CN1337994A - Bleaching compositions - Google Patents
Bleaching compositions Download PDFInfo
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- CN1337994A CN1337994A CN99814928.4A CN99814928A CN1337994A CN 1337994 A CN1337994 A CN 1337994A CN 99814928 A CN99814928 A CN 99814928A CN 1337994 A CN1337994 A CN 1337994A
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- alkyl
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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 process for preparing a pre-formed peroxycarboxylic acid and a bleaching 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 present invention relates to prepare the method for average particle size particle size less than 100 microns percarboxylic acids raw material.
Background of invention
The common liquid aqueous bleaching compositions that is applicable to bleached woven fabric and crust spot is with halogen bleaching agent, especially based on hypochlorite bleaching.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, especially chlorine bleach in use with after using can 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 is in higher concentration and/or when using repeatedly, fabric had strong aggressive and can damage.Particularly, the human consumer can observe the destruction of fabric itself (as the forfeiture of tensile strength) or fabric pigment intensity.Though can reduce destruction to pigment and fabric by adopting relatively mild oxygen bleaching agent such as hydrogen peroxide, the bleachability of these peroxygen bleachs is far short of what is expected than those halogen bleaching agents.Therefore, people have developed the composition that contains liquid aqueous active peroxygen bleach, and it contains activator, promptly strengthen the compound of peroxide bleaching performance.But these SYNTHETIC OPTICAL WHITNER are not so good as the hypohalite SYNTHETIC OPTICAL WHITNER at the greasiness removal aspect of performance.
Therefore a target of the present invention provides a kind of bleaching raw material and a kind of bleaching composition, this bleaching composition is not only used and/or household application arbitrarily at clothes washing) as bleaching/disinfecting hard surfaces) time can effectively transmit bleachability, and for treated surface) as fabric itself) and/or fabric pigment also be safe.
A particular problem that runs into when the preparation bleaching composition is that chemically unstable appears in bleaching raw material easily in the period of storage that is prolonging.Therefore another target of the present invention provides bleaching raw material and effective bleaching composition that transmits bleachability, and they keep chemically stable in the period of storage that prolongs.
Raw material of the present invention and composition can be used in any laundry applications, as cloth-washing detergent or detergent additive with as the clothing pretreating agent.A special advantage of composition of the present invention is that they are applicable to the dissimilar fabric of bleaching, these fabrics 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 commercially available 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 the soft water and under the condition of pure state (neat) or dilution.More specifically, we have found that liquid aqueous composition of the present invention preferably with they dilute form in any application, especially in any conventional clothes washing is used, use.Really, (be diluted to 20 milliliters/liter or bigger (composition: water)) usually, the acidity of composition of the present invention diminishes, and fades to about 6.5 or bigger as pH by about 1.5 in when dilution.Although composition of the present invention can effectively transmit bleachability under pure form, their dilute form still shows the bleachability of wonderful further raising.In fact, this " pH hop " effect can be in order to preparating 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 the period of storage that prolongs, and transmit outstanding bleachability under the application conditions of dilution.
Another advantage of composition of the present invention is that they also have effective greasiness removal performance to the various spots that comprise enzyme spot and/or grease spot.
General introduction of the present invention
According to the present invention, provide a kind of preparation to have the method that forms the percarboxylic acids raw material less than the solid of 100 microns average particle size particle size in advance, wherein at least two continuously grinding steps, grind percarboxylic acids in (step (i) and step are (ii)).
The present invention also comprises a kind of bleaching composition that contains preformed percarboxylic acids.
Detailed description method of the present invention
The present invention relates to a kind of method for preparing average particle size particle size less than 100 microns pre-formation percarboxylic acids (after this being called peracid) raw material.Present method relates to ground granulates to obtain required average particle size particle size herein.Peracid has multiple available form.The most useful a kind of available form that is used for bleaching composition is wet cake, and it forms about 0.16 millimeter-1.4 millimeters particle by peracid and water.Though the cake that wets can be added bleaching composition, the applicant has been found that there are two problems usually in the size of the peracid of this form.First problem is the outward appearance of bleaching composition.Especially when bleaching composition existed with liquid form, bore hole can be seen wet cake easily.The applicant has been found that the human consumer does not accept to contain the outward appearance of the bleaching composition of wet cake.Second problem relates to performance.Adopt peracid to be and to compare as the hypochlorite SYNTHETIC OPTICAL WHITNER as an advantage of SYNTHETIC OPTICAL WHITNER, they are less usually to the nocuity of fabric.But cake is used for bleaching composition and comes clean textile if the applicant finds to wet, and the macrobead of wet cake deposits on the fabric sometimes, because the bleaching of the intensive on this zone behavior may cause partial turn pale/fading.
Thereby the applicant find to adopt the inventive method process peracid can obtain than small-particle accept for the human consumer and do not cause eclipsed/fade.
The inventive method relates in two consecutive steps grinds peracid.In first step, adopt silverson rotar mill, two water-cooled taper sand milling (as runner milling) or its array configuration based on corundumite.Last at this grinding steps, peracid grinds to form the average particle size particle size of 100-200 micron from the particle size of 0.16-1.4 millimeter.In second step, adopt cobaltmill that the product of first step is ground to the average particle size particle size of peracid less than 100 microns.The average particle size particle size of preferred peracid is the 10-80 micron, most preferably is the 20-50 micron.
