CN1333814A - Bleaching compositions - Google Patents
Bleaching compositions Download PDFInfo
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- CN1333814A CN1333814A CN99815482.2A CN99815482A CN1333814A CN 1333814 A CN1333814 A CN 1333814A CN 99815482 A CN99815482 A CN 99815482A CN 1333814 A CN1333814 A CN 1333814A
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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
- C11D3/3945—Organic per-compounds
Abstract
The present invention relates to a bleaching comprising a pre-formed peroxy carboxylic acid raw material and bleaching compositions comprising same. These compositions are suitable to deliver improved bleaching performance whilst also being safe to colour and fabric. Furthermore the compositions herein are also chemically and physically stable upon prolonged periods of storage time.
Description
Technical field
The bleaching composition that the present invention relates to can be used for to bleach the pre-formation percarboxylic acids on various surfaces and contain described percarboxylic acids, wherein said surface include, but is not limited to crust and fabric, clothing, carpet etc.
Background of the present invention
The common liquid aqueous bleaching compositions that is applicable to bleached woven fabric and crust stain is with halogen bleaching agent, and particularly hypochlorite bleaching is the basis.Halogen bleaching agent is very effective SYNTHETIC OPTICAL WHITNER, yet also there are many shortcomings in they, and these shortcomings hinder the human consumer sometimes and select halogen-containing product.For example halogen bleaching agent, particularly chlorine bleach in use with after using discharge the smell (as to human consumer's hand and/or with the surface of its processing) of stimulation, and some human consumers are not felt well.
In addition, the composition (being generally hypochlorite) that is known in the art halogen-containing SYNTHETIC OPTICAL WHITNER has in higher concentration and/or when using repeatedly strong aggressive and can damage to fabric.Particularly, the human consumer can be observed the destruction (as the forfeiture of tensile strength) of fabric itself or the destruction of fabric color intensity.Though can farthest reduce destruction by adopting relatively mild oxygen bleaching agent such as hydrogen peroxide, yet the bleachability of these peroxygen bleachs is very different than those halogen bleaching agents to color and fabric.Therefore, people have developed the liquid aqueous composition that contains active peroxygen bleach, and it contains activator, promptly strengthens the compound of peroxide bleaching performance.But the performance of these SYNTHETIC OPTICAL WHITNER aspect the stain removal is not as the hypohalite SYNTHETIC OPTICAL WHITNER.
Therefore a target of the present invention provides a kind of bleaching raw material and a kind of bleaching composition, this bleaching composition not only can effectively transmit bleachability in laundry applications and/or any household application (as bleaching/disinfecting hard surfaces), and also is safe for treated surface (as fabric itself and/or fabric pigment).
The proneness that particular problem is the chemical instability of described bleaching raw material that when the preparation bleaching composition, runs into, particularly like this in the period of storage that prolongs.Therefore further target of the present invention provides and can effectively transmit bleachability, and keeps chemically stable bleaching raw material and bleaching composition in prolonging period of storage.
Raw material of the present invention and composition can be used in any laundry applications, as cloth-washing detergent or laundry additive with as the laundry pretreating agent.A special advantage of the present composition is that they are applicable to the dissimilar fabric of bleaching, comprise natural fabric (as the fabric of making by cotton and flax), synthetic textiles as by the synthetic source polymer fiber (as the fabric of polymeric amide-elasthane) make and by the natural fabric made from synthon.For example, the present invention's bleaching composition herein can be used for synthetic textiles, although the prejudice that exists opposes to use SYNTHETIC OPTICAL WHITNER on synthetic textiles, as clothes label and commodity bleaching composition (as containing the composition of hypochlorite) warning.
Another advantage of bleaching composition of the present invention is that they can use under various conditions, promptly uses in hard water and soft water and under pure state (neat) or diluting condition.More specifically, we found liquid aqueous composition of the present invention preferably with they dilute form in any application, in the laundry applications of any routine, use especially.Really, (be diluted to 20 milliliters/liter or lower concentration (composition: water)) usually, the acidity of composition of the present invention diminishes, and becomes about 6.5 or bigger as pH by about 1.5 when dilution.Although composition of the present invention can effectively transmit bleachability under pure form, their dilute form still shows wonderful further enhanced bleachability.In fact, this " pH hop " effect can be used for preparing acid liquid aqueous composition (be pH less than 7, preferably less than 3, be more preferably less than 2), they keep physics and chemically stable in prolonging period of storage, and transmit outstanding bleachability under the working conditions of dilution.
It is that they also have effective stain removal performance to the various stains that comprise enzyme stain and/or grease stain that the present composition also has another advantage.
The present invention's general introduction
The invention provides a kind of pre-formation percarboxylic acids raw material of 5% impurity of the weight that contains no more than described raw material.
The present invention further comprises the bleaching composition that contains described raw material.
The present invention describes preformed percarboxylic acids in detail
The raw material that is specially adapted to bleaching composition that preformed percarboxylic acids (peracid hereinafter referred to as) is known in the art.Term " raw material " is interpreted as being used in for example component in the bleaching composition of other article of preparation.
The most frequently used method for preparing peracid is by making carboxylic acid and the hydroperoxidation corresponding to described peracid under strong acidic condition.The reaction product that obtains during equilibrium establishment is described peracid.We believe the decomposition that exists impurity will impel described peracid in reaction product.Term used herein " impurity " does not comprise water.We also believe be beneficial to as having of reagent (being carboxylic acid and/or hydroperoxidation agent) as described in the decomposition of peracid.In addition, we find that the existence of carboxylic acid has promoted the dissolving of peracid in aqueous solution when the peracid preparation of raw material is become aqueous composition, and it further impels the decomposition of described peracid again.The applicant finds can reduce by the amount that is limited in impurity in the described raw material peracid decomposition of described peracid.With regard to the object of the invention, the amount of the impurity in described raw material percarboxylic acids no more than 5%, preferred no more than 3%.The ratio of percarboxylic acids and impurity is greater than 19, more preferably greater than 32.
Preferred used peracid is water-insoluble substantially solid.
Have following general formula at peracid described in the embodiment preferred of the present invention:
R is that linear or branched alkyl chain and the X with at least 1 carbon atom is hydrogen or is selected from following substituting group: phthalyl amido, imide, hydroxide radical, sulphur root, sulfate radical, sulfonate radical, carboxylate radical, heterocycle, nitrate radical, aldehyde, phosphonate radical, phosphine or their mixture of alkyl (alkyl chain that particularly has 1 to 24 carbon atom), aryl, halogen, ester, ether, amine, acid amides, replacement in X-R-C (O) the OOH formula.
More particularly, preferred described R base contains 2 to 24 carbon atoms.Perhaps described R base can be the branched alkyl chain that contains one or more side chains, and wherein said side chain contains and is selected from following substituting group: the phthalyl amido of aryl, halogen, ester, ether, amine, acid amides, replacement, imide, hydroxide radical, sulphur root, sulfate radical, sulfonate radical, carboxyl, heterocycle, nitrate radical, aldehyde, ketone or their mixture.
In preferred peracid, be phthalimide-based according to the X group of above general formula.Therefore, particularly preferred peracid has the compound of following general formula for those:
R is that alkyl and A, B, C and the D of C1-20 independently are hydrogen or the substituting group that is selected from alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyano group, carboxyl, sulfate radical, sulfonate radical, aldehyde or their mixture separately in the formula.
In preferred aspects of the invention, R has 3 to 12 carbon atoms, the more preferably alkyl of 5 to 9 carbon atoms.Preferred substituted A, B, C and D are the alkyl with linear or branching of 1 to 5 carbon atom, but more preferably hydrogen.
Preferred peracid is selected from phthalic diamide and crosses acid (its another kind of expression formula is phthaloyl amido-peroxy caproic acid), phthalic diamide and cross that enanthic acid, phthalic diamide are sad excessively, phthalic diamide is crossed n-nonanoic acid, phthalic diamide is crossed capric acid and composition thereof.
Even preferred peracid is any peracid with following general formula:
To be selected from the alkyl of C1-4 and n be 1 to 5 integer to R in the formula.
Of the present invention particularly preferred aspect, described peracid has wherein that R is CH
2With n be 5 formula, promptly phthalic diamide is crossed caproic acid or PAP.
