselink promulgation.
Useful polymerization soil releasing agent also comprises derivatived cellulose such as hydroxy ethers cellulose polymer compound among the present invention, the copolymerization block thing of ethylene terephthalate or propylene terephthalate and polyoxyethylene or polyoxytrimethylene terephthalate etc.These reagent can be used as commodity and buy and comprise cellulosic hydroxy ethers such as METHOCEL (Dow).The Mierocrystalline cellulose soil releasing agent that the present invention uses also comprises and is selected from C 1-C 4Alkyl and C 4The Mierocrystalline cellulose soil releasing agent of hydroxy alkyl cellulose; Referring on December 28th, 1976 to Nicol, the U.S.Patent4 of et al promulgation, 000,093.
The soil releasing agent that is feature with poly-(vinyl acetate) hydrophobic group comprises poly-(vinyl acetate), for example C 1-C 6Ethene fat, preferred poly-(vinyl acetate between to for plastic) is to polyoxyalkylene hydrocarbon skeleton such as polyoxyethylene skeleton grafted graft copolymer.Referring to the EuropeanPatent Application 0 219 048 that delivered on April 22nd, 1987, Kud, et al.This class soil releasing agent of can commodity buying comprises SOKALAN class material, and as SOKALAN HP-22, it can be obtained by BASF (West Germany).
The preferred soil releasing agent of one class is a kind of multipolymer that contains the block at random of ethylene terephthalate and polyoxyethylene (PEO) terephthalate.The molecular weight of this polymerization soil releasing agent about 25,000 to about 55,000 scopes.Referring on May 25th, 1976 to U.S.Patent on July 8th, 3,959,230 and 1975 of Hays promulgation the U.S.Patent 3,893,929 to the Basadur promulgation.
Another kind of preferred polymerization soil releasing agent is a kind of polyester with ethylene terephthalate repeating unit, it contain the ethylene terephthalate unit of 10-15% weight and 90-80% weight by molecular-weight average 300-5, the polyoxyethylene terephthalate units that 000 polyoxyethylene enediol obtains.The example of this polymkeric substance comprises and can be used as material ZELCON 5126 (by Dupont) and the MILEASE T (by ICI) that commodity are bought.Also can be referring to the U.S.Patent 4,702,857 of on October 27th, 1987 to the Gosselink promulgation.
Another kind of preferred polymerization soil releasing agent be a kind of be the sulfonated products of the ester oligomer of line formula basically, this ester oligomer is made up of a kind of oligomer ester skeleton of paraphenylene terephthalamide and oxyalkylene oxygen repeating unit and the end sections that is covalently attached to skeleton.These soil releasing agents have been done abundant description in November 6 nineteen ninety in the U.S.Patent 4,968,451 of J.J.Scheibel and E.P.Gosselink promulgation.Other suitable polymerization soil releasing agent comprises the U.S.Patent 4 of on December 8th, 1987 to people such as Gosselink promulgation, 711, terephthalic polyester in 730, on January 26th, 1988 is to 4 of the Gosselink promulgation, 721, negatively charged ion end-blocking oligomer ester in 580 and on October 27th, 1987 the block polyester oligomeric compound in the U.S.Patent 4,702,857 of Gosselink promulgation.
Preferred polymerization soil releasing agent also comprises the soil releasing agent of on October 31st, 1989 in the U.S.Patent 4,877,896 of people such as Maldonado promulgation, this patent disclosure negatively charged ion, particularly sulfonation virtue acyl, end envelope terephthalate.
Also having a kind of preferred soil releasing agent is to have paraphenylene terephthalamide unit, the different paraphenylene terephthalamide of sulfonation unit, ethylene oxide oxygen and oxidation-1, a kind of oligopolymer of 2-propylene repeating unit.These repeating units form the oligopolymer skeleton, and preferably stop with the isethionic acid base end-blocking of modifying.The particularly preferred a kind of about different phthalyl of sulfonation unit that contains in this class soil releasing agent, 5 paraphenylene terephthalamide unit, ratio is about 1.7 to 1.8 ethylene oxide oxygen and oxidation-1,2-propylene oxygen unit and two 2-(2-hydroxy ethoxy)-ethane sulfonic acid sodium end-blocking unit.Said soil releasing agent also contains about 0.5% and reduces the oligopolymer of stablizer to a kind of crystallization of about 20% weight, and they preferably are selected from xylenesulfonate, cumene sulfonate, tosylate and their mixture.
If usefulness, the weight of soil releasing agent be the present composition about 0.01% to about 10.0%, be typically about 0.1% to about 5%, preferably about 0.2% to about 3.0%.
Sequestrant-cleaning composition of the present invention also can randomly contain one or more iron and/or manganese sequestrant.This sequestrant can be selected from the aminocarboxylic acid class, the aminophosphonic acid class, and polyfunctional group substituted arene sequestrant and their mixture will all define them below.Do not think bound by theory, but can believe that these materials are benefit, part is by the special ability of removing iron and mn ion in the washing soln because they pass through to form the soluble chelating thing.
The aminocarboxylic acids that can be used as optional sequestrant comprises ethylenediamine tetraacetic acid (EDTA), the N-Oxyethylethylenediaminetriacetic acid, nitrilotriacetic acid(NTA), ethylenediamine tetrapropionic acid(EDTP), triethylenetetraaminehexaacetic acid, the salt of diethylenetriamine pentaacetic acid and ethanol Diglycocol and basic metal thereof, ammonium and replacement ammonium and their mixture.
When a small amount of total phosphorus of minimum tolerable existed in the cleaning composition, the aminophosphonic acid class also was suitable for use as the sequestrant in the present composition, and it comprises with DEQUEST being the ethylenediamine tetraacetic (methylene phosphonic acid class) of trade(brand)name.Preferably, these aminophosphonic acid classes do not contain the alkyl or alkenyl more than 6 carbon atoms.
Polyfunctional group substituted arene sequestrant also is applicable in the present composition.Referring to the U.S.Patent 3,812,044 of on May 21st, 1974 to people such as Connor promulgation.The preferred compound of this class that exists with sour form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.
Be used for a kind of preferred biological degradation sequestrant of the present invention and be particularly (S, S) isomer of the quadrol disuccinate (" EDDS ") in the U.S.Patent 4,704,233 of Hartman and Perkins promulgation, described on November 3rd, 1987.
If use, the consumption of these sequestrants is about 0.1% to about 10% of a cleaning composition weight of the present invention.About 0.1% to about 3.0% more preferably.