Any peracid known in the art all is applicable to herein and uses.In an embodiment preferred of the present invention, the general formula of peracid is
X-R-C (O) OOH wherein R is the straight or branched alkyl chain with at least one carbon atom, X is hydrogen or is selected from following substituting group: alkyl especially has alkyl, aryl, halogen, ester, ether, amine, the acid amides of 1-24 carbon atom, phthalyl amido, imide, hydroxide radical, sulfenyl (sulphide), sulfate radical, sulfonate radical, carboxylate radical, heterocycle, nitrate radical, aldehyde, phosphonate radical, phosphine hydroxyl (phosphonic) or its mixture of replacement.
More preferably the R group preferably contains 2-24 carbon atom.Perhaps, the R group can be for containing branch's alkyl chain of one or more side chains, and its substituting group that contains is selected from phthalyl amido, imide, hydroxide radical, sulfenyl, sulfate radical, sulfonate radical, carboxylate radical, heterocycle, nitrate radical, aldehyde, ketone or its mixture of aryl, halogen, ester, ether, amine, acid amides, replacement.
According to above-mentioned general formula, the X group in the preferred peracid is the phthalimide base.Therefore, particularly preferred peracid has the compound of following general formula for those:
R is C in the formula
1-20Alkyl, and A, B, C and D independently are hydrogen or are selected from following substituting group separately: alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyano group, carboxylate radical, sulfate radical, sulfonate radical, aldehyde or its mixture.
Of the present invention one preferred aspect, R is for having 3-12 carbon atom, the more preferably alkyl of 5-9 carbon atom.Preferred substituents A, B, C and D are the straight or branched alkyl with 1-5 carbon atom, but more preferably hydrogen.
Preferred peracid is selected from phthalic diamide and crosses caproic acid (phthaloyl amido peroxyhexanoic acid) (being also referred to as (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.
Preferred peracid is any peracid with following general formula:
Wherein R is selected from C
1-4Alkyl, n are the integer of 1-5.
Of the present invention one particularly preferred aspect, peracid has wherein that R is CH
2, n is 5 formula, promptly phthalic diamide is crossed caproic acid or PAP.
The preferred peracid that uses is basic water-insoluble solid or wet cake, and available from the commodity of the Euroco by name of Ausimont.Bleaching composition
The present invention also relates to comprise the bleaching composition of the peracid of method for preparing.Composition of the present invention is preferably liquid, is not solid or gas." liquid " used herein comprises " paste " composition.Preferred liquid composition herein is an aqueous composition, preferably contains the 10-99% of the weight that accounts for bleaching composition, more preferably the water of 50%-98%.The pH of liquid composition of the present invention is less than 7.The pH of preferred composition of the present invention is 0.1-6.5,0.5-5 more preferably, even be more preferably 2-4.Preparing composition of the present invention in the acid pH scope is crucial for the chemical stability of composition of the present invention.The pH of preferred described composition is lower than the pKa value of used peracid.We think that acid pH 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 of described composition by any acidity well known by persons skilled in the art or alkaline matter.The example that is applicable to acidic substance herein has organic acid (as citric acid) and mineral acid (as sulfuric acid, sulfonic acid and/or methylsulfonic acid).The example of alkaline matter has sodium hydroxide, potassium hydroxide and/or yellow soda ash.
But the bleachability of composition of the present invention can be assessed dissimilar bleach spots by following testing method.
The appropriate methodology of under diluting condition the bleachability of stained fabrics 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 (compositions: dilution level water), then stained fabrics is immersed in wherein 20 minutes-6 hours, rinsing then.Perhaps, with described bleaching composition with typical 1-100 milliliter/liter) composition: dilution level water) is used for washing machine.In washing machine, the washing stained fabrics is 10-100 minute under 30-70 ℃ temperature, rinsing then.In this compare test, the reference group compound is carried out identical processing.Having can be available from E.M.C.Co.Inc. as the stained fabrics/soiled cotton of spots such as tea, coffee.
Compare side by side by the stained fabrics that composition of the present invention and object of reference (as same composition but do not contain SYNTHETIC OPTICAL WHITNER or other SYNTHETIC OPTICAL WHITNER) were handled then and estimate bleachability.Discussion group can give the value of 0-4 with the range estimation ranking method to difference.
Advantage of composition of the present invention is that they keep physics and chemically stable in the storage period that prolongs.
Can behind the described composition of preparation, assess the chemical stability of composition herein by the concentration of in given period of storage, measuring available oxygen (available oxygen)." chemical stability " herein is meant that the composition of the present invention that contains peracid does not have greater than 15% in one month at 25 ℃, preferably is not more than 10% AvO loss.