Preferred described peracid uses and can derive from the commodity of Ausimont Euroco by name with the form of basic water-insoluble solid or wet piece.
The content of described peracid in described composition is 0.1% to 10%, more preferably 0.5% to 8% and most preferably 1% to 6%.Perhaps described peracid can exist as 10% to 40%, more preferably 15% to 30%, most preferably 15% to 25% much higher content.Bleaching composition
The invention still further relates to the bleaching composition that contains percarboxylic acids raw material described herein.
Preferred composition of the present invention is a liquid, preferably contain water and preferred aqueous amount and be described bleaching composition weight 10% to 99%, more preferably 50% to 98%.Composition of the present invention has the pH value less than 7.The pH value of preferred composition of the present invention is 0.1 to 6.5, more preferably 0.5 to 5, even more preferably 2 to 4.Preparation composition of the present invention is crucial for the chemical stability of the present composition in the acid ph value scope.The pH value of preferred described composition is lower than the pKa value of used peracid.We think that acid ph value is controlled/limited in acidic medium and form unsettled high reactivity material when storing, and therefore help the stability of composition in the storage period that prolongs.
Can regulate the pH value of described composition with acidity known to those skilled in the art or alkaline matter.The example that is applicable to acidic substance herein is organic acid (as citric acid) and mineral acid (as sulfuric acid), sulfonic acid and/or methylsulfonic acid.The example of alkaline matter is sodium hydroxide, potassium hydroxide and/or yellow soda ash.
The bleachability of this composition can be assessed by following testing method to dissimilar bleaching stains.
The suitable testing method of under diluting condition the bleachability of dirty fabric being assessed is as follows: generally composition of the present invention is diluted with water to the 1-100 milliliter/liter, preferred 20 milliliters/liter (composition: dilution level water) is immersed in dirty fabric wherein 20 minutes then to 6 hours and with post rinsing.Perhaps, described bleaching composition can the 1-100 milliliter/and liter (composition: general dilution level water) is used for washing machine.In washing machine, washing is described dirty fabric 10-100 minute under 30-70 ℃ temperature, rinsing then.In this compare test, the reference group compound is carried out identical processing.Various having can be available from E.M.C.Co.Inc. as the dirty fabric/soiled cotton of spots such as tea, coffee.
By being compared side by side, the dirty fabric that adopts composition of the present invention and object of reference (as same composition but do not contain SYNTHETIC OPTICAL WHITNER or contain other SYNTHETIC OPTICAL WHITNER) to handle estimates bleachability then.Available range estimation ranking method is specified the difference of 0-4 scope group unit (psu).
An advantage of the present composition is that they keep physics and chemically stable in the storage period that prolongs.
Can behind the described composition of preparation, estimate the chemical stability of composition herein by the concentration of in given period of storage, measuring available oxygen.Term " chemical stability " is meant that the composition that contains peracid of the present invention does not have greater than 15% in following 10 days at 35 ℃, preferably is not more than 10% AvO loss herein.
Can after adopting the l ferrous ammonium sulfate solution reduction, measure the loss that includes the available oxygen (AvO) of the composition of peracid in for some time by adopting permanganate titration.This stability test method is known in the art and as Curox
RTechnical intelligence volume (available from Interox) in report.Perhaps, also can adopt the chromatography of in document, describing (F.Di Furia etc., the gas-liquid chromatography of measurement peracid, Analyst, the 113rd volume, in May, 1988,793-795 page or leaf) to measure acid concentration about peracid.
Term " physically stable " is meant that composition of the present invention storage under 50 ℃ did not occur being separated in 7 days herein.Optional components
Compositions herein also can contain various other optional components such as tensio-active agent, sequestrant, free-radical scavengers, oxidation inhibitor, stablizer, washing assistant, stain suspension polymer, polymerization stain releasing agent, pH control agent, dye transfer inhibitor, solvent, Foam Control, suds booster, whitening agent, spices, pigment, dyestuff etc.Tensio-active agent
The present composition can contain tensio-active agent or surfactant mixtures, and it is selected from nonionogenic tenside, anion surfactant, cats product, zwitterionics and/or amphoterics.
Composition of the present invention can contain 0.01% to 50%, preferred 0.1% to 30% and more preferably 0.2% to 10% tensio-active agent or its mixture that accounts for its gross weight.
Be applicable to that the anion surfactant of composition comprises formula ROSO herein
3The water-soluble salt of M or acid, wherein preferred R is C
10-C
24Alkyl preferably has C
10-C
20The alkyl of moieties or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, as alkali metal cation (as sodium, potassium, lithium), ammonium or replace ammonium (as methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion with derived from the quaternary ammonium cation of alkylamine such as ethamine, diethylamine, triethylamine and composition thereof etc.).Common C
12-C
16Alkyl chain be preferred for cold washing (as being lower than about 50 ℃), C
16-C
18Alkyl chain is preferred for high-temperature wash (as being higher than about 50 ℃).
Other anion surfactant that is fit to that is used for herein is formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is unsubstituted C
10-C
24Alkyl or have C
10-C
24The hydroxyalkyl of moieties, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are the ethoxy or the third oxygen unit, and m is greater than zero, be generally about 0.5 to about 6, more preferably about 0.5 to about 3, M is H or positively charged ion, described positively charged ion can be as metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), the ammonium cation of ammonium or replacement.Can consider to use alkyl ethoxylated sulfate and alkyl propoxylated sulphates herein.The object lesson that replaces ammonium cation comprise methyl-, dimethyl-, trimethylammonium-ammonium and quaternary ammonium cation such as tetramethyl-ammonium, lupetidine and derived from the positively charged ion of alkanolamine such as ethamine, diethylamine, triethylamine, its mixture etc.Exemplary tensio-active agent is C
12-C
18Alkyl polyethoxylated (1.0) vitriol, C
12-C
18E (1.0) M), C
12-C
18Alkyl gathers ethoxyquin (2.25) vitriol, C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylated (3.0) vitriol C
12-C
18E (3.0) and C
12-C
18Alkyl polyethoxylated (4.0) vitriol C
12-C
18E (4.0) M), wherein M conveniently is selected from sodium and potassium.
The anion surfactant that is used for other particularly suitable herein is an alkylsulfonate, comprises formula RSO
3The water-soluble salt of M or acid, wherein R is C
6-C
22Straight or branched, saturated or unsaturated alkyl, preferred C
12-C
18Alkyl, and more preferably C
14-C
16Alkyl, M is H or positively charged ion such as alkali metal cation (as sodium, potassium, lithium), or ammonium or replace ammonium (as methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion and derived from the quaternary ammonium cation of alkylamine such as ethamine, diethylamine, triethylamine and composition thereof etc.).
The alkylaryl sulphonate that is fit to that is used for herein comprises formula RSO
3The water-soluble salt of M or acid, R is an aryl in the formula, preferably by C
6-C
22Straight or branched, saturated or undersaturated alkyl, preferred C
12-C
18Alkyl, more preferably C
14-C
16The benzyl that alkyl replaces, M be H or positively charged ion such as alkali metal cation (as sodium, potassium, lithium, calcium, magnesium etc.) or ammonium or replace ammonium (as methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion and derived from the quaternary ammonium cation of alkylamine such as ethamine, diethylamine, triethylamine and composition thereof etc.).
The alkylsulfonate and the alkylaryl sulphonate that are used for herein comprise primary and secondary alkylsulfonate and primary and secondary alkylaryl sulphonate.Term " secondary C herein
6-C
22Alkyl or C
6-C
22Alkylaryl sulphonate " be meant as formula defined above in, SO
3M or aryl-SO
3The M group links to each other with the carbon atom of alkyl chain, and this carbon atom is between two other carbon atoms of described alkyl chain (secondary carbon(atom)).
C for example
14-C
16Alkylsulfonate can be available from the Hostapur by name of Hoechst
The commodity of SAS, C
8-mersolates is available from the Witconate NAS 8 by name of Witco SA
Commodity.The example of commodity alkylaryl sulphonate is the lauryl arylsulphonate that derives from Su.Ma.Particularly preferred alkylaryl sulphonate is available from Albright﹠amp; The Nansa by name of Wilson
The alkylbenzene sulfonate of commodity.