Clay soil removal/anti deposition agent-present composition more also can randomly contain the water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.The particle cleaning composition that contains these compounds typically contains the about 0.01% water-soluble ethoxylated amine to about 10.0% weight; Liquid detergent compositions typically contains about 0.01% to about 5%.
Most preferred dirt discharges and anti redeposition agent is the ethoxyquin tetren.Typical ethoxylated amine has been done among the VanderMeer to further describe at the U.S.Patent 4,597,898 of promulgation on July 1st, 1986.Another kind of preferred clay soil removal-anti redeposition agent is the European Patent Application 111,965 that delivers on June 27th, 1984, disclosed cation compound among the Oh andGosselink.Other operable clay soil removal/anti deposition agent again is included in the European Patent Application111 that delivered on June 27th, 1984,984, disclosed ethoxylated amine polymkeric substance among the Gosselink; The European Patent Application 112,592 that delivers on July 4th, 1984, disclosed amphoteric ion polymer among the Gosselink; With the U.S.Patent 4,548,744 of promulgation on October 22nd, 1985, disclosed amine oxide among the Connor.Other clay soil known in the art removes and/or anti redeposition agent also can be used for the present composition.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.
Polymeric dispersant-use is useful by about 0.1% polymeric dispersant to about 7% weight in the present composition.Suitable polymeric dispersant comprises poly-polycarboxylate and polyoxyethylene glycol, though also can use other polymeric dispersant known in the art.
Polymeric polycarboxylic acid class material can prepare by polymerization or the suitable unsaturated monomer of copolymerization, and monomer preferably exists with the form of acid.The unsaturated monomer acid that can polymerization generates suitable polymeric polycarboxylic acid class comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid, having not carboxylic monomer segment in polymeric polycarboxylic acid class of the present invention is to suit as methoxy ethylene, vinylbenzene, ethene etc., as long as these parts are no more than 40% weight.
Shi Yi polymeric polycarboxylic acid class can be obtained by vinylformic acid especially.This is the water soluble salt of polymeric acrylic acid to the useful acrylic acid based polymer of the present invention.The molecular-weight average preferable range of this acid-based polymer is about 2,000 to 10,000, is more preferably approximately 4,000 to 7,000, and most preferably is about 4,000 to 5,000.The water-soluble salt of this acrylate copolymer for example can comprise, the salt of basic metal ammonium and replacement ammonium.This class soluble polymer is a known materials.This multi-carboxylate's application in cleaning composition of birdsing of the same feather flock together has been disclosed in for example promulgation on March 7th, 1967 among the U.S.Patent 3,308,067 of Diehl.
Vinylformic acid/maleic copolymer also can be used as a kind of preferred component of dispersion/anti redeposition agent.This class material comprises the soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this multipolymer that exists with acid type is preferably between about 2,000 to 100,000.A kind of preferred multipolymer has about molecular-weight average of 2,000 to 15,000, and about 6,000 to about 13,000 more preferably, and about 7,000 to about 12,000 most preferably.Other preferred multipolymer has about molecular-weight average of 5,000 to 75,000, and about 7,000 to 65,000 most preferably.Generally between about 30: 1 to about 1: 2, about 10: 1 to 1: 1 are more preferably for the ratio of acrylic and maleic in this base polymer, and about 2.5: 1 to 1: 1 most preferably.The soluble salt of this class vinylformic acid/maleic acid can comprise for example basic metal, ammonium and substituted ammonium salt.European Patent Application No.66915 that delivers in December 15 nineteen eighty-two and the EP 193 that delivered on September 3rd, 1986, this class solubility acrylic/maleic copolymer of describing in 360 is a known materials, and back one document has also been described this base polymer that contains the hydroxypropyl acrylic.There is the useful dispersion agent of a class to comprise the terpolymer of Malaysia alcohol/vinylcarbinol/vinyl alcohol again.This class material also is disclosed among the EP 193,360, and they comprise for example 45/45/10 terpolymer of vinylcarbinol/Malaysia alcohol/vinyl alcohol.
Particularly preferred polymer dispersant is low-molecular-weight modified polypropene acid copolymer.This analog copolymer contains as monomeric unit: a) about 90% to about 10%, preferably approximately 80% is to vinylformic acid or its esters and the b of about 20% weight) about 10% substitutional crylic acid monomer or its esters to about 90% weight preferably approximately 20% to about 80% weight, and have general formula-(C (R 2) C (R 1) (C (O) OR 3))-, wherein the incomplete chemical combination valency is hydrogen and substituent R in the square brackets 1, R 2And R 3In at least one, best R 1Or R 2Be the alkyl or the hydroxyalkyl of 1 to 4 carbon, R 1And R 2Can be hydrogen, R 3Can be hydrogen or an alkali metal salt.Most preferably a kind of wherein R 1Be methyl, R 2Be hydrogen, R 3It is the substitutional crylic acid monomer of sodium.
Low-molecular-weight polypropylene acids polymer dispersant molecular weight is preferred less than about 15,000, about 500 to about 10,000 preferably, and about 1,000 to about 5,000 for most preferably.The most preferably polyacrylic acid analog copolymer that the present invention uses has 3500 molecular weight, be contain about 70% weight percent acrylic acid and about 30% weight methylacrylic acid multipolymer fully in and form.
Other suitable modified polypropene acid copolymer is included in U.S.Patent 4,530, the low-molecular weight copolymer of disclosed unsaturated aliphatic carboxylic acid in 766 and 5,084,535, and these two pieces of patents are hereby incorporated by.
The aqueous solution of cohesion form usable polymers dispersion agent of the present invention prepares condensation product (particularly when composition is made up of the mixture of Trisodium Citrate and yellow soda ash) as liquid-containing binder.Particularly preferably be molecular-weight average by about 1,000 to about 10,000 polyacrylic, with molecular weight by about 2,000 to about 80,000 and acrylic to the ratio of maleic or fumaric acid-based by about 30: 1 to about 1: 2 acrylic/maleic or acrylic/fumaric acid-based multipolymer.This class based on unsaturation single-and the example of the multipolymer of two carboxylic acid group's monomer mixtures openly be hereby incorporated by, the European PatentApplication No.66 that deliver December 15 nineteen eighty-two is in 915.