Can be by behind solution reduction with the sulfur acid ferrous ammonium, the loss (AvO) of adopting permanganate titration to measure the available oxygen of the composition that contains peracid within a certain period of time.This stability test method is known in the art and as Curox
RTechnical intelligence volume (available from Interox) in the report.Perhaps, crossing acid concentration also can adopt the chromatography of describing in the literature that is used for peracid (F.Di Furia etc., the gas-liquid chromatography of mensuration peracid, Ahalyst, the 113rd volume, 1988,793-795 page or leaf) to measure.
Peracid in composition level can be the 0.1%-70% of the weight of bleaching composition, more preferably 0.5%-50%, most preferably 1%-30%.Optional components
Compositions herein also can contain many other optional components such as tensio-active agents, sequestrant, free-radical scavengers, oxidation inhibitor, stablizer, washing assistant, spot suspension polymer, polymerization spot releasing agent, pH control agent, dye transfer inhibitor, solvent, Foam Control, suds booster, whitening agent, spices, pigment, dyestuff etc.Tensio-active agent
Composition of the present invention can contain tensio-active agent or its mixture, comprises nonionogenic tenside, anion surfactant, cats product, zwitterionics and/or amphoterics.
Common composition of the present invention can contain the 0.01%-50% of composition total weight, preferred 0.1%-30%, the more preferably tensio-active agent of 0.2%-10% or its mixture.
Being used for herein, the suitable anion surfactant of composition comprises formula ROSO
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.).Usually preferred C
12-C
16Alkyl chain is used for cold washing (as being lower than about 50 ℃), and preferred C
16-C
18Alkyl chain is used for high-temperature wash (as being higher than about 50 ℃).
Other is applicable to that anion surfactant 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, usually between about 0.5 and about 6, more preferably between about 0.5 and about 3, M is H or positively charged ion, described positively charged ion can be for as metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), the ammonium cation of ammonium or replacement.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, 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 polyethoxylated (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 is selected from sodium and potassium usually.
Other anion surfactant that is specially adapted to 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, 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.).
Be applicable to that alkylaryl sulphonate herein comprises formula RSO
3The water-soluble salt of M or acid, wherein R is by C
6-C
22Saturated or the undersaturated alkyl of straight or branched, preferred C
12-C
18Alkyl, more preferably C
14-C
16The aryl that alkyl replaces, preferred benzyl, 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." secondary C herein
16-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 Hostapu by name of Hoechst
The commodity of SAS, C
8-alkylsulfonate 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 applicable to 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
24The sulfonation poly carboxylic acid of alkene sulfonate, the preparation of the pyrolysis product by the sulfonation alkaline earth metal citrate (as English Patent the 1st, 082, No. 179 described like that), C
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 vitriol, alkylphosphonic, isethionate such as acyl-hydroxyethyl sulfonate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (especially saturated and undersaturated C
12-C
18Monoesters), sulfosuccinate diester (especially saturated and undersaturated C
6-C
14Diester), the vitriol of the vitriol of alkyl polysaccharide such as alkyl polyglucoside) below with the compound of the nonionic non-sulfuric acidization that is described), the primary alkyl sulphates of side chain, the many ethoxy carboxylates of alkyl be 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, the resinous acid and the hydrogenated resin acid that exist as rosin, staybelite, with Yatall MA or its derivative form.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 attached to herein by reference at this) 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 is applicable to that anion surfactant herein is to have 4-24 on the alkyl chain, preferred 8-18, the more preferably alkyl carboxylate of 8-16 carbon atom and alkyl alcoxyl carboxylate salt, wherein alkoxyl group is third oxygen and/or oxyethyl group, preferred extent of alkoxylation is 0.5-20, the oxyethyl group of preferred 5-15.The alkyl alcoxyl carboxylate salt that is preferred 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
Commodity.
Be applicable to that amphoterics herein comprises following formula R
1R
2R
3The amine oxide of NO, wherein R
1, R
2And R
3Independent separately is the hydrocarbon chain with 1-30 carbon atom saturated or unsaturated, straight or branched.Be preferred for amine oxide surfactant of the present invention 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, more preferably methyl.R
1Can be saturated, replacement or unsubstituted straight or branched hydrocarbon chain.Be applicable to that amine oxide herein is as natural mixture C
8-C
10Amine oxide and C
12-C
16Amine oxide (available from Hoechst).
Be applicable to that zwitterionics herein contains cationic hydrophilic groups (being quaternary ammonium group) and anionic hydrophilic group in the pH of broad scope in a part.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 wherein
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
6Alkyl, hydroxyalkyl or other replacement C
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.Owing to preferred these the simple alkyl of the reason of 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 hydrocarbon 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 (C (R arbitrarily
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 examples 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 attached to herein by reference.
Especially the example that is fit to 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 propylidene (hydrogenation propylidene hydropropylene) sultaine.C for example
10-C
14Fatty acyl amido propylidene (hydrogenation propylidene) sultaine is available from " the Varion CAS by name of Sherex Company
Sultaine " commodity.
Other example of trimethyl-glycine is the Mirataine H2C-HA by name available from Rhone-Poulenc
Commodity lauryl-immino-dipropionate.