Other anion surfactant that is used for the decontamination purpose also can be used for herein.They can comprise soap salt (comprise as the ammonium salt of sodium, potassium, ammonium and replacement as one, two and triethanolamine salt), C
8-C
24Alkene sulfonate, the sulfonation poly carboxylic acid (as british patent specification the 1st, 082, the description in No. 179), the C that carry out sulfonation preparation by pyrolysis product to alkali earth salt
8-C
24Alkyl polyglycol ether sulfate (containing 10 moles oxyethane at the most); Alkyl ester sulfonate such as C
14-C
16Methyl ester sulfonate; Acylglycerol sulfonate, fatty oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, alkane belong to sulfonate, alkylphosphonic, isethionate such as acyl-hydroxyethyl sulfonate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (particularly saturated and undersaturated C
12-C
18Monoesters), sulfosuccinate diester (particularly saturated and undersaturated C
6-C
14Diester), the vitriol of the vitriol of alkyl polysaccharide such as alkyl polyglucoside (nonionic non-sulfuric acid compound described below), the primary alkyl sulphates of side chain, the many ethoxy carboxylates of alkyl are suc as formula RO (CH
2CH
2O)
kCH
2COO
-M
+Those materials, wherein R is C
8-C
22Alkyl, k are the integer of 0-10, and M is soluble salt-forming cation.Resinous acid and hydrogenated resin acid also are suitable for, as rosin, staybelite, be present in the Yatall MA or derived from the resinous acid and the hydrogenated resin acid of Yatall MA.In " tensio-active agent and washing composition " (I volume and II volume, Schwartz, Perry and Berch), provided other example.Various these class tensio-active agents mainly walk in 29 hurdles, 23 row open (being combined in this by reference) on the 23rd hurdle 58 of the United States Patent (USP) 3,929,678 of mandate on December 30th, 1975 people such as Laughlin.
Other the particularly suitable anion surfactant that is used for herein is to have 4-24 on alkyl chain, preferred 8-18, the more preferably alkyl carboxylate of 8-16 carbon atom and alkyl alkoxy carboxylate salt, wherein said alkoxyl group is propoxy-and/or oxyethyl group, and preferably the alkoxide degree is 0.5-20, the oxyethyl group of preferred 5-15.The preferred alkyl alkoxy carboxylate salt that is used for herein is that lauryl ether 11 carboxylic acid sodium (are RO (C
2H
4O)
10-CH
2COONa, R=C
12-C
14), available from the Akyposoft by name of Kao Chemical Gbmh
The commodity of 100NV.
The amphoterics that is fit to that is used for herein comprises having following formula R
1R
2R
3The amine oxide of NO, R in the formula
1, R
2And R
3Independent separately for saturated replacement or do not replace, the hydrocarbon chain with 1-30 carbon atom of straight or branched.Amine oxide surfactant preferably used according to the invention is for having following formula R
1R
2R
3The amine oxide of NO, wherein R
1For containing 1-30, preferred 6-20, more preferably 8-16, the hydrocarbon chain of 8-12 carbon atom most preferably, and R wherein
2And R
3Independently for having 1-4 carbon atom, the replacement of preferred 1-3 carbon atom or not replacement, straight or branched hydrocarbon chain, more preferably methyl.R
1Can be saturated, replacement or unsubstituted straight or branched hydrocarbon chain.The amine oxide that is fit to that is used for herein is as natural C
8-C
10Amine oxide mixture and available from the C of Hoechst
12-C
16Amine oxide.
The zwitterionics that is fit to that is used for is herein containing cationic hydrophilic groups (being quaternary ammonium group) and anionic hydrophilic group with a part in the pH of broad value scope.Typical anionic hydrophilic group is carboxylate salt and sulfonate, although can use other group such as vitriol, phosphonate etc.The general formula of zwitterionics used herein is:
R
1-N
+(R
2) (R
3) R
4X
-R in the formula
1Be hydrophobic group; R
2Be hydrogen, C
1-C
6The C of alkyl, hydroxyalkyl or other replacement
1-C
6Alkyl; R
3Be C
1-C
6The C of alkyl, hydroxyalkyl or other replacement
1-C
6Alkyl, they also can with R
2Continuous formation has the ring texture of N, perhaps C
1-C
6Hydroxy-acid group or C
1-C
6Sulfonate groups; R
4Be the part that the cationic nitrogen atom is connected to hydrophilic radical, be generally alkylidene group, hydroxy alkylidene or contain the poly-alkoxy grp of 1-10 carbon atom; X is the hydrophilic radical of carboxylate salt or sulfonate.
Preferred hydrophobic group R
1Be aliphatic series or aromatics, saturated or unsaturated, replacement or unsubstituted hydrocarbon chain, they can contain the linking group just like amide group, ester group.More preferably R
1For containing 1-24, preferred 8-18, the more preferably alkyl of 10-16 carbon atom.Preferred these simple alkyl are the reasons owing to price and stability.But, hydrophobic group R
1Also can be formula R
a-C (O)-NH-(C (R
b)
2)
mAmide group, R wherein
aFor aliphatic series or aromatics, saturated or unsaturated, replacement or unsubstituted hydrocarbyl chain, preferably contain 8 to up to 20, preferably up to 18, more preferably up to the alkyl of 16 carbon atoms, R
bBe selected from hydrogen and hydroxyl, m is 1-4, preferred 2-3, and more preferably 3, at any (C (R
b)
2) part on have a no more than hydroxyl.
Preferred R
2Be hydrogen, or C
1-C
3Alkyl, more preferably methyl.Preferred R
3Be C
1-C
4Hydroxy-acid group or C
1-C
4Sulfonate groups, or C
1-C
3Alkyl, more preferably methyl.Preferred R
4Be (CH
2)
n, wherein n is 1-10, preferred 1-6, the more preferably integer of 1-3.
Some common example of trimethyl-glycine/sulfonation trimethyl-glycine are described in United States Patent (USP) the 2nd, 082, and 275,2,702,279 and 2,255, No. 082, be combined in this by reference.
The particularly suitable example of alkyl dimethyl trimethyl-glycine comprises cocounut oil-dimethyl betaine, lauryl dimethyl trimethyl-glycine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia) acetate, 2-(N-cocounut oil N, N-Dimethyl Ammonium) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, hexadecyl dimethyl betaine, stearyl dimethyl betaine.For example the coco dimethyl trimethyl-glycine is available from the Amonyl by name 265 of Seppic
Commodity.Lauryl betaine is available from Albright ﹠amp; The Empigen BB/L by name of Wilson
Commodity.
The example of amido betaine comprises cocamidopropyl ethyl trimethyl-glycine, cocamidopropyl betaine or C
10-C
14Fatty acyl amido propylene (hydrogenation propylene, hydropropylene) sultaine.C for example
10-C
14Fatty acyl amido propylene (hydrogenation propylene) sultaine is available from " the Varion CAS by name of Sherex Company
Sultaine " commodity.
Other example of trimethyl-glycine is the Mirataine H by name available from Rhone-Poulenc
2C-HA
Commodity lauryl-immino-dipropionate.
Be applicable to that herein cats product comprises the derivative of quaternary ammonium, Phosphonium, imidazoles and sulfonium compound.The cats product that is preferred for herein is a quaternary ammonium compound, one or two alkyl that wherein connects nitrogen is to have 6-30, preferred 10-25, more preferably saturated, the straight or branched alkyl of 12-20 carbon atom, and other alkyl that wherein links to each other (promptly three (when an alkyl during) or two (when two alkyl during) for described long chain hydrocarbon groups before this for a described long chain hydrocarbon groups before this with nitrogen) independently of one another for having 1-4 carbon atom, the replacement of preferred 1-3 carbon atom or not replacement, the alkyl chain of straight or branched, more preferably methyl.Be applicable to that preferred quaternary ammonium compound herein is the quaternary ammonium compound of achloride/non-halogen.The gegenion that is used for described quaternary ammonium compound is compatible with any persulphate, and is selected from Methylsulfate or metilsulfate etc.