The useful polymer dispersant of other the present invention comprises molecular weight by about 950 to about 30,000 polyoxyethylene glycol and polypropylene glycol, and they can be by Dow Chemical Company ofMidland, and Michigan obtains.These compounds, its fusing point person between about 30 ℃ to about 100 ℃ for example can be with 1450,3400,4500,6000,7400,9500 and 20,000 molecular weight and obtain.Thereby make these compounds with molecular weight and the fusing point that the ethylene oxide of required mole number and propylene oxide carry out polymerization and provide polyoxyethylene glycol and polypropylene glycol to need separately.Polyoxyethylene glycol, polypropylene glycol and the poly-glycol useful molecules formula HO (CH that mixes 2CH 2O) m(CH 2CH (CH 3) O) n(CH (CH 3) (CH 2O) oH represents that wherein m, n and o are the integers that satisfies above-mentioned molecular weight and temperature needs.
Also the useful polymer dispersant of some the present invention comprises sulfate cellulose ester such as sulfovinic acid Mierocrystalline cellulose, sulfate cellulose, sulfuric acid Natvosol, sulfuric acid methylcellulose gum and sulfuric acid hydroxypropylcellulose.Ushercell is a most preferred polymkeric substance in this class.
Other suitable polymer dispersant is the U.S.Pat.No.3 that Diehl is given in promulgation on March 27th, 1973,723, the carboxylated polysaccharides of describing in 322, particularly starch, Mierocrystalline cellulose and alginate, on November 11st, 1975, the U.S.Patent No.3 of Tompson was given in promulgation, disclosed poly carboxylic acid dextrin ester in 929,107; The U.S.Pat.No.3 of Jesen is given on April 9th, 1974 promulgation, hydroxyalkyl starch ether, starch ester, Sumstar 190, dextrin and the starch hydrolysate described in 803,285; The U.S.Pat.No.3 of Eldib is given on December 21st, 1971 promulgation, the carboxylation starch of describing in 629,121; With the U.S.Pat.No.4 that issued on February 27th, 1979 to McDanald, the dextrin starch of describing in 141,841; All be incorporated herein by reference at this.Preferred cellulose-derived polymer dispersant is a carbonyl methyl cellulose.
The adoptable dispersion agent of a class is organic dispersing agent polymkeric substance such as polyaspartic acid again.
The another kind of polymeric material that can be comprised is polyoxyethylene glycol (PEG).Except that can be used as a kind of clay soil removal-anti redeposition agent works, PEG also shows the performance of dispersion agent, the typical molecular weight scope that is used for these purposes is by about 500 to about 100,000, preferably from about 1,000 to about 50,000, be more preferably from about 1,500 to about 10,000.
Polyaspartic acid and polyglutamic acids dispersion agent also can use, and particularly combine with zeolite builders.Though do not think bound by theory, but can believe, in containing the composition of detergent builder compound, polymeric dispersant is by suppressing crystalline growth, particulate fouling discharges effect such as peptization and antiredeposition and strengthens whole detergent builder compound performance, particularly when zeolite and/or silicate-like builder and other washing assistant (comprising the lower molecular weight polycarboxylate) are united use.Dispersion agent such as polyaspartic acid preferably have about 10,000 molecular weight (on average).
Brightener-any optical brightener known in the art or other blast or whitening agent can about 0.05% typical amounts to about 1.2% weight be incorporated in the cleaning composition of the present invention.Can be used for commodity optical brightener of the present invention and can be divided into some subclass, including but not necessarily limited to derivative, pyrazoline, tonka bean camphor carboxylic acid, methyne cyanine, the dibenzothiophen-5 of stilbene, 5-dioxide.Pyrroles 5-and 6-membered heterocyclic compound and other all ingredients.The example of these brighteners is disclosed in " production of brightener and application " (" The Production and Application ofFluorescent Brightening Agents "), M Zahradnik, Published by JohnWiley ﹠amp; Sons is among the New York (1982).
The brightener of pointing out in the U.S.Patent 4,790,856 of Wixon promulgation on December 13rd, 1988 is the object lesson of optical brightener useful in the present composition.The PHORWHITE series brightener that is provided by Verona is provided these brighteners.Disclosed other brightener comprises in this reference: Tinopal UNPA, Tinopal CBS and the Tinopal 5BM that can be obtained by Ciba-Geigy; Can be by being positioned at White CC and the Artic White CWD that gondola Hilton-Davis obtains; 2-(4-styryl phenyl) 2H-naphthols (1,2-dextrorotation) triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The object lesson of these brighteners comprises 4-methyl-7-diethyl-aminocoumarin; 1,2-two (Wen Zimi azoles-2-yl) ethene; 1,3-xenyl-Fu pyrroles; 2,5-two (benzoxazole-2-yl) thiophene; 2-styryl-naphthalene-(1,2-Er 〕 oxazole; And 2-(stilbene-4-yl)-2H-naphtho--(1,2-two) triazole.Also can be referring to the U.S.Patent3 that announced on February 29th, 1972,646,015 to Hamilton.Preferred anionic brightener wherein.
Suds suppressor-can will mix in the composition of the present invention in order to the compound that reduces or the inhibition foam forms.At U.S.4, in what is called of describing in 489,455 and 4,489,574 " high dense washing methods " and the anterior Europe class washing machine that feeds in raw material, foam inhibition particularly important.
A variety of materials can be used as suds suppressor, and those skilled in the art are very familiar to suds suppressor.For example, can be referring to Kirk Othmer Encyclopedia of ChemicalTechnology, Third Edition, Volume 7, pages 430-447 (JohnWiley ﹠amp; , Sons, Inc 1979).One class suds suppressor of particularly important comprises mono carboxylic lipid acid and soluble salt thereof.Referring to the U.S.Patent 2,954,347 of September 27 nineteen sixty to Wayne St.John promulgation.The mono carboxylic lipid acid and the salt thereof that use as suds suppressor typically contain 10 to about 24 carbon atoms, the preferably alkyl of 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt such as sodium, potassium and lithium salts, and ammonium and pure ammonium salt.