Be applicable to that cats product herein comprises 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 with nitrogen (promptly three (when being long chain hydrocarbon groups in the previously described alkyl) or two (when being long chain hydrocarbon groups for two in the previously described alkyl)) is independently of one another for having the 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 preferably 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 cats product that is particularly preferred for composition of the present invention 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 nonionogenic tenside, alkoxy-based non-ionic surface active agent and especially ethoxylated non-ionic surface active agent are applicable to herein.
The nonionogenic tenside that is particularly preferred for herein is end capped alkoxy-based non-ionic surface active agent.
The formula that is applicable to end capped alkoxy-based non-ionic surface active agent herein is:
R
1(O-CH
2-CH
2)
n-(OR
2)
m-O-R
3R wherein
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
15 alkyl;
R wherein
2Be C
1-C
10The straight or branched alkyl, preferred C
2-C
10The straight or branched alkyl;
R wherein
3Be C
1-C
10Alkyl or alkenyl, preferred C
1-C
5Alkyl, more preferably methyl;
Wherein n and m independently are 1-20, preferred 1-10, the more preferably integer of 1-5 scope; 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
Composition of the present invention can preferably contain suspension agent.Suspension agent is the special a kind of component that adds composition of the present invention with the solid particulate components of the described composition that suspends.For the present invention, suspension agent is used in particular for the PAP that suspends.
The suspension agent that is fit to is known in the art those.The example of suspension agent comprises polysaccharide polymer (as xanthan gum), polyvinyl alcohol and derivative, Mierocrystalline cellulose and derivative thereof and polycarboxylic acid polymer.
In particularly preferred embodiment of the present invention, 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 of polymkeric substance is crosslinked polycarboxylic acid polymer.Described composition also can contain other polymkeric substance.
The gum-type polymkeric substance can be selected from: derivative of polysaccharide hydrocolloids, xanthan gum, melon ear wood glue, succinoglucan glue, Mierocrystalline cellulose, above-mentioned any material and composition thereof.Of the present invention one preferred aspect, the gum-type polymkeric substance is the xanthan gum or derivatives thereof.
The level that exists of described gum-type polymkeric substance is 0.01%-10%, more preferably 0.1%-3%.
Polycarboxylate polymer can be homopolymer and 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 from BF Goodrich.The molecular weight ranges of the polymkeric substance that is fit to is 10000-10000000, more preferably 100000-10000000.
The level 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 can also contain other polymkeric substance.
The gum-type polymkeric substance is 100 with the ratio of crosslinked polycarboxylate polymer: 1-1: 100, more preferably 10: 1-1: 10.Sequestrant
Composition of the present invention can contain sequestrant as the preferred optional component.The sequestrant that is fit to can be known any of those skilled in the art, 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, polyfunctional group replacement, or its mixture.
Exist sequestrant to help further to improve the chemical stability of described composition.Sequestrant also may be needed in the composition of the present invention, and therefore the ionic strength of composition also strengthens them at various lip-deep decontaminations and bleachability because it can improve herein.
Be applicable to that herein phosphine acid salt chelator can comprise basic metal ethane 1-hydroxyl diphosphonate (HEDP), alkylidene group poly-(alkylene phosphonic acids salt), and aminophosphonic acid salt compound (comprise 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 phosphine acid salt chelator that is preferred 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 that polyfunctional group replaces also can be used in the compositions herein.License 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, especially (S, S) isomer is described in detail in the United States Patent (USP) 4,704,233 in 3,1 987 on the November of Hartman and Perkins.Quadrol N, N '-disuccinic acid are for example available from the ssEDDS by name of Palmer Research Laboratories
Commodity.
Be applicable to that aminocarboxylate herein comprises edetate, 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.Especially the aminocarboxylate that is suitable 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 another kind of sequestrant that is used for herein has following formula:
R wherein
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 sequestrant that is particularly preferred for herein is amino three (methylene phosphonic acids), diethylidene triamino pentaacetic acid, diethylenetriamine pentylidene phosphonate, 1-hydroxyl ethane diphosphonate, quadrol N, N '-disuccinic acid, and composition thereof.
Common composition of the present invention comprises and accounts for 5% of its gross 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 applicable to that herein free-radical scavengers comprises 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 Sl by name of Nipa Laboratories
Commodity.
When using free-radical scavengers, its amount is at most 10% of composition total weight usually, is preferably 0.001%-0.5%.
The free-radical scavengers that exists can help the chemical stability of bleaching composition of the present invention and the safety distribution (safety profile) of composition of the present invention.Foam Control
Composition of the present invention also can comprise Foam Control such as 2-alkyl chain triacontanol, or its mixture is as the preferred optional component.Being specially adapted to of the present invention is to contain 6-16, the alkyl chain of preferred 8-12 carbon atom and the 2-alkyl chain triacontanol of 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 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 be by the glyceryl ester (as plam oil, cocounut oil, babassu oil, soybean oil, Viscotrol C, butter, whale oil, fish oil, butter, fat, lard and composition thereof) of natural source such as plant or animal derived.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 preparation 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, have about 2.5% C usually with fatty acid mixt
14, 29% C
16, 23% C
18, 2% physetoleic acid, 41.5% oleic acid and 3% linolic acid (first three that list planted and be saturated fatty acid) carbon chain length distribution.Other mixture with similar distribution is as being also included within the term butter derived from the grease of various animals and the lipid acid of lard.Also butter can be hardened (being hydrogenation) thus part or all of unsaturated fatty acids acid moieties is converted into the saturated fatty acid moieties.