The particularly preferred quaternary ammonium compound that is used for the present composition is QAE compound such as myristyl trimethylammonium vitriol, hexadecyl trimethylammonium vitriol and/or tallow trimethylammonium vitriol.These QAE compounds are available from Hoechst, perhaps available from Albright ﹠amp; The EMPIGEN CM by name of Wilson
Commodity.
In the middle of nonionogenic tenside, alkoxy-based non-ionic surface active agent and particularly ethoxylated non-ionic surface active agent are applicable to herein.The nonionogenic tenside that is preferably used as especially herein is end capped alkoxide nonionogenic tenside.
The end capped alkoxy-based non-ionic surface active agent that is fit to that is used for herein has formula:
R
1(O-CH
2-CH
2)
n-(OR
2)
m-O-R
3R in the formula
1Be C
8-C
24Straight or branched alkyl or alkenyl, aryl, alkaryl, preferred R
1Be C
8-C
18Alkyl or alkenyl, more preferably C
10-C
15Alkyl or alkenyl, even more preferably C
10-C
15Alkyl;
R in the formula
2Be C
1-C
10The straight or branched alkyl, preferred C
2-C
10The straight or branched alkyl;
R in the formula
3Be C
1-C
10Alkyl or alkenyl, preferred C
1-C
5Alkyl, more preferably methyl;
With n in the formula and m independently be 1-20, preferred 1-10, the more preferably integer of 1-5; Or its combination.
These tensio-active agents are available from the Plurafac by name of BASF
Commodity, available from the Genapol by name of HOECHST
Commodity or available from the Symperonic by name of ICI
Commodity.The preferred end-blocking nonionic of following formula alkoxy-based surface-active agent is the Genapol by name available from Hoechst
The commodity of L2.5NR and available from the Plurafac by name of BASF
Commodity.Suspension agent
The present composition can preferably contain suspension agent.Suspension agent is a kind of composition that adds especially in the present composition with the solid particulate components of the described composition that suspends.For the present invention, the suspension agent described PAP that is specially adapted to suspend.
The suspension agent that is fit to is known in the art.The example of suspension agent comprises gum-type polymkeric substance (as xanthan gum), polyvinyl alcohol and derivative, Mierocrystalline cellulose and derivative thereof and polycarboxylate polymer.
In particularly preferred embodiment of the present invention, suspension agent is selected from gum-type polymkeric substance or polycarboxylate polymer.
The gum-type polymkeric substance can be selected from derivative of polysaccharide hydrocolloids (hydrocolloids), xanthan gum, guar gum, succinoglucan glue, Mierocrystalline cellulose, above-mentioned any material and composition thereof.Of the present invention one preferred aspect, described gum-type polymkeric substance is the xanthan gum or derivatives thereof.
The concentration that exists of described glue type polymkeric substance is 0.01%-10%, more preferably 0.1%-3%.
Polycarboxylate polymer can be homopolymer or the multipolymer that is selected from following monomeric unit: vinylformic acid, methacrylic acid, toxilic acid, oxysuccinic acid, maleic anhydride.Preferred polycarboxylate polymer is the Carbopol available from BF Goodrich.The molecular weight ranges of the polymkeric substance that is fit to is 10000-100000000, most preferably 1000000-10000000.
The concentration that exists of preferred crosslinked polycarboxylate polymer is 0.01%-2%, and more preferably 0.01%-1% most preferably is 0.1%-0.8%.
In as the embodiment of selecting, described suspension agent comprises the combination of at least two kinds of polymkeric substance.In this embodiment, first kind of polymkeric substance is the gum-type polymkeric substance, and second kind is crosslinked polycarboxylate polymer.Described composition also can contain other polymkeric substance.
The gum-type polymkeric substance is 100 with the ratio of crosslinked polycarboxylate polymer: 1-1: 100, more preferably 1: 10-10: 1.Sequestrant
The present composition can contain sequestrant as the preferred optional component.The sequestrant that is fit to can be known to those skilled in the art any, for example be selected from aromatic chelating agent, quadrol N ' the N-disuccinic acid of phosphine acid salt chelator, aminocarboxylate sequestrant, other carboxy acid salt chelator, multifunctional replacement or its mixture.
Exist sequestrant to help further to strengthen the chemical stability of described composition.The ionic strength of composition also strengthens them thus at various lip-deep decontaminations and bleachability because sequestrant can improve herein, so it also may be that composition of the present invention is needed.
The suitable phosphine acid salt chelator that is used for herein can comprise basic metal ethane 1-hydroxyl diphosphonate (HEDP), alkylidene group poly-(alkylene phosphonic acids salt), and aminophosphonic acid salt compound (comprising that amino three (methylene phosphonic acids) (ATMP)), nitrilo propylidene phosphonate (NTP), quadrol butylidene phosphonate and diethylenetriamine pentylidene phosphonate (DTPMP).Described phosphonate compounds can acid form exist or exist with the form of the different cationic salt on their some or all acid functional groups.The preferred phosphine acid salt chelator that is used for herein is diethylenetriamine pentylidene phosphonate (DTPMP) and ethane 1-hydroxyl diphosphonate (HEDP).These phosphine acid salt chelators are available from the DEQUEST by name of Monsanto
Commodity.
The aromatic chelating agent of multifunctional replacement also can be used in the compositions herein.Be issued to people's such as Connor United States Patent (USP) 3,812,044 referring on May 21st, 1974.This compounds of preferred acid form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.
The biodegradable cheating agent that is preferred for herein is quadrol N, N '-disuccinic acid or its an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt or its mixture.Quadrol N, N '-disuccinic acid, particularly (S, S) isomer is described in detail in the United States Patent (USP) 4,704,233 in the 3 days November in 1987 of Hartman and Perkins.Quadrol N, N '-disuccinic acid are for example available from the ssEDDS by name of Palmer Research Laboratories
Commodity.
The suitable aminocarboxylate that is used for herein comprises edetate, diethylentriamine pentacetate, diethylentriamine pentacetate (DTPA), N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, ethanol-Diglycocol, trimethylenedinitrilo-tertraacetic acid (PDTA) and methylglycine oxalic acid (MGDA), they are all with the form of acid, or exist with the form of an alkali metal salt, ammonium salt, substituted ammonium salt.The particularly suitable aminocarboxylate that is used for herein is that diethylene triaminepentaacetic acid(DTPA), trimethylenedinitrilo-tertraacetic acid (PDTA) are (as the Trilon FS by name available from BASF
Commodity) and methylglycine oxalic acid (MGDA).
Other carboxy acid salt chelator who is used for herein comprises Whitfield's ointment, aspartic acid, L-glutamic acid, glycine, propanedioic acid or its mixture.
The sequestrant that another kind is used for herein has following formula:
R in the formula
1, R
2, R
3And R
4Independently be selected from-H, alkyl, alkoxyl group, aryl, aryloxy ,-Cl ,-Br ,-NO
2,-C (O) R ' and-SO
2R ", wherein R ' be selected from-H ,-OH, alkyl, alkoxyl group, aryl and aryloxy; R " be selected from alkyl, alkoxyl group, aryl and aryloxy; R
5, R
6, R
7And R
8Independently be selected from-H and alkyl.
The particularly preferred sequestrant that is used for herein is amino three (methylene phosphonic acids), diethylidene triamino pentaacetic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP) salt, 1-hydroxyl ethane diphosphonate, quadrol N, N '-disuccinic acid, and composition thereof.
General composition of the present invention comprises and accounts for 5% of described composition total weight at the most, preferred 0.01%-1.5%, the more preferably sequestrant of 0.01%-0.5% or its mixture.Free-radical scavengers
Composition of the present invention can contain free-radical scavengers or its mixture.
Be suitable for herein free-radical scavengers and comprise list and dihydroxy-benzene and their homologue, alkyl and aryl carboxylic acid salt and composition thereof of well-known replacement.These free-radical scavengerss that are preferred for herein comprise di-tert-butyl hydroxy toluene (BHT), quinhydrones, di-tert-butyl hydroquinone, single tertiary butylated hydroquinone, tertiary butyl hydroxyl anysole, phenylformic acid, toluic acid, catechol, tert-butyl catechol, benzylamine, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, gallic acid n-propyl or its mixture, highly preferred di-tert-butyl hydroxy toluene.These free-radical scavengerss such as N-propyl gallate ester can be available from the Nipanox S1 by name of Nipa Laboratories
Commodity.