Cleaning composition of the present invention also can contain the on-surface-active suds suppressor.They for example comprise: high-molecular weight hydrocarbon such as paraffinic hydrocarbon, fatty acid ester (as fatty acid triglycercide), the fatty acid ester of monovalent alcohol, aliphatics C 18-C 40Ketone (as stearone) etc.Other suds suppressor comprise N-alkylation aminotriazine as three-six-alkyl melamine or as cyanuryl chloride and 2 or 3 moles contain the product of the uncle of 1 to 24 carbon atom or secondary amine and form two-to four-alkyl diamine chlorotriazine, propylene oxide and single stearyl phosphoric acid salt such as Stearinsaeure alcohol phosphate ester and single stearyl two-basic metal (as K, Na and Li) phosphoric acid salt and phosphate ester.Hydro carbons such as paraffinic hydrocarbon and halo paraffinic hydrocarbon can use with liquid form.Liquid hydrocarbon should be liquid under room temperature and barometric point, and its yield point is approximately-40 ℃ and between about 50 ℃, and its minimum boiling point is not less than about 110 ℃ (under barometric points).People know that also the use fusing point is preferably lower than about 100 ℃ wax shape hydrocarbon.Hydro carbons constitutes the suds suppressor that a class preferably is used for cleaning composition.For example, in the U.S.Patent 4,265,779 of people such as Gandolfo promulgation, the hydro carbons suds suppressor was described on May 5th, 1981.These hydrocarbon comprise for example having about 12 aliphatics to about 70 carbon atoms, alicyclic ring, fragrance and heterocycle is saturated or unsaturated hydrocarbons.Real paraffinic hydrocarbon and cyclic hydrocarbon only wanted to comprise in used term " paraffinic hydrocarbon " in about this discussion of suds suppressor.
Another kind of preferred on-surface-active suds suppressor comprises the polysiloxane suds suppressor.It comprises uses organopolysiloxane oil as polydimethylsiloxane, and dispersion and emulsification organopolysiloxane oil or resin combine organopolysiloxane with silicon dioxide granule, and wherein organopolysiloxane oil is by chemisorption or be fused on the silicon-dioxide.The polysiloxane suds suppressor is that the present technique field is known and is disclosed in the U.S.Patent 4 to people such as Gandolfo promulgation on May 5th, 1981 for example, 265,779 and the European Patent Application No.89307851.9 that delivers February 7 nineteen ninety, among the Starch M.S..
Other polysiloxane suds suppressor is disclosed in U.S.Patent 3,455, and in 839, this patent relates to composition and the method that makes aqueous solution froth breaking with the way of mixing a small amount of polydimethylsiloxane fluid.
The mixture of the silicon-dioxide of polysiloxane and silanization for example is being described among the German PatentApplication DOS 2,124,526.Polysiloxane defoamers in the particle cleaning composition and Foam Control are disclosed in the U.S.Patent3 of Bartolotta et al, and the U.S.Patent4 of Baginski et al is given on March 24th, 933,672 and 1987 promulgation, in 652,392.
Being used for a kind of typical polysiloxane group suds suppressor of the present invention is the main Foam Control that presses down the bubble amount composed as follows:
(i) 25 ℃ of following viscosity by about 20cs. to about 1, the polydimethylsiloxane liquid of 500cs.;
(i) about 5 silicone resins to about 50 parts of weight of (ii) per 100 parts of weight, this resin is by (CH 3) 3SiO 1/2Unit and SiO 2The unit is formed with about 0.6: 1 to about 1.2: 1 ratio.
(i) about 1 solid silicone of (iii) per 100 parts of weight to about 20 parts of weight.
In the used preferred polysiloxane suds suppressor of the present invention, the external phase solvent is by some polyoxyethylene glycol or ethylene glycol and 1,2-propylene glycol multipolymer or their mixture (preferably), or polypropylene glycol is formed.Main polysiloxane suds suppressor is side chain/commissure type and non-linearity preferably.
For further specifying this point, typical liquid clothes washing composition with suds suppressing properties should randomly contain the about 0.001% said polysiloxane suds suppressor to about 1% weight, about 0.01% to about 0.7% is preferred, about 0.05% to about 0.5% for most preferably, suds suppressor contains: the nonaqueous phase emulsion of (1) a kind of main suds suppressor, it is a kind of mixture of following ingredients: (a) a kind of organopolysiloxane, (b) a kind of resin siloxanes or a kind of polysiloxane compound of producing polyorganosiloxane resin, (c) a kind of particulate packing material and (d) a kind of accelerating mixture composition (a), (b) and (c) react the catalyzer that forms the silane alkoxide; (2) at least a non-ionic type polysiloxane surfactant; (3) a kind of multipolymer of polyoxyethylene glycol or ethylene glycol and 1,2-propylene glycol, at room temperature the solubleness in water should be greater than about 2 weight % for they; And do not conform to polypropylene glycol.Similarly amount can be suitable for particulate composition, gel etc.Also can be referring to the U.S.Patent 4,978,471 that issues December 18 nineteen ninety to Starch, with issued on January 8th, 1991 to 4,983,316 of Starch, on February 22nd, 1994,5,288,431 of Huberet al was given in promulgation, U.S.Patents 4,639,489 and 4 with Aizawa et al, 749,740 the 1st hurdle, the 46th walks to the 4th hurdle, the 35th row.
Polysiloxane suds suppressor of the present invention preferably contains a kind of multipolymer of polyoxyethylene glycol and ethylene glycol/propylene glycol, and its molecular-weight average all less than about 1000, is preferably between about 100 and 800.Solubleness under polyoxyethylene glycol here and the ethylene glycol/propylene glycol copolymers room temperature in water is greater than 2 weight %, more preferably greater than 5 weight %.
The preferred solvent of the present invention is that molecular-weight average is lower than about 1,000 polyoxyethylene glycol, and about 100 to 800 more preferably, and 200 to 400 most preferably, and preferred solvent also has a kind of multipolymer of ethylene glycol/propylene glycol, PPG 200/PEG 300.Preferred polyoxyethylene glycol: ethylene glycol and 1,2-propylene glycol multipolymer weight ratio is between about 1: 1 to 1: 10, most preferably between 1: 3 to 1: 6.
It is 4,000 that the present invention used preferred polysiloxane suds suppressor should not contain propylene glycol, particularly molecular weight.They preferably do not contain the such segmented copolymer that does not contain oxyethane and propylene oxide of PLURONIC L101 yet.
The suds suppressor that other the present invention is suitable for comprises the mixture of secondary alcohol (as the 2-alkyl chain triacontanol) and they and polysiloxane oil, and the example of polysiloxane is disclosed in U.S.4,798,679; 4,075,118 and EP 150,872 in.Secondary alcohol comprises having C 1-C 16The C of chain 6-C 16Alkanol.A kind of preferred alcohol is 2-butyl octanol, and it can have been bought with trade mark ISOFOL 12 from Condea.The secondary alcohol mixture can have been bought with trade mark ISALCHEM 123 by Enichem.The typical suds suppressor that mixes contains alcohol-polysiloxane mixture of 1: 5 to 5: 1 of weight ratio.
For any cleaning composition that is used for automatic washing machine, the foam of formation should not reach from the degree of washing machine overflow.When using suds suppressor, they preferably exist with " pressing down the bubble amount ".The meaning of so-called " pressing down the bubble amount " is that the composite formula Designers can select enough suds suppressor consumptions to obtain being used for the low foam laundry detergent of automatic washing machine.