When adopting term " cocounut oil " herein, it is meant fatty acid mixt, has roughly about 8% C usually
8, 7% C
10, 48% C
12, 17% C
14, 9% C
16, 2% C
18, 7% oleic acid and 2% linolic acid (the first six that list 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 silicon-dioxide in small, broken bits usually, and example has silicon-dioxide aerosol and silica xerogel and various types of water drain silica.These materials can particle form add, wherein Foam Control preferably add 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) 3933672.The polysiloxane Foam Control that other useful especially Foam Control is a self-emulsifying, they are described among the German patent application DTOS2646126 that announced on April 28th, 1977.An example of this compound is DC-544 (silane oxygen-glycol copolymer), available from Dow Corning.
The empty preparation of particularly preferred polysiloxane foam is disclosed in common unsettled european patent application N ° 92201649.8.Described composition can comprise and made up pyrolysis method atresia silicon-dioxide such as Aerosil
RPolysiloxane/silica mixture.
Particularly preferred Foam Control is the Foam Control system that comprises silicone oil and 2-alkyl chain triacontanol mixture.
Usually composition can contain and accounts for 4% of its gross weight at the most, preferred 0.1-1.5%, the most preferably Foam Control of 0.1-0.8%, or its mixture herein.Stablizer
Composition of the present invention also can comprise and accounts for 10% of its gross weight at the most, the formula HO-CR ' R of preferred 2%-4% "-alcohol of OH, wherein R ' and R " independent be H or C
2-C
10Hydrocarbon chain and/or hydrocarbon ring.Preferably the alcohol according to this formula is propylene glycol.We observe the chemical stability that these alcohol, particularly propylene glycol generally also can improve described composition really.
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 spot suspension polymer
Composition of the present invention also can contain spot suspension polymer such as polyamine spot suspension polymer as optional components.Can use any spot suspension polyamine polymer well known by persons skilled in the art at this.Be particularly suitable for using herein polyamine polymer be the poly-alkoxylation polyamine.These materials can be represented with the molecule of the experience structure with following repeating unit easily:
The amine type and
Quaternized type wherein R is an alkyl, 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 halogen anion or Methylsulfate (coming 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 its general formula is as follows:
Y=2-30 wherein.Be particularly preferred for herein be the ethoxylation polyvinylamine, particularly ethoxylation tetracthylene pentamine and quaternised ethoxylation hexamethylenediamine.
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 (enzymatic stains), clay/mud stain and the stain that can bleach.
Usually composition comprises and accounts for 10% of its gross weight at the most, preferred 0.1%-5%, more preferably this spot suspension polyamine polymer or its mixture of 0.3%-2%.
Composition also can contain other aggretion type spot releasing agent well known by persons skilled in the art herein.These polymerization spot 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 whole washing and rinse cycle, keep adhering on it, and serve as the anchor of hydrophilic segment thus).Can make subsequently spot be easier in the washing procedure of back, be eliminated like this with the spot release-agent-treated.
Be applicable to that polymerization spot releasing agent herein especially comprises those spot releasing agents with following feature: (a) one or more nonionic hydrophilic segments, mainly be made up of following: (i) polymerization degree is at least 2 polyoxyethylene part, or (ii) the polymerization degree is propylene oxide or the polyoxytrimethylene 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 oxygen ethylene unit of capacity, make when the spot releasing agent is deposited on the surface of normal polyester synthon, hydrophilic segment has enough wetting abilities and strengthens these surperficial wetting abilities, preferred described hydrophilic segment comprises at least about 25% oxygen ethylene unit, more preferably especially these parts have about 20 to 30 oxypropylene unit, the oxygen ethylene unit at least about 50%; Perhaps (b) one or more hydrophobic parts comprise (i) C
3Oxyalkylene terephthalic acid ester moiety is if wherein described hydrophobic part also comprises oxygen ethylene terephthalate unit, oxygen ethylene terephthalate: C so
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, these derivatived celluloses are amphiphilic substance, and they have the C of q.s thus
1-C
4Alkyl oxide and/or C
4Thereby the hydroxyalkyl ether unit deposits on the conventional polyethylene terephthalate surface and keep the hydroxyl of enough levels (on adhering to these conventional synthon surfaces time) to increase the wetting ability of fiber surface; Perhaps (a) and combination (b).
Usually polyoxyethylene part (a) (i) has about 1 to about 200 (although can adopt higher level), and preferred 3 to about 150, more preferably 6 to about 100 the polymerization degree.The oxygen C that is fit to
4-C
6The alkylidene group hydrophobic part includes, but is not limited to end capped polymerization spot releasing agent such as MO
3S (CH
2)
nOCH
2CH
2O-, wherein M is a sodium, n is the integer (as authorizing the United States Patent (USP) 4,721 that gives Gosselink on January 26th, 1988,580 is described) of 4-6.
