CN1242798A - Liquid aqueous bleaching compositions and pretreatment process - Google Patents
Liquid aqueous bleaching compositions and pretreatment process Download PDFInfo
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- CN1242798A CN1242798A CN 97181136 CN97181136A CN1242798A CN 1242798 A CN1242798 A CN 1242798A CN 97181136 CN97181136 CN 97181136 CN 97181136 A CN97181136 A CN 97181136A CN 1242798 A CN1242798 A CN 1242798A
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Abstract
The present invention relates to an acidic aqueous composition suitable for pretreating soiled fabrics comprising a peroxygen bleach and a soil suspending agent selected from the group consisting of an ethoxylated cationic diamine, an ethoxylated cationic polyamine, an ethoxylated cationic amine polymer and mixtures thereof. This invention is also a process for pretreating soiled fabrics with such a composition.
Description
Technical field
The present invention relates to be especially suitable for use as the acidic liquid aqueous bleaching compositions of pretreating agent and the method for pretreating fabrics.
Background of invention
The multiple liquid aqueous cleaning combination that is particularly suitable for pretreating fabrics has been described in the prior art.
The moisture cleaning combination of common liq, those cleaning combinations that particularly contain peroxygen bleach, when being used for the different types of fabric of pre-treatment, comprise cotton and synthetic textiles for example polyester, polymeric amide etc., the problem relevant with these cleaning combinations be they can not provide satisfy consumer demand satisfactorily all types of spots are comprised the effective performance that oil stain, enzyme stain, mud/soil steep etc.Although also finding this problem that contains the liquid composition of peroxygen bleach is that the peroxygen bleach tendency migrates to fabric face, it can not interact with the spot that can bleach or dirt component on demand fully.Found on peroxygen bleach have other active ingredient through the being deposited on fabric of (in this liquid composition that contains peroxygen bleach, can exist), suppressed to migrate to for example native dirty particle place on the fabric of the stain (for example mud coal stain) that to bleach.Therefore, their bleachability can be slackened.The result reduced that the cleaning of peroxygen bleach can bleach/performance of dirty dirt.
Therefore, the objective of the invention is various spots are provided the decontamination stain performance and the good bleachability of improvement, particularly under the laundry pretreatment condition, promptly before the fabric of washing band dirt, when at least a portion of liquid aqueous composition being applied to respective pure form on the described fabric.
Must select to be used for to contain the suitable component of the liquid aqueous composition of peroxygen bleach, make them can be fit to give this based composition required decontamination stain performance.But the use of this component must not cause the chemical stability of unacceptable degree.
As mentioned above, obviously still need to determine and provide the liquid aqueous composition that contains peroxygen bleach that is applicable to pretreating fabrics, it has commercial acceptable chemical stability and good total decontamination stain performance and bleachability.
Have now found that, that comprise peroxygen bleach and soil-suspending agent by use and be mixed with the fabric that pH is lower than the aqueous composition pre-treatment band dirt of 6 acid pH scope, the decontamination stain performance that is improved, kept enough chemical stabilities simultaneously, wherein said soil-suspending agent is selected from ethoxylation cationic diamine, ethoxylation cationic polyamine, ethoxylation cationic amine polymkeric substance and their mixture as used herein.In fact, have now found that soil-suspending agent as defined herein is worked into easily according in the acidic aqueous compositions that comprises peroxygen bleach of the present invention, has reduced the influence to the chemical stability of described composition.In other words, specific soil-suspending agent as defined herein is compatible with the peroxygen bleach in the acidic medium fully.
In fact, the acidic aqueous compositions of the present invention that comprises peroxygen bleach and soil-suspending agent as defined herein is under the laundry pretreatment condition, the decontamination stain performance that provides with the same composition that does not contain described soil-suspending agent compares, and various types of spots are comprised that oil stain, enzyme stain, soil/slurry stain etc. provide the decontamination stain of improving performance.In addition, find surprisingly that the acidic aqueous compositions that comprises peroxygen bleach and described soil-suspending agent compares with the same composition that does not contain described soil-suspending agent, and the bleaching effect that improves is provided when being used for pretreating fabrics.Therefore find to add in containing the acidic aqueous compositions of peroxygen bleach the simplification compound, promptly this soil-suspending agent provides the decontamination that improves to steep the bleachability of performance and improvement.In addition, find the bleachability that goes to steep performance and improvement of this improvement of various spots is held, even also be like this for the acidic aqueous compositions that contains peroxygen bleach through standing storage.
Advantage of the present invention has provided the acidic aqueous compositions of