The present composition generally contains 0% to about 5% suds suppressor.When as suds suppressor, the typical amount of mono carboxylic lipid acid and its esters may be up to 5% of cleaning composition weight.Fat monocarboxylic acid class suds suppressor preferable amount is about 0.5% to about 3%.The typical amounts height of polysiloxane suds suppressor is about 2.0% to cleaning composition weight, though higher content also can use.This upper limit in fact mainly be since consider to reduce cost as far as possible and low levels to suppressing foamy validity.Preferably, use by about 0.01% to about 1% polysiloxane suds suppressor, more preferably by about 0.25% to about 0.5%.Here used weight percent rate score comprises the silicon-dioxide that may unite use with organopolysiloxane.The general consumption of single stearyl phosphoric acid class suds suppressor is about 0.1% to about 2% of a composition weight.The typical amounts of hydro carbons suds suppressor is about 0.01% to about 5.0%, though also can use higher amount.The typical amounts of alcohols suds suppressor is 0.2% to 3% of a final product composition having weight.
Fabric softener-various journey the fabric softeners of washing entirely, particularly the U.S.Patent 4 of Storm and Nirschl is given in promulgation on December 13rd, 1977,062, no touch sense smectic clays in 647 and other softening agent clay known in the art can randomly be used for the present composition with about 0.5% typical amount to about 10% weight, so that provide the fabric sofetening performance with the fabric washing performance.Just as, for example the U.S.Patent 4,375 of Crisp et al is given in promulgation on March 1 nineteen eighty-three, on September 22nd, 416 and 1981, the U.S.Patent 4,291 of Harris et al was given in promulgation, 071 is disclosed such, and the clay softening agent can be united use with amine and cationic softener.
Dye transfer inhibitor-present composition can comprise that also one or more can effectively prevent the material that dyestuff is shifted to another fabric by a kind of fabric in washing process.Usually, these dye transfer inhibitors comprise polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-V-Pyrol RC and N-ethene imidazoles multipolymer, manganese phthalocyanine, peroxidase and their mixture.If use, the typical content of these reagent in composition is about 0.01% to about 10% weight.About 0.01% to about 5% is preferred, and about 0.05% to about 2% for more preferably.
Say that more specifically the preferred N-oxide polymer that uses contains the unit with following structural formula: R-A here x-P; Wherein P is a N-O group bonded polymerizable unit with it, and perhaps the N-O group can become the part of polymerizable unit, and perhaps the N-O group can be attached on two kinds of unit; A be down one of array structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is aliphatics, ethoxyquin aliphatics, aromatic series, heterocycle or alicyclic radical or their arbitrary combination, and the nitrogen of N-O group can combine with them or the N-O group is the part of these groups.Preferred polyamine N-oxide compound is that wherein R is the polyamine N-oxide of heterocyclic group such as pyridine, pyrroles, imidazoles, pyridine, piperidines and their derivative.
The N-O group can be represented with following universal architecture:
Figure A9519443200371
R wherein 1, R 2, R 3Be aliphatics, aromatic series, heterocycle or alicyclic group or their associating; X, y and z are 0 or 1; The nitrogen of N-O group can be combined on any above-mentioned group or constitute their part.The unitary pKa of the unitary amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
Any polymer backbone all can use, as long as the amine oxide polymkeric substance that generates is water miscible, and has the dye transfer rejection characteristic.The example of suitable polymer blend skeleton is polyethylene, polyolefine, polyester, polyethers, polymeric amide, polyimide, polyacrylic and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer is an amine n-oxide, and another kind is the N-oxide compound.Amine is 10: 1 to 1: 1 to the ratio of amine n-oxide in the typical amine n-oxide polymkeric substance, 000,000.But by suitable copolymerization or the suitably N-oxidation of degree, the number of the amine oxide group that exists in the polyamine oxide polymer can change.The polyamine oxide compound can be with any polymerization degree almost and is obtained.Typically, molecular-weight average is 500 to 1,000, between 000; 1,000 to 500,000 more preferably; 5,000 to 100,000 most preferably.This class preferable material can be called " PVNO ".
Useful most preferably polyamine N-oxide is poly-(4-vinylpridine-N-oxide compound) in the cleaning composition of the present invention, and its molecular-weight average approximately is 50,000, and amine is 1: 4 to the amine n-oxide ratio.
N-vinyl pyrrolidone and N-vinyl imidazole multipolymer (being called " PVPVI " class) also can be preferably in this uses.Preferably, the PVPVI molecular-weight average is 5,000 to 1, between 000,000,5,000 to 200,000 more preferably, and 10,000 to 20,000 most preferably (molecular-weight average Barch, et al., Chemical Analysis.Vol 113 " Modern Methods ofPolymer Characterization " (" modern polymer characterization method "), the middle light scattering method measuring of describing, the disclosure of the document is hereby incorporated by).The PVPVI multipolymer typically has 1: 1 to 0.2: 1 N-vinyl imidazole to N-vinyl pyrrolidone mol ratio, and 0.8: 1 to 0.3: 1 more preferably, and 0.6: 1 to 0.4: 1 most preferably.These copolymerization are line formula both, also a chain type.
The present composition also can use molecular-weight average by polyvinyl-pyrrolidone (" PVP ") of about 5,000 to about 400,000, and about 5,000 to about 200,000 is preferred, and about 5,000 to about 50,000 for more preferably.For a person skilled in the art, PVP is known; Can be referring to for example, the EP-A-262 that is hereby incorporated by, 897 and EP-A-256,696.The composition that contains PVP also can contain molecular-weight average by about 500 to about 100,000 polyoxyethylene glycol (" PEG "), and about 1,000 to about 10,000 is preferred.Preferably, the PEG that transmits in solution with the ppm base is about 2: 1 to about 50: 1 to the ratio of PVP, and about 3: 1 to about 10: 1 more preferably.
Some kind that cleaning composition of the present invention also can randomly contain about 0.005% to 5% weight also can provide dye transfer inhibiting hydrophilic optical brightener.If use, the present composition preferably contains this class chemical brightener of about 0.01% to 1% weight.
The useful hydrophilic optical brightener of the present invention is the hydrophilic optical brightener with following structural formula:
Figure A9519443200381
R wherein 1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R 2Be selected from N-2-dihydroxy ethyl, N-2-hydroxyethyl-N-methylamino-, morphine quinoline, chloro and amido; M is salt-forming cation such as sodium or potassium.