Be applicable to that polymerization spot releasing agent of the present invention also comprises the copolymerization block thing 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 can obtain commercial offers, comprise cellulosic hydroxy ethers such as METHOCEL (Dow).Being used for herein Mierocrystalline cellulose spot releasing agent also comprises and is selected from C
1-C
4Alkyl and C
4Those Mierocrystalline cellulose spot releasing agents of hydroxy alkyl cellulose; Authorize the United States Patent (USP) 4,000,093 that gives people such as Nicol referring on December 28th, 1976.
Spot releasing agent with poly-(vinyl acetate) hydrophobic part feature comprises the graft copolymer of poly-(vinyl acetate), as C
1-C
6Vinyl acetate preferably is grafted to poly-(vinyl-acetic ester) on the 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.This commodity spot releasing agent comprises the SOKALAN section bar material of carrying available from West Germany BASF, as SOKALAN HP-22.
The preferred spot releasing agent of one class is the statistic copolymer of ethylene glycol terephthalate and polyethylene oxide (PEO) terephthalate.The molecular weight ranges of this polymerization spot releasing agent is about 25,000 to about 55,000.Give the United States Patent (USP) 3,893,929 of Basadur referring to authorizing the United States Patent (USP) mandate on July 8th, 3,959,230 and 1975 of giving Hays on May 25th, 1976.
Another kind of preferred polymerization spot 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) (by molecular-weight average is 300-5, and 000 dimerization oxygen ethene dibasic alcohol is derived).The example of this polymkeric substance comprises proprietary concentrate ZELCON 5126 (from Du Pont) and MILEASE T (from ICI).Also referring to authorizing the United States Patent (USP) 4,702,857 that gives Gosselink on October 27th, 1987.
Another kind of preferred polymerization spot releasing agent is the sulfonated products of basic linear ester oligopolymer, and it 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 spot releasing agents are authorized in the United States Patent (USP) 4,968,451 that gives J.J.Scheibel and E.P.Gosselink in November 6 nineteen ninety and have been carried out abundant description.Other polymerization spot releasing agent that is fit to comprises authorized the United States Patent (USP) 4 that gives people such as Gosselink on December 8th, 1987,711, authorize the United States Patent (USP) 4 that gives Gosselink in terephthalate polyester in 730, on January 26th, 1988,721, authorize the United States Patent (USP) 4 that gives Gosselink in the end capped oligomer ester of negatively charged ion in 580 and on October 27th, 1987, block polyester oligomeric compound in 702,857.
Preferred polymerization spot releasing agent also comprises authorized the spot releasing agent in the United States Patent (USP) 4,877,896 that gives people such as Maldonado on October 31st, 1989, and it discloses negatively charged ion, especially the end capped terephthalate of sulfonation aroyl.
Also having another kind of preferred spot releasing agent 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 oligopolymer and preferably adopts modification hydroxyethylsulfonic acid ester terminal to carry out end-blocking.The especially preferred spot releasing agent of this class 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-hydroxyl ethoxy)-ethyl sulfonic acid sodium end group unit.Described spot releasing agent also contains the minimizing crystalline stablizer that accounts for polymer weight about 0.5% to about 20%, is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and composition thereof.Authorize the United States Patent (USP) 5,415,807 that gives people such as Gosselink referring to May 16 nineteen ninety-five.
If use described spot releasing agent, it will account for the 0.01%-10.0% of detergent composition weight herein, be generally 0.1%-5%, preferred 0.2%-3.0%.Dye transfer inhibitor
Composition of the present invention also can contain one or more and can effectively suppress dyestuff migrate to another surperficial material from a dyestuff surface in cleaning course.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 you are using, these reagent account for the 0.01%-10% of composition weight usually, preferred 0.01%-5%, more preferably 0.05%-2%.
More specifically, the polyamine N-oxide pllymers that is preferred for herein comprises having R-A
xThe unit of-P-structure formula; Wherein P is a polymerizable unit, and wherein a part or the N-O group that the N-O group can be connected thereto or the N-O group can form described polymerizable unit can connect two described 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 non-cyclic group or its arbitrary 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 be those wherein the R group be compound as the heterocyclic group of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and derivative thereof.