When using free-radical scavengers, its amount generally is at most 10% of composition total weight, is preferably 0.001%-0.5% (weight).
Exist free-radical scavengers can help the chemical stability of bleaching composition of the present invention and the form of security of composition of the present invention (safety profile).Foam Control
Composition of the present invention also can comprise Foam Control such as 2-alkyl chain triacontanol or its mixture as the preferred optional component.Being specially adapted to of the present invention is to contain 6-16, the 2-alkyl chain triacontanol of preferred 8-12 carbon atom alkyl chain and terminal hydroxy group, and described alkyl chain is contained 1-10 at alpha position, preferred 2-8, more preferably the alkyl chain of 3-6 carbon atom replaces.These compounds that are fit to are for for example available from Isofol
Series is as Isofol
12 (2-butyl octanol) or Isofol
16 (2-hexyl decyl alcohol).
Other Foam Control can comprise basic metal (as sodium or potassium) lipid acid or its soap, and they contain has an appointment 8 to about 24, and preferred about 10 to about 20 carbon atoms.
Comprise that those lipid acid that use in the soapmaking can derive from the glyceryl ester of natural source such as plant or animal derived (as plam oil, cocounut oil, babassu oil, soybean oil, Viscotrol C, butter, whale oil, fish oil, butter, fat, lard and composition thereof).Lipid acid also can be by synthetic preparation (as by the oxidation of petroleum or by the preparation of Fischer-Tropsch method).
Can by direct saponification fat and oil or by in and the free fatty acids that in production method independently, prepares prepare alkali metal soap.Useful especially is sodium salt and sylvite derived from the fatty acid mixt of cocounut oil and butter, i.e. the soda soap of butter and cocounut oil and potash soap.
Use the term " butter " relevant at this, generally have about 2.5% C with fatty acid mixt
14, 29% C
16, 23% C
18, 2% physetoleic acid, 41.5% oleic acid and 3% linolic acid (listed first three planted and be saturated fatty acid) carbon chain length distribution.Other mixture with similar distribution is also included within the term butter as the lipid acid derived from various butter and lard.Also butter can be hardened (being hydrogenation) so that part or all of unsaturated fatty acids acid moieties is converted into the saturated fatty acid moieties.
When using term " cocounut oil " herein, it is meant fatty acid mixt, generally has about 8% C
8, 7% C
10, 48% C
12, 17% C
14, 9% C
16, 2% C
18, 7% oleic acid and 2% linolic acid (listed the first six planted and be saturated fatty acid) carbon chain length distribution.Other source with similar carbon chain length distribution is included in the term cocounut oil as palm-kernel oil and babassu oil.
The example polysiloxane and the silicon dioxide-poly-mixture of siloxanes of the Foam Control that other is fit to.Polysiloxane is represented by alkylating silicone materials usually, and uses the silicon-dioxide of form in small, broken bits, example that silicon-dioxide aerosol and silica xerogel and various types of water drain silica are arranged usually.These materials can particle form mix, wherein Foam Control preferably mix releasedly water-soluble or water-dispersion, do not have in the opacity carrier of surface-active detergent substantially.Perhaps described Foam Control can be dissolved in or be dispersed in the liquid vehicle and by being sprayed on one or more other components and use.
Preferred polysiloxane Foam Control is disclosed in people's such as Bartollota the United States Patent (USP) 3,933 672.The polysiloxane Foam Control that other useful especially Foam Control is a self-emulsifying, it is described among the German patent application DTOS2646126 that announced on April 28th, 1977.An example of this compound is the commodity DC-544 (silane oxygen-glycol copolymer) available from Dow Corning.
Particularly preferred polysiloxane Foam Control is described in common unsettled european patent application N ° 92201649.8.Described composition can comprise the polysiloxane/silica mixture that has made up pyrolysis method atresia silicon-dioxide such as AerosilR.
Particularly preferred Foam Control is the foam control system that comprises silicone oil and described 2-alkyl chain triacontanol mixture.
General composition herein can contain and accounts for 4% of described composition total weight at the most, preferred 0.1-1.5%, the most preferably Foam Control of 0.1-0.8% or its mixture.Stablizer
Composition of the present invention also can comprise 10% of the gross weight that accounts for described composition at the most, the formula HO-CR ' R of preferred 2%-4% "-alcohol of OH, R ' and R in the formula " independent be H or C
2-C
10Hydrocarbon chain and/or hydrocarbon ring.Preferably the alcohol according to this formula is propylene glycol.In fact we observe the chemical stability that these alcohol, particularly propylene glycol have generally also strengthened described composition.
Other stablizer such as inorganic stabilizers can be used for herein.The example of inorganic stabilizers comprises sodium stannate and various alkali metal phosphate, tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate as everyone knows.The stain suspension polymer
The present composition can further contain the suspension polymer that has a stain (as polyamine stain suspension polymer) as optional components.Can use any stain suspension polyamine polymer well known by persons skilled in the art at this.The polyamine polymer that is specially adapted to herein is the poly-alkoxylation polyamine.These materials can be represented with the molecule of the experience structure with following repeating unit easily:
The amine form and
R is an alkyl in the quaternized form formula, has 2-6 carbon atom usually; R
1Can be C
1-C
20Hydrocarbon; Described alkoxyl group is oxyethyl group, propoxy-etc., and y is 2-30, most preferably 10-20; N is at least 2, preferred 2-20, and the integer of 3-5 most preferably, X-is negatively charged ion such as halogenide or Methylsulfate (deriving from quaterisation).
The polyamine that most preferably is used for herein is so-called ethoxylation polyvinylamine, i.e. the polymeric reaction product of oxyethane and piperazine, and it has following general formula:
Y=2-30 in the formula.Be particularly preferred for herein be the ethoxylation polyvinylamine, particularly ethoxylation tetracthylene pentamine and quaternised ethoxylation inferior hexyl diamines.
Stain suspension polyamine polymer helps advantage of the present invention; when promptly except described diacyl peroxide, also adding described stain suspension polyamine polymer, further strengthened the detergency ability (particularly under the clothes washing pretreatment condition of describing) of the composition that contains them here.They have strengthened the detergency ability to various stains really, and these stains comprise grease stain, enzyme stain, clay/mud stain and the stain that can bleach.
Described composition generally comprises and accounts for 10% of its gross weight at the most, preferred 0.1%-5%, more preferably this stain suspension polyamine polymer or its mixture of 0.3%-2%.
Composition also can contain other polymerization stain releasing agent known to those skilled in the art herein.These polymerization stain releasing agents are characterised in that to have hydrophilic segment simultaneously (making hydrophobic fiber such as polyester and hydrophilic nylonization) and hydrophobic part (are deposited on the hydrophobic fiber, in finishing washing and rinse cycle, keep adhering to thereon, and serve as the anchoring group of hydrophilic segment thus).Can make like this in the stain after the stain release-agent-treated is easier to washing procedure in the back and be eliminated.
The polymerization stain releasing agent of Shi Yonging is particularly including the stain releasing agent with following feature herein: (a) one or more nonionic hydrophilic segments; Perhaps (b) one or more hydrophobic parts; Perhaps (a) and combination (b).Wherein (a) mainly is made up of following: (i) polymerization degree is at least 2 polyoxyethylene part, or (ii) the polymerization degree is propylene oxide or the polyoxypropylene part of 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless it is linked to each other with adjacent part by ehter bond at each end, perhaps (iii) comprise ethylene oxide and 1 mixture to the oxyalkylene units of about 30 propylene oxide units, wherein said mixture contains the ethylene oxide unit of capacity, like this when the stain releasing agent is deposited on the surface of normal polyester synthon, enough wetting abilities that has hydrophilic segment improve these surperficial wetting abilities, preferred described hydrophilic segment comprises the ethylene oxide unit at least about 25%, more preferably have about 20 to 30 propylene oxide units, ethylene oxide unit for these parts especially at least about 50%; Wherein (b) comprising: (i) C
3Oxyalkylene terephthalic acid ester moiety, if wherein described hydrophobic part also comprises the ethylene oxide terephthalate, ethylene oxide terephthalate: C then
3The ratio of oxyalkylene terephthalate units is about 2: 1 or lower, (ii) C
4-C
6Alkylidene group or oxygen C
4-C
6Alkylene moiety, or its mixture, (iii) the polymerization degree is at least poly-(vinyl acetate) part of 2, preferred polyvinyl acetate, perhaps (iv) C
1-C
4Alkyl oxide or C
4Hydroxyalkyl ether substituting group, or its mixture, wherein said substituent existence form is C
1-C
4Alkyl oxide or C
4Hydroxyalkyl ether derivatived cellulose, or its mixture, and these derivatived celluloses are amphiphilic substance, and they have enough C thus
1-C
4Alkyl oxide and/or C
4In a single day thereby the hydroxyalkyl ether unit deposits on the conventional polyethylene terephthalate surface and keeps the hydroxyl of enough concentration, can improve the wetting ability of fiber surface when consequently adhering on these conventional synthon surfaces.