As R in the said structure formula 1Be anilino, R 2Be N-2-two-hydroxyethyl and M when being a kind of positively charged ion such as sodium, then brightener is 4,4 '-two ((4-anilino-6-(N-2-two-hydroxyethyl)-symmetry-triazine-2-yl) amidos)-2,2 '-stilbene disulfonic acid and disodium salt.This special brightener by Ciba-Geigy Corporation with trade(brand)name Tinopal-UNPA-GX as commodity selling.Tinopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the cleaning composition of the present invention.
When in the said structure formula, R 1Be anilino, R 2Be N-2-hydroxyethyl-N-2-methylamino-and M when being a kind of positively charged ion such as sodium, then brightener is 4,4 '-two ((4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-symmetry-triazine-2-yl) amidos) 2,2 '-stilbene disulfonic acid and disodium salt.This special brightener by Ciba-GeigyCorporation with trade(brand)name 5BM-GX as commodity selling.
When in the said structure formula, R 1Be anilino, R 2Be morphine quinoline and M when being a kind of positively charged ion such as sodium, then brightener is 4,4 '-two ((4-anilino-6-morphine quinoline-symmetry-triazine-2-yl) amidos) 2,2 '-stilbene disulfonic acid, sodium salt.This special brightener by Ciba-Geigy Corporation with trade(brand)name AMS-GX as commodity selling.
When using the concrete optical brightener selects to unite use for the present invention, can provide effective especially dye transfer rejection with selected foregoing polymeric dye transfer inhibitor.These selected polymeric materials (as PVNO and/or PVPVI) and these selected optical brighteners (as Tinopal UNPA-GX, Tinopal 5BM-GX, Tinopal-PLC and/or Tinopal AMS-GX) coupling can provide dye transfer restraining effect much better when using separately than these two kinds of cleaning composition compositions in the water washings.Though bound by theory not it is believed that, this behavior of these brighteners is owing to they height avidities to fabric in washings, therefore can deposit to quickly on these fabrics.Brightener in washings on fabric sedimentary degree can define with a parameter that is called " consumption coefficient ".Consumption coefficient is commonly defined as the brightener material that a) deposits on the fabric to b) ratio of brightener starting point concentration in the washings.Brightener with higher consumption coefficient is suitable for use in the present invention as the inhibition dye transfer most.
Certainly, wish that also other ordinary optical blast formulation compound randomly is used for the present composition, so that common fabric " blast " effect to be provided, rather than real dye transfer suppresses effect.This usage is common to detergent formulation and knows.
Other composition-useful various other components can be contained in the present composition in cleaning composition, and they comprise the solvent of other activeconstituents, carrier, solubilizing agent, processing material, dyestuff or pigment, liquid formulations, the solid filler of bar composition etc.If wish highly to bubble, can be with foam promotor such as C 10-C 16Alkylolamide mixes in the composition, and typical amounts is 1% to 10%.C 10-C 14The pure and mild diglycollic amide in unit can illustrate these foam promotors of a quasi-representative.With these foam promotors with highly bubble additional surfactants as previously mentioned amine oxide, trimethyl-glycine and Trolone to use also be useful.If desired, can add solubility magnesium salts such as MgCl with typical amounts 0.1% to 2% 2, MgSO 4Deng removing performance to produce more foams and to strengthen grease.
Used various cleaning ingredients can apply the further stabilization of method of said matrix then randomly by they being absorbed in the porous hydrophobic matrix in the present composition with hydrophobic coat.Be preferably in absorb cleaning ingredients in the porous matrix before, it is mixed with a kind of tensio-active agent.In use, cleaning ingredients discharges from matrix in the water washings of going forward side by side, and finishes its predetermined washing responsibility.
In order to illustrate in greater detail this technology, with a kind of porous hydrophobic silicon dioxide (trade mark is SIPERNAT D10, DeGussa) with contain 3%-5%C 13-15The protease of ethoxylated alcohol (EO7) nonionic surface active agent mixes.Typically, enzyme/surfactant soln is 2.5 times of silica weight.The gained powder is dispersed in (viscosity is at 500-12, and the various polysiloxane oils in 500 scopes all can use) in the polysiloxane oil with stirring means.With the dispersion liquid emulsification of gained polysiloxane oil or be added in the finished product detergent base.In this way; various compositions enzyme, SYNTHETIC OPTICAL WHITNER, bleach activator, bleaching catalyst, light activating agent, dyestuff, fluorescent substance, fabric regulator and hydrolyzable tensio-active agent as previously mentioned can be " protected " when comprising the liquid laundry cleaning composition when being used for washing composition.
Liquid detergent compositions can contain water and other solvent as carrier.Low-molecular-weight uncle or secondary alcohol for example methyl alcohol, ethanol, propyl alcohol and Virahol are suitable for.Single hydroxyl alcohol is preferred to surface of stability promoting agent, but also can use polyvalent alcohol for example contain 2 to about 6 carbon atoms and 2 polyvalent alcohols to about 6 hydroxyls (for example 1, ammediol, ethylene glycol, glycerol and 1,2-propylene glycol.Composition can contain 5% to 90%, typically these carriers of 10% to 50%.
Can prepare granulated detergent with for example spraying drying (the about 520g/l of the finished product density) or with the method for basic granules cohesion (the finished product density surpasses about 600g/l).Other dry ingredient for example can mixed in the drum tumbler with basic granules with particle or powder type then, liquid component (for example nonionic surface active agent and spices) then can spray up.
Cleaning composition of the present invention is preferably modulated to such an extent that make its washing water pH value in the water cleaning operation between about 6.5 and about 11, and about 7.5 to 10.5 is preferred.Liquid is washed the dish formula for a product and is preferably had about 6.8 to about 9.0 pH value.The typical pH of clothes washing product is at 9-11.PH is controlled at the technology of recommending usage level comprises use buffer reagent, alkali, acid etc., these technology are well known to those skilled in the art.
Following embodiment explanation is based on composition of the present invention, but is not thought of as the restriction into them.
Example I
A kind of dry laundry bleach is as follows: composition % (weight) SPC-D 20 benzoyl caprolactams 10 Citrate trianion 10Mn-catalyzer *0.2C 12-C 18Alkyl ethoxyquin (0.6) vitriol 12 oleoyl sarcosinates 12 water-soluble stopping composition *Surplus *U.S.Pat Nos 5,246,621 and 5,244,594 Mn that describe IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2 *Yellow soda ash, sodium silicate mixture (1: 1).
In above-mentioned composition, SPC-D can replace with the Sodium peroxoborate of equivalent.