The N-O group can be represented by following universal architecture:
R wherein
1, R
2, R
3Be aliphatic series, aromatics, heterocycle or non-cyclic group or its combination; X, y and z are 0 or 1; Nitrogen in the N-O group can link to each other or form the part of above-mentioned group.The unitary pKa of the amine oxide of 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, 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 polyoxygenated amine polymer by the N-oxidation of suitable degree by suitable copolymerization.Almost can obtain the polyamine oxide compound of any polymerization degree.Usually average molecular weight range is 500-1,000,000; More preferably 1,000-500,000; Most preferably 5,000-100,000.This class preferable material can be called " PVNO ".The polyamine N-oxide that most preferably is used for 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.The average molecular weight range of preferred PVPVI is 5,000-1, and 000,000, more preferably 5,000-200,000, most preferably be 10,000-20,000.(at Chemical Analysis, the 113rd rolls up average molecular weight range according to people such as Barth, and the described scattering of light of " modernism of polymer characterization " (its open part is attached to herein by reference) is determined).The N-vinyl imidazole in the PVPVI multipolymer and the mol ratio of N-V-Pyrol RC are 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 composition of the present invention also can adopt molecular-weight average, 000-400, and 000, preferred 5,000-200,000, more preferably 5,000-50,000 polyvinylpyrrolidone (" PVP ").PVP has been known to the technician of detergent applications; Referring to as EP-A-262,897 and EP-A-256,696, be 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 (amount of 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 these suds boosters 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 can adding other foam to be provided and to improve the degrease performance as the level of 0.1%-2%.Whitening agent
When being designed for fabric treating or washing clothes, 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 account for cleaning composition weight herein usually 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-toluylene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines family (methinecyanines), dibenzothiophene-5,5-dioxide, pyrroles, 5-and 6-unit heterocycle whitening agent, listed only as an illustration, tool is not restricted.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--[1,2-d] 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
Can adopt various suitable materials to regulate (comprising organic acid or mineral acid, alkanolamine etc.) pH of composition.Preferably use alkanolamine, monoethanolamine especially, they also have other 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.These inanimate surfaces include, but is not limited to indoor as the crust in kitchen, bathroom or the car such as ceramic tile, wall, floor, chromium, glass, level and smooth ethene, any kind of plastics, plasticizing wood, desktop, washtub, cook top, 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 composition of the present invention 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.
Therefore, the present invention also comprises processing, especially the method for bleached woven fabric (as non-life surface).In this method, composition of the present invention is contacted with pending fabric.
Can so-called " pre-treatment pattern " carry out, wherein at rinse fabric or before washing then rinse fabric, the liquid bleaching composition packed of definition herein is applied on the described fabric with pure state, perhaps carry out with " immersion pattern ", wherein the liquid bleaching composition packed that will herein define at first dilutes in water-bath, before carrying out rinsing, fabric is immersed and in bath, soak, perhaps carry out, wherein except adding 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 of bleaching surface, especially bleached woven fabric of the present invention and effective detergency ability.
Preferred composition of the present invention contacts with fabric with liquid form.In fact herein " liquid form " is meant the pure state of composition itself of the present invention or with their dilute form.
Composition of the present invention is used in the middle of the laundry operations with dilute form usually." dilute form " herein is meant that the composition that is used for bleached woven fabric of the present invention can be diluted by the 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 500 times at the most, 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 (1-60 minute usually 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 of 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 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, make (common 5 seconds to the 30 minutes time that described fabric and described bleaching composition keep in touch is enough to bleach described fabric, 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 for the treatment of on the bleached woven 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, with their (being generally the dilution bleaching process) of composition bleaching of the present invention, use the less energy and washing composition that excellent whiteness and detergency ability is 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 in accordance with the present invention crust, the form that Ding Yi composition can its pure state or with at the most 200 times usually herein, preferred 80-2 doubly, more preferably 60-2 doubly the dilute form of the water of their weight be applied to pending surface.
When as crust bleaching/sanitizing composition, composition of the present invention is easy to provide good gloss characteristics on the surface of handling.
Crust that " crust " is interpreted as mentioning before this and plate.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, spring, 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 second kind of composition is loaded in second container.Aspect particularly preferred one, second kind of composition is conventional heavy duty liquid laundry detergent composition, and it preferably contains various components, especially bleaches sensitive ingredients such as tensio-active agent, enzyme and spices.
The invention will be further described by following examples.
Embodiment
By (% (weight) except as otherwise noted) mixes listed component and prepares following composition in the ratio of listing.Form I II III IV V (% weight) sodium alkyl benzene sulfonate-1-1.5-linear alkyl benzene sulphonic acid--1 0.5-C
12-C
15Alkyl 7 b-oxides-1---Akyposoft 100 NV
--2-PAP, 3241 20 hydroxyl ethane diphosphonates, 0.1 0.05 0.16 0.1 0.1 spices-0.2 0.2 0.3-brightening agent-0.01,0.05 0.03-xanthans, 0.3 0.2 0.3-0.5Carbopol ETD, 2691 0.2-0.1-Carbopol ETD 2623---0.3-carboxyl methoxyl group cellulose-1 0.5 1-alkali/acidulant is regulated pH value to 3.9 2.5 3.5 44
Akyposoft 100 NV
Be commodity C available from Kao Chemicala Gmbh
12-C
14Alkyl ethoxy 10 carboxylate salts.
Witkonate NAS 8
Be alkylsulfonate available from Witco AS.
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 phthalimido cross caproic acid.
Carbopol
ETD 2623 and 2991 is the polymkeric substance available from BFGoodrich.
When with pure state with when under diluting condition, being used for bleached woven fabric or treatment of hard surfaces especially, above all composition exhibiting go out excellent bleachability and good detergency ability.
These compositions are physics and chemically stable, and promptly they are after one month time of storage under 25 ℃, and the loss of AvO is no more than 15%.
Claims (9)
1. the preparation average particle size particle size is less than the method for 100 microns solid percarboxylic acids raw material, wherein at least two successive grinding steps-steps (i) and step (ii)-the described percarboxylic acids of middle grinding.
2. according to the process of claim 1 wherein that the average particle size particle size of described percarboxylic acids is the 10-80 micron.