General polyoxyethylene part (a) (i) has about 1 to about 200, preferred 3 to about 150, and more preferably 6 to about 100 the polymerization degree is although can adopt higher level.The oxygen C that is fit to
4-C
6The alkylidene group hydrophobic part includes, but is not limited to end capped polymerization stain releasing agent such as MO
3S (CH
2)
nOCH
2CH
2O-, M is a sodium in the formula, n is the integer (being issued to the description in the United States Patent (USP) 4,721,580 of Gosselink as on January 26th, 1988) of 4-6.
Be applicable to that polymerization stain releasing agent of the present invention also comprises the segmented copolymer of derivatived cellulose such as hydroxy ethers cellulose polymer compound, ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate etc.These reagent are that commodity can get, and comprise cellulosic hydroxy ethers such as METHOCEL (Dow).Being used for herein Mierocrystalline cellulose stain releasing agent also comprises and is selected from C
1-C
4Alkyl and C
4Those Mierocrystalline cellulose stain releasing agents of hydroxy alkyl cellulose; Be issued to people's such as Nicol United States Patent (USP) 4,000,093 referring on December 28th, 1976.
Stain releasing agent with poly-(vinyl acetate) hydrophobic part feature comprises that poly-(vinyl acetate) is (as C
1-C
6Vinyl acetate) graft copolymer, polyvinyl ester preferably are grafted to poly-(vinyl-acetic ester) on polyalkylene oxide backbone (as the polyethylene oxide) main chain.The european patent application 0219048 that is disclosed on April 22nd, 1987 referring to people such as Kud.The commodity of this stain releasing agent comprise the SOKALAN section bar material available from West Germany BASF, as SOKALAN HP-22.
The preferred stain releasing agent of one class is the statistic copolymer of ethylene glycol terephthalate and polyethylene oxide (PEO) terephthalate.The molecular weight of this polymerization stain releasing agent is about 25,000 to about 55,000.Be issued to the United States Patent (USP) 3,893,929 of Basadur on July 8th, 3,959,230 and 1975 referring to the United States Patent (USP) that was issued to Hays on May 25th, 1976.
Another kind of preferred polymerization stain releasing agent is the polyester with ethylene glycol terephthalate repeating unit, it contains the ethylene glycol terephthalate unit of 10-15% (weight) and the polyoxyethylene terephthalate units of 90-80% (weight) (derived from molecular-weight average is 300-5,000 polyoxyethylene dibasic alcohol).The example of this polymkeric substance comprises proprietary concentrate ZELCON 5126 (available from Du Pont) and MILEASE T (available from ICI).Also be issued to the United States Patent (USP) 4,702,857 of Gosselink referring on October 27th, 1987.
Another kind of preferred polymerization stain releasing agent is the sulfonated products of linear substantially ester oligomer, comprises paraphenylene terephthalamide and the oligomer ester main chain of oxyalkylene oxygen repeating unit and the terminal portions that links to each other with the main chain covalency.These stain releasing agents are issued in November 6 nineteen ninety in the United States Patent (USP) 4,968,451 of J.J.Scheibel and E.P.Gosselink and have done comprehensive description.Other polymerization stain releasing agent that is fit to comprises the United States Patent (USP) 4 that was issued to people such as Gosselink on December 8th, 1987,711, terephthalate polyester in 730, be issued to the United States Patent (USP) 4 of Gosselink on January 26th, 1988,721, end capped oligomer ester of negatively charged ion in 580 and the United States Patent (USP) 4 that was issued to Gosselink on October 27th, 1987, block polyester oligomeric compound in 702,857.
Preferred polymerization stain releasing agent also comprises the stain releasing agent in the United States Patent (USP) 4,877,896 that was issued to people such as Maldonado on October 31st, 1989, and it discloses negatively charged ion, the special end capped terephthalate of sulfonation aroyl.
The another kind of preferred stain releasing agent that also has is the oligopolymer with terephthaloyl unit between terephthaloyl unit, sulfonation, oxygen ethylidene oxygen and the unitary repeating unit of oxygen-propylene.Described repeating unit forms the main chain of described oligopolymer and preferably adopts modification hydroxyethylsulfonic acid ester terminal to carry out end-blocking.Preferred especially this class stain releasing agent comprises an about sulfonation isophthaloyl unit, 5 terephthaloyl unit, oxygen ethylidene oxygen and oxygen-1; 2-propylidene oxygen unit (ratio is about 1.7 to about 1.8), and two 2-(2-hydroxy ethoxy)-ethane sulfonic acid sodium end group unit.Described stain releasing agent also contains the reduction crystalline stablizer that accounts for oligopolymer weight about 0.5% to about 20%, is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and composition thereof.Be issued to people's such as Gosselink United States Patent (USP) 5,415,807 referring to May 16 nineteen ninety-five.
If you are using, described stain releasing agent mainly accounts for the 0.01%-10.0% of detergent composition weight herein, is generally 0.1%-5%, preferred 0.2%-3.0%.Dye transfer inhibitor
The present composition also can contain one or more and can effectively suppress dyestuff migrate to another surperficial material from a dyestuff surface in cleaning process.Usually these dye transfer inhibitors comprise multipolymer, manganese phthalocyanine, peroxidase of polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole and composition thereof.If use, these reagent generally account for the 0.01%-10% of described composition weight, preferred 0.01%-5%, more preferably 0.05%-2%.
More specifically, the polyamine N-oxide pllymers that is used for herein comprises having R-A
xThe unit of-P-structure formula; Wherein P can connect two unit for connecting the polymerizable unit of N-O group or part or N-O group that the N-O group can form polymerizable unit; A be in the following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or its any combination, and the nitrogen in the N-O group can be coupled, and perhaps the N-O group is the part of these groups.Preferred polyamine N-oxide compound is those compounds as the heterocyclic group of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and derivative thereof for the R group.
The N-O group can be represented by following universal architecture:
R in the formula
1, R
2, R
3Be aliphatic series, aromatics, heterocycle or alicyclic group or its combination; X, y and z are 0 or 1; Nitrogen in the N-O group can be connected or form the part of above-mentioned group.The unitary pKa of the amine oxide of described polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
Can use any main polymer chain, as long as the amine oxide polymers that forms is water-soluble and has the dye migration inhibition activity.The example of the main polymer chain that is fit to is polyethylene kind, polyolefine, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and composition thereof.These polymkeric substance comprise random or segmented copolymer, and wherein a class monomer is an amine n-oxide, and another kind of monomer is the N-oxide compound.The ratio of amine and amine n-oxide is generally 10 in the amine n-oxide polymkeric substance: 1-1: 1,000,000.Yet, can or change the number of the amine oxide group that is present in the polyamine oxide polymer by the N-oxidation of suitable degree by copolymerization suitably.Almost can obtain the polyamine oxide compound of any polymerization degree. the average molecular weight ranges is 500-1,000,000; More preferably 1,000-500,000; Most preferably 5,000-100,000. this class preferable material can be described as " PVNO ".The most preferred polyamine oxide compound that is used for detergent composition herein is poly-(4-vinylpridine-N-oxide compound), its molecular-weight average be about 50,000 and the ratio of amine and amine n-oxide be about 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being called " PVPVI " class) also is preferred for herein.Preferred PVPVI has 5,000-1,000,000, more preferably 5,000-200,000, most preferably 10,000-20,000 molecular-weight average (average molecular weight range according to people such as Barth at Chemical Analysis, the 113rd volume, scattering of light described in " modernism of polymer characterization " (its open part be attached to herein by reference) is determined) N-vinyl imidazole in the .PVPVI multipolymer and the mol ratio of N-vinyl pyrrolidone be generally 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1.These multipolymers can be straight or branched.