In addition, in above-mentioned composition, bleach-activating agent can replace with the following activator of equivalent: benzoyl caprolactam, the benzoyl Valerolactim, the nonanoyl hexanolactam, the nonanoyl Valerolactim, 4-nitro-benzoyl caprolactam, 4-nitro-benzoyl Valerolactim, the decoyl hexanolactam, the decoyl Valerolactim, the caprinoyl hexanolactam, the caprinoyl Valerolactim, undecylene acyl hexanolactam, undecylene acyl Valerolactim, 3,5,5-trimethyl acetyl hexanolactam, 3,5,5-trimethyl acetyl Valerolactim, the dinitrobenzene benzoyl caprolactam, dinitrobenzene carbamoyl pentyl lactan, the terephthaloyl dicaprolactam, terephthaloyl two Valerolactims, (6-decoylamide hexanoyl) oxygen benzene sulfonate, (6-pelargonamide hexanoyl) oxygen benzene sulfonate, (6-decyl amide hexanoyl) oxygen benzene sulfonate and their mixture.
The composition itself of embodiment 1 can be used as SYNTHETIC OPTICAL WHITNER, or is added to a kind of preimpregnation or contains in the cleaning composition of tensio-active agent to provide bleachability to them.
When being used for the fabric cleaning, composition uses with common mode and common concentration.For example, in a typical way, composition is placed aqueous phase liquid with the consumption of about 100ppm to about 10,000 and stir with the fabric of making dirty, what of dirt the consumption of composition depend on.
Example II
Prepare following liquid detergent compositions (mark is represented with weight) composition weight % oleoyl sarcosinates 9C 12-18Alkyl ethoxyquin (0.6) vitriol 12C 12-14N-methyl glucose amide 6C 9-11Alkyl ethoxylates (eo=8) 3C 12-20Aliphatic acid 4 citric acids 0.5 percarbonate 5 nonanoyl caprolactams 5 proteinase-10 .5 lipase 0.2 amylase 0.1 cellulose enzyme 0.1 blast agent 0.9 soil release polymers 0.2
Water and miscellany add as surplus
Above-mentioned composition can be with the further in addition modification of the method for specified bleaching catalyst in the example I that adds equivalent.
Above-mentioned composition can be by replacing the method for nonanoyl hexanolactam to carry out modification with specified SYNTHETIC OPTICAL WHITNER in the equivalent example I.
EXAMPLE III
Preparation contains a kind of bleach system that following composition can be used as the SYNTHETIC OPTICAL WHITNER additive.Composition weight % nonanoyl Valerolactim 15 SPC-D *25 ethylene diamine disuccinate sequestrants, 10 oleoyl sarcosinates, 25 minor constituents, filler *Add to 100% with water *400 to 1200 microns of mean particle sizes *Optional material such as the CaCO of making things convenient for 3, talcum, clay, silicate etc.
Above-mentioned composition can carry out modification with the method that adds lipase.
Above-mentioned composition also can be by replacing the nonanoyl Valerolactim and/or adding the in addition modification of method of 0.1% metal catalyst with the specified activator of bleaching agent of equivalent example I.
Above-mentioned composition also can be by replacing the method change of percarbonic acid with the equivalent Sodium peroxoborate.
EXAMPLE IV
Prepare the block scouring agent that contains SYNTHETIC OPTICAL WHITNER with the standard extrusion molding, it contains: oleoyl sarcosinates (20%); Three sodium polyphosphates (20%); Water glass (7%); Monohydrate sodium stannate (10%); (6-decyl amide hexanoyl) oxygen benzene sulfonate (10%); (1.0%); MgSO 4Or talc filler; And water (5%).
Above-mentioned composition can be with in addition modification of the method that adds lipase.
Above-mentioned composition also can replace (6-decyl amide hexanoyl) oxygen benzene sulfonate activator of bleaching agent and/or add the in addition modification of method of 0.1% metal catalyst by specified activator of bleaching agent in the example I with equivalent.
Above-mentioned composition also can be by replacing the method change of perborate with percarbonate.
EXAMPLE V
A kind of to wash the dish composition automatically as follows: composition % (weight) oleoyl sarcosinates 6 trisodium citrates 15 yellow soda ash 20 silicate 19 nonionic surface active agent 23 sodium polyacrylates (m.w.4000) 35 end amyl group (Termamyl) enzymes (60T), 1.1 husky fragrant enzymes (12T), 3.0 monohydrate sodium stannates, 10 benzoyl caprolactam 2Mn catalyzer 40.03 minor constituent surplus 1.BRITESLL, PQ Corporation2. polyethylene/polypropylene oxides is hanged down whipping agent 3.ACCUSOL, and the mol ratio of Rohm and Haas4.Mn positively charged ion and part is 1: 1 and the on-the-spot Mn of generation IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2
In above-mentioned composition, Sodium peroxoborate can replace with the SPC-D of equivalent.
In above-mentioned composition, bleaching catalyst can replace with specified pre-formation bleaching catalyst in equivalent such as the example I, or replaces to form specified bleaching catalyst in the example I with metallic cation and part.
Above-mentioned composition also can be by replacing benzoyl caprolactam to come change with specified bleach-activating agent in the equivalent example I.
In above-mentioned composition, tensio-active agent can replace with any low-foaming honionic surfactant of equivalent.Example comprises the Plurafac that low foam or non-foam ethoxylated linear alcohols such as Eurane Co. provide TMRA series, the Lutensol that BASF Co. provides TMLF series, Rohm ﹠amp; The Triton that Haas Co. provides TMThe Synperonic that DF series and ICI Co provide TMLF series.
Automatically wash the shape that the dish composition can be particle, sheet, bar or rinse aid.The method for preparing particle, sheet, bar or rinse aid is for known to the present technique field.Can be referring to for example, U.S.Pat.Serial Nos.08/106,022,08/147,222,08/147,224,08/147,219,08/052,860,07/867,941.
All above-mentioned particulate compositions can provide with spray-dried granules or high-density (more than the 600g/l) particle or aggregate.If desired, can be adsorbed on the Mn-catalyzer on the water-soluble granular or, thereby additional stability in storage is provided wherein so that catalyzer leaves composition equilibrated.These particles (they should not contain oxidable composition) for example can contain water-soluble silicate, carbonate etc.