3. each method in requiring according to aforesaid right, wherein step (i) adopts silversonrotar mill, two water-cooled taper sand milling or its to make up to implement, and step (ii) adopts two water-cooled taper sand millings (cobal mill) to implement.
4. bleaching composition, described bleaching composition is included in the solid percarboxylic acids of each preparation in the aforesaid right requirement.
5. according to the bleaching composition of claim 4, the level that exists of wherein said percarboxylic acids is the 0.1-70% of described composition weight, preferred 0.1-50%.
6. according to the bleaching composition on top, one in claim 4 or 5, also comprise tensio-active agent less than 5% level.
7. according to each bleaching composition among the claim 4-6, also comprise a kind of suspension agent.
8. bleach the method for surface, preferred bleached woven fabric, described method adopts the bleaching composition according to any one of claim 4 to 8 to contact with described surface.
In bleaching composition according to any one prepared percarboxylic acids of claim 1 to 3 purposes in bleaching surface, preferred bleached woven fabric.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1998/023987 WO2000027966A1 (en) | 1998-11-10 | 1998-11-10 | Bleaching compositions |
| WOPCT/US98/23987 | 1998-11-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1337994A true CN1337994A (en) | 2002-02-27 |
Family
ID=22268273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99814928.4A Pending CN1337994A (en) | 1998-11-10 | 1999-11-10 | Bleaching compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1129167A1 (en) |
| JP (1) | JP2003526700A (en) |
| CN (1) | CN1337994A (en) |
| AU (2) | AU1583499A (en) |
| BR (1) | BR9915175A (en) |
| CA (1) | CA2347228A1 (en) |
| CO (1) | CO5210988A1 (en) |
| WO (2) | WO2000027966A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20021537A1 (en) | 2002-07-12 | 2004-01-12 | Ausimont Spa | IMMIDOALCANPERCARBOXYLIC ACIDS |
| DE10259262B3 (en) | 2002-12-17 | 2004-08-05 | Henkel Kgaa | Process for the production of suspensions containing bleach |
| DE102004019139A1 (en) * | 2004-04-16 | 2005-11-10 | Henkel Kgaa | Liquid-crystalline washing or cleaning agent with particulate bleach |
| GB0509377D0 (en) * | 2005-05-09 | 2005-06-15 | Reckitt Benckiser Nv | Detergent composition |
| US10060073B2 (en) | 2013-05-23 | 2018-08-28 | Washing Systems, Llc | Method of laundering industrial garments |
| JP2018203931A (en) * | 2017-06-07 | 2018-12-27 | 花王株式会社 | Detergent composition for fiber products |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ216987A (en) * | 1985-08-20 | 1988-09-29 | Colgate Palmolive Co | Nonaqueous liquid low phosphate laundry detergent |
| US5503765A (en) * | 1993-08-27 | 1996-04-02 | Lever Brothers Company, Division Of Conopco, Inc. | Stable non-aqueous compositions containing peracids which are substantially insoluble |
| CA2215949A1 (en) * | 1995-04-17 | 1996-10-24 | The Procter & Gamble Company | Preparation and use of composite particles containing diacyl peroxide |
| IT1289155B1 (en) * | 1997-01-03 | 1998-09-29 | Ausimont Spa | GRANULAR COMPOSITIONS OF PEROXYESANOIC E-PHTHALYMIDIC ACID |
| IT1293587B1 (en) * | 1997-07-08 | 1999-03-08 | Manitoba Italia Spa | COMPOSITIONS BASED ON PERCARBOXYLIC ACIDS AS STAIN REMOVER AND SANITIZERS |
-
1998
- 1998-11-10 WO PCT/US1998/023987 patent/WO2000027966A1/en not_active Application Discontinuation
- 1998-11-10 AU AU15834/99A patent/AU1583499A/en not_active Withdrawn
-
1999
- 1999-11-10 WO PCT/US1999/026600 patent/WO2000027969A1/en not_active Application Discontinuation
- 1999-11-10 CN CN99814928.4A patent/CN1337994A/en active Pending
- 1999-11-10 JP JP2000581136A patent/JP2003526700A/en not_active Withdrawn
- 1999-11-10 AU AU20233/00A patent/AU2023300A/en not_active Abandoned
- 1999-11-10 CA CA002347228A patent/CA2347228A1/en not_active Abandoned
- 1999-11-10 CO CO99070889A patent/CO5210988A1/en not_active Application Discontinuation
- 1999-11-10 EP EP99963884A patent/EP1129167A1/en not_active Withdrawn
- 1999-11-10 BR BR9915175-8A patent/BR9915175A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2347228A1 (en) | 2000-05-18 |
| AU1583499A (en) | 2000-05-29 |
| CO5210988A1 (en) | 2002-10-30 |
| WO2000027966A1 (en) | 2000-05-18 |
| EP1129167A1 (en) | 2001-09-05 |
| AU2023300A (en) | 2000-05-29 |
| WO2000027969A1 (en) | 2000-05-18 |
| JP2003526700A (en) | 2003-09-09 |
| BR9915175A (en) | 2001-08-14 |
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