It is 5 that the present composition also can adopt molecular-weight average, 000-400, and 000, preferred 5,000-200,000, more preferably 5,000-50,000 Polyvinylpyrolidone (PVP) (" PVP ").PVP is that the technician of detergent applications is known; Referring to as EP-A-262,897 and EP-A-256,696 (being attached to herein by reference).It is 500-100 that the composition that contains PVP also can comprise molecular-weight average, 000, and preferred 1,000-10,000 polyoxyethylene glycol (" PEG ").The PEG that preferably transmits in washing soln is 2 with the ratio of PVP: 1-50: 1, more preferably 3: 1-10: 1 (in ppm).Suds booster
High if desired foam can add as C in the described in the past composition
10-C
16The suds booster of alkanolamide, add-on are generally the level of 1%-10%.C
10-C
14Monoethanolamine and diglycollic amide are the suds boosters of a quasi-representative.It also is favourable using this class suds booster with above-mentioned height bubble cosurfactant as amine oxide, trimethyl-glycine and sultaine.If desired, the magnesium salts of solubility such as MgCl
2, MgSO
4Deng the foam and the enhancing degrease performance that can add as the concentration of 0.1%-2% so that other to be provided.Whitening agent
When design composition of the present invention is used for fabric treating or when laundry, about 0.05% to about 1.2% the level that any brightening agent known in the art, white dyes or other brightening agent or whitening agent can generally account for cleaning composition weight herein adds in the composition of the present invention.Can be used for white dyes commodity of the present invention and can be divided into several subclass, include, but is not limited to 1,2-diphenyl ethylene derivatives, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines family (methinecyanines), dibenzothiophene-5,5-dioxide, pyrroles, 5-and 6-unit heterocycle whitening agent, listed just be used for explanation, but not be used for limiting.The example of these whitening agent is disclosed in " production of white dyes and application " (M.Zahradnik, John Wiley ﹠amp; Sons, NeW York (1982) publishes).
The object lesson that is used for the white dyes of composition of the present invention is to be issued to pointed those in the United States Patent (USP) 4,790,856 of Wixon on December 13rd, 1988.These whitening agent comprise the PHORWHITE series whitening agent available from Verona.Other whitening agent that is disclosed in this bibliography comprises: available from Tinopal UNPA, Tinopal CBS and Tinopal 5BM, the Tinopal PLC of Ciba-Geigy; Available from ArticWhite CC that is positioned at gondola Hilton-Davis and Artic White CWD; 2-(4-styryl-phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) biphenyl and aminocoumarin.The object lesson of these whitening agent comprises: 4-methyl-7-diethyl-aminocoumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho--[1, the 2-d1 triazole.Also be issued to the United States Patent (USP) 3,646,015 of Hamilton referring on February 29th, 1972.General herein preferred anionic whitening agent.The pH control agent
The pH value that can adopt various suitable materials to regulate (comprising organic acid or mineral acid, alkanolamine etc.) described composition.It is best using alkanolamine, particularly monoethanolamine, and they also have the additional effect of regulating emulsion viscosity in this scope, and do not influence its physical stability.Trace ingredients
Composition described herein also can comprise trace ingredients such as pigment or dyestuff and spices.The method of treat surface
In the present invention, aqueous solution composition of the present invention need be contacted with pending surface.
Term " surface " is meant any inanimate surfaces herein.These inanimate surfaces include, but is not limited to generally indoor as kitchen, bathroom or car in being seen crust such as ceramic tile, wall, floor, chromium, glass, level and smooth ethene, any kind of plastics, plasticizing wood, desktop, washtub, cooker cover, dish, sanitary facility such as washtub, shower, shower curtain, washtub, lavatory etc. and comprise that clothes, curtain, coverlet, bed linen, bath are with fabric and carpets such as fabric, tablecloth, sleeping bag, tent, ornament furnishings.Inanimate surfaces also comprises household supplies, includes, but is not limited to refrigerator, refrigerator, washing machine, automatic drier, electric furnace, microwave oven dishwasher etc.
Term " treat surface " is meant bleaching and/or sterilization (when the present composition comprises bleaching system based on peracid compound) and optional cleaning (when described composition can contain tensio-active agent or any other conventional sanitising agent) described surface herein.
Therefore, the present invention comprises that also processing, particularly bleached woven fabric are (as the method on lifeless surface.In this method, composition of the present invention is contacted with pending fabric.
Can so-called " pre-treatment pattern " carry out,, the liquid bleaching composition packed of definition is herein put on the described fabric with pure state wherein at rinse fabric or before washing then rinse fabric; Perhaps carry out with " immersion pattern ", wherein the liquid bleaching composition packed that at first will herein define dilutes in water-bath, before carrying out rinsing fabric is immersed and soaks in bath; Perhaps carry out, wherein except by dissolving or the liquid bleaching composition packed that defines that also adds of washings that disperses general cloth-washing detergent to form herein with " full washing mode ".In these situations, importantly before described composition parches fully, described fabric with should carry out rinsing after described composition contacts.
The effective whitening performance of method transmission on bleaching surface of the present invention (particularly fabric) and effective detergency ability.
Preferred composition of the present invention contacts with fabric with liquid form.The term in fact, here " liquid form " is meant the pure state of composition itself of the present invention or their dilute form.
Composition of the present invention is used in the middle of the laundry operations with dilute form usually.The term here " dilute form " is meant that the composition that is used for bleached woven fabric of the present invention can be diluted by user (preferred water).This dilution can be used for that hand washing is used and other method as in the machine washing.Described composition can be diluted to many 500 times, and preferred 5-200 times, more preferably 10-80 doubly.
More specifically, the method of bleached woven fabric of the present invention may further comprise the steps: described fabric is contacted with the bleaching composition of the present invention of dilute form, make described fabric and described composition keep in touch one (general 1-60 minute period that is enough to bleach described fabric then, preferred 5-30 minute), use the described fabric of water rinse then.If described fabric will wash with the conventional composition that comprises at least a tensio-active agent, can described washing and the described fabric of bleaching be carried out simultaneously by described fabric and bleaching composition of the present invention are contacted with described detergent composition, perhaps before or after the described fabric of bleaching, implement described washing.Therefore, method according to the present invention can bleached woven fabric and choose wantonly before making described fabric and step that described bleaching composition contacts and/or at described fabric with during described bleaching composition contacts and/or after described fabric and step that described bleaching composition contacts and before rinse step and/or after rinse step, adopt the detergent composition laundering of textile fabrics that comprises at least a tensio-active agent.
In another embodiment of the invention, the method of bleached woven fabric may further comprise the steps: the liquid bleaching composition packed of the present invention with pure state contacts with fabric, the time that described fabric and described bleaching composition keep in touch is enough to bleach described fabric (was generally 5 seconds to 30 minutes, preferred 1 minute to 10 minutes), use the described fabric of water rinse then.If laundering of textile fabrics, promptly with comprising that the conventional composition of at least a tensio-active agent washs described fabric, described washing can be carried out before or after the described fabric of bleaching.Advantageously the invention provides and a kind ofly can pure state be applied to the liquid bleaching composition packed of bleaching on the fabric, although the prejudice that exists opposes to use the composition that contains SYNTHETIC OPTICAL WHITNER of pure state on fabric, composition of the present invention is safe to color and fabric itself.
Perhaps after pure state bleaching process described above (pretreating agent application), do not adopt by with water rinse and/or with the conventional washing step of the conventional washing composition of liquid or powder, also can be after described bleaching pre-treatment in bucket (manual manipulation) or in washing machine, dilute bleaching method as described above.
Preferably after washing described fabric, implement bleaching process herein with conventional laundry detergent composition.We observe really and at first bleach then washing with described fabric and compare, after washing described fabric with detergent composition, bleach their (are commonly referred to as dilution bleaching process) with the present composition, uses the less energy and washing composition and the whiteness and the detergency ability of excellence are provided.