Though above-mentioned composition is the typical case of useful composition of the present invention, most preferably: (1) composition does not contain the STPP washing assistant, (2) nonionic: the anion surfactant ratio was greater than 1: 1, and be preferred at least 1.5: 1; (3) exist 1% perborate or other to contain chlorine scavenger in the composition at least, so that form minimum MnO when using 2
Though the foregoing description has been set forth present technique for laundry with wash dish and use use in the cleaning/bleaching composition that designs, those skilled in the art wish that catalytically bleaching system of the present invention can improve all can using in any case of oxygen bleaching performance at needs.For example, the technology of the present invention can be used to bleached pulp, and the bleaching hair cleans and sterilizes repairing device such as artificial tooth, is used for tooth paste product with cleaning teeth and kill oral cavity bacterium, and other bleaching situation useful to the user.

Claims (13)

1. bleaching composition, it contains a kind of bleaching compounds and oleoyl sarcosine salt surfactant that hydrogen peroxide can be provided in waterborne liquid.
2. according to a kind of bleaching composition of claim 1, wherein said oleoyl sarcosine salts contg is 0.1% of bleaching composition weight at least.
3. according to a kind of bleaching composition of claim 1, it also contains one or more bleach-activating agents, and wherein said bleach-activating agent is selected from following one group of material:
A) alkyloyl oxygen benzene sulfonate bleach-activating agent;
B) tetra acetyl ethylene diamine;
C) the following a kind of acid amides of the general formula bleach-activating agent of deriving: Perhaps their mixture, wherein R 1Be alkyl, aryl or the alkaryl that contains 1 to 14 carbon atom, R 2Be alkylidene group, arylidene or the alkyl arylene that contains 1 to 14 carbon atom, R 5Be H or alkyl, aryl or the alkaryl that contains 1 to 10 carbon atom, L is a leavings group;
D) the following a kind of benzoxazine type bleach-activating agent of structural formula:
Figure A9519443200022
R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, wherein R 2, R 3, R 4And R 5Be be selected from H, halogen, alkyl, thiazolinyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino ,-COOR 6Identical or different substituting group, R wherein 6Be H or alkyl and carbonyl functional group;
C) the following N-acyl lactam of structural formula:
Figure A9519443200023
Wherein n is by 0 to 8, and is preferred 0 to 2, R 6Be H, contain alkyl, aryl, alkoxy aromatic yl or the alkaryl of 1 to 12 carbon atom, or contain the substituted-phenyl of 6 to 18 carbon atoms; With
, b) and mixture c) d) a).
4. according to a kind of bleaching composition of claim 3, wherein said bleaching compounds is percarbonate or perborate, or their mixture, wherein said bleach-activating agent is selected from benzoyl caprolactam, the benzoyl Valerolactim, the nonanoyl hexanolactam, the nonanoyl Valerolactim, 4-oil of mirbane formyl hexanolactam, 4-oil of mirbane formyl Valerolactim, the decoyl hexanolactam, the decoyl Valerolactim, the caprinoyl hexanolactam, the caprinoyl Valerolactim, undecylene acyl hexanolactam, undecylene acyl Valerolactim, 3,5,5-trimethyl acetyl hexanolactam, 3,5,5-trimethyl acetyl Valerolactim, the dinitrobenzene benzoyl caprolactam, dinitrobenzene carbamoyl pentyl lactan, paraphenylene terephthalamide's dicaprolactam, paraphenylene terephthalamide's two Valerolactims, (6-decoylamide hexanoyl) oxygen benzene sulfonate, (6-pelargonamide hexanoyl) oxygen benzene sulfonate.(6-decyl amide hexanoyl) oxygen benzene sulfonate, nonanoyl oxygen benzene sulfonate, benzoyl oxygen benzene sulfonate, tetraacetyl ethylene diamine and their mixture.
5. according to a kind of cleaning composition of claim 1, it also contains one or more bleaching catalysts of catalytically effective amount.
6. according to a kind of cleaning composition of claim 4, it also contains one or more bleaching catalysts of catalytically effective amount.
7. according to a kind of composition of claim 5, wherein bleaching catalyst is selected from Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2Mn III 2(u-O) 1(u-OAc) 2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 2Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4(ClO 4) 4Mn IIIMn IV 4(u-O) 1(u-OAc) 2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 3Mn IV(1,4,7-trimethylammonium-1,4,7-three azepines-cyclononane (OCH 3) (PF 6)); Co (2,2 '-two pyridine amine) Cl 2Two (isothiocyanato) two pyridine amine-cobalts (II); Three or two pyridine amine-cobalt (II) perchlorate; Co (2,2-two pyridine amine) 2O 2ClO 4Two-(2,2 '-two pyridine amine) copper (II) perchlorate; Three (two-2-pyridine amine) iron (II) perchlorate; Managanese gluconate; Mn (CF 3SO 3) 2Co (NH 3) 5Cl; The double-core Mn that cooperates with four-N coordination and two-N ligand comprises N 4Mn III(u-O) 2-Mn IVN 4) +(Bipy 2Mn III(u-O) 2Mn IVBipy 2)-(ClO 4) 3With their mixture.
8. clothes washing composition, it contains other detergent surfactant, other cleaning ingredients and according to a kind of bleaching composition of claim 1.
9. clothes washing composition, it contains other detergent surfactant, other cleaning ingredients and according to a kind of bleaching composition of claim 4.
10. method of improving the bleaching composition bleachability, bleaching composition contains oxygen or peracid SYNTHETIC OPTICAL WHITNER or a kind of bleaching compounds that can produce hydrogen peroxide in waterborne liquid, and wherein said improvement comprises the oleoyl sarcosine salt surfactant that adds significant quantity in composition.
11. one kind is got on except that the method for spot by fabric or sulphur dish, it comprises said fabric or bowl dish is contacted with the aqueous media that contains a kind of bleaching composition according to claim 1.
12. one kind is got on except that the method for spot by fabric or sulphur dish, it comprises said fabric or bowl dish is contacted with the aqueous media that contains a kind of bleaching composition according to claim 4.
13. a bleaching composition, it contains preformed peracid bleaching compounds and oleoyl sarcosine salt surfactant.
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GB201117252D0 (en) * 2011-10-06 2011-11-16 Croda Int Plc Improved treatment of hard surfaces
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BR9507831A (en) 1997-09-16
EP0763096A1 (en) 1997-03-19
ZA954278B (en) 1996-01-24
AU2517795A (en) 1995-12-21
DE69513974D1 (en) 2000-01-20
IL113880A0 (en) 1995-08-31
WO1995033043A1 (en) 1995-12-07
MA23569A1 (en) 1995-12-31
ATE187766T1 (en) 2000-01-15
JPH10501566A (en) 1998-02-10
EP0763096B1 (en) 1999-12-15

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