Another embodiment of the invention also comprises the method for treatment of hard surfaces (inanimate surfaces).In this method, the composition that makes herein definition contacts with pending crust.Therefore the present invention comprises that also using the method for the compositions-treated crust of definition herein, wherein said method to comprise is applied to described composition on the described crust, preferably only is applied to the step that it is got dirty partly and chooses the described crust of rinsing wantonly.
In the method for treatment of hard surfaces of the present invention, the form that Ding Yi composition can its pure state or with generally at the most 200 times herein, preferred 80-2 doubly, more preferably 60-2 doubly is applied on the pending surface to their the water-reducible form of weight.
When as crust bleaching/sanitizing composition, composition of the present invention is easy to rinsing and good gloss characteristics is provided on treated surface.
Crust and plate that term " crust " is interpreted as mentioning before this.The packaged form of liquid composition
According to end-use, compositions herein can be packaged in the various containers, and these containers comprise conventional bottle, the bottle of ball, sponge, brush or atomizer is housed.
In one embodiment of the invention, described composition is packaged in the two-compartment container, wherein bleaching composition described herein is packaged in the chamber, and with second kind of composition pack into second indoor.Aspect particularly preferred one, second kind of composition is conventional heavy duty liquid laundry detergent composition, and it preferably contains various compositions, particularly bleaches sensitive composition such as tensio-active agent, enzyme and spices.
The invention will be further described by following examples.
Embodiment
Following composition by assign to by the listed one-tenth of the mixed of listing the preparation (% (weight), except as otherwise noted).Form (% weight) I II III IV V sodium alkyl benzene sulfonate 21 0.5 1.5 3 linear alkyl benzene sulphonic acid 211 0.5 1C
12-C
15Alkyl 7 ethoxylates-1 2 0.2-Akyposoft, 100 NV
0.5 0.5-0.3 0.4PAP 32415 hydroxyl ethane diphosphonates 0.1 0.05 0.16 0.1-di-tert-butyl hydroxy toluene 0.05---0.1 n-propyl gallates-0.1-0.05-spices-0.2 0.2 0.3 0.1 brightening agent-0.01 0.05 0.03-NaOH--0.1 0.05-xanthans-0.2 0.3 0.5 0.8CarbopolETD 2,691 0.5 0.3 0.1-0.2CarbopolETD 2,623 0.3 0.5 0.8 1-carboxymethoxyl cellulose-1 0.5 1 0.8 alkali/acidulants are to pH value 3.9 2.5 3.5 43
Akyposoft 100 NV
Be merchant C available from Kao Chemicala Gmbh
12-C
14Alkyl (oxyethyl group) 10 carboxylate salts.
WitkonateNAS 8
Be alkylsulfonate available from WitcoAS.
BHT is a di-tert-butyl hydroxy toluene.
HEDP is an ethane 1-hydroxyl diphosphonate, available from the Dequest of Monsanto
Series.
PAP is the Euroco by name available from Ausimont
The commodity phthaloyl imino cross caproic acid.
Carbopol
ETD 2623 and 2991 is the polymkeric substance available from BFGoodrich.
When being used for bleached woven fabric or treatment of hard surfaces under with pure state and special diluting condition, above all composition exhibiting go out excellent bleachability and good detergency ability.
These composition physics and chemically stables, promptly they are after one month time of storage under 25 ℃, and the loss of AvO is no more than 15%.
Claims (11)
1. form the percarboxylic acids raw material in advance, described raw material contains 5% impurity of no more than its weight.
2. according to the percarboxylic acids of claim 1, wherein said impurity is the reagent that is used in the method for preparing described percarboxylic acids.
3. according to the percarboxylic acids of claim 1, wherein said impurity is the carboxylic acid corresponding to described percarboxylic acids.
4. according to the percarboxylic acids of claim 1 or 2, wherein said impurity is hydrogen peroxide.
5. according to any one percarboxylic acids of aforementioned claim, wherein said percarboxylic acids to the ratio of impurity greater than 19: 1.
6. bleaching composition, described composition contain any one percarboxylic acids of with good grounds aforementioned claim.
7. according to the bleaching composition of claim 6, wherein 35 ℃ store 10 days down after the loss percentage ratios no more than 15% of described active oxygen.
8. according to the bleaching composition of claim 6 or 7, described bleaching composition has and is lower than 7, preferred 2.5 to 6.5 pH value.
9. according to any one bleaching composition of claim 6 to 8, described bleaching composition contains suspension agent in addition.
10. bleach the method for surface, preferred bleached woven fabric, described method adopts the bleaching composition according to any one of claim 6 to 9.
11. contain the purposes of percarboxylic acids in bleaching surface, preferred bleached woven fabric of no more than 5% impurity.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1998/023986 WO2000027965A1 (en) | 1998-11-10 | 1998-11-10 | Bleaching compositions |
| WOPCT/US98/23986 | 1998-11-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1333814A true CN1333814A (en) | 2002-01-30 |
Family
ID=22268272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99815482.2A Pending CN1333814A (en) | 1998-11-10 | 1999-11-10 | Bleaching compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1129169A2 (en) |
| JP (1) | JP2003528932A (en) |
| CN (1) | CN1333814A (en) |
| AU (2) | AU1583399A (en) |
| BR (1) | BR9915180A (en) |
| CA (1) | CA2347496A1 (en) |
| CO (1) | CO5210995A1 (en) |
| WO (2) | WO2000027965A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20021537A1 (en) | 2002-07-12 | 2004-01-12 | Ausimont Spa | IMMIDOALCANPERCARBOXYLIC ACIDS |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3823172C2 (en) * | 1988-07-08 | 1998-01-22 | Hoechst Ag | Omega-phthalimidoperoxihexanoic acid, process for its preparation and its use |
| DE3906768A1 (en) * | 1989-03-03 | 1990-09-06 | Henkel Kgaa | Peroxycarboxylic acids and their use |
| GB8911957D0 (en) * | 1989-05-24 | 1989-07-12 | Interox Chemicals Ltd | Peroxyacid manufacture |
| EP0435379A3 (en) * | 1989-12-22 | 1991-07-31 | Akzo N.V. | Suspension, coating, agglomeration and uses of imidoperoxycarboxylic acids |
| GB9027975D0 (en) * | 1990-12-22 | 1991-02-13 | Interox Chemicals Ltd | Peroxycarboxylic acid |
| IT1277685B1 (en) * | 1995-12-21 | 1997-11-11 | Ausimont Spa | PROCEDURE FOR THE REDUCTION OF WATER AND POLAR IMPURITIES IN IMMIDO-ALCANPERCARBOXYLIC ACIDS |
-
1998
- 1998-11-10 AU AU15833/99A patent/AU1583399A/en not_active Withdrawn
- 1998-11-10 WO PCT/US1998/023986 patent/WO2000027965A1/en not_active Application Discontinuation
-
1999
- 1999-11-10 WO PCT/US1999/026602 patent/WO2000027982A2/en not_active Application Discontinuation
- 1999-11-10 CO CO99070901A patent/CO5210995A1/en not_active Application Discontinuation
- 1999-11-10 CA CA002347496A patent/CA2347496A1/en not_active Abandoned
- 1999-11-10 AU AU21475/00A patent/AU2147500A/en not_active Abandoned
- 1999-11-10 JP JP2000581149A patent/JP2003528932A/en not_active Withdrawn
- 1999-11-10 BR BR9915180-4A patent/BR9915180A/en not_active IP Right Cessation
- 1999-11-10 EP EP99965781A patent/EP1129169A2/en not_active Withdrawn
- 1999-11-10 CN CN99815482.2A patent/CN1333814A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000027982A3 (en) | 2000-08-31 |
| CO5210995A1 (en) | 2002-10-30 |
| WO2000027982A2 (en) | 2000-05-18 |
| AU1583399A (en) | 2000-05-29 |
| JP2003528932A (en) | 2003-09-30 |
| AU2147500A (en) | 2000-05-29 |
| CA2347496A1 (en) | 2000-05-18 |
| BR9915180A (en) | 2001-08-21 |
| EP1129169A2 (en) | 2001-09-05 |
| WO2000027965A1 (en) | 2000-05-18 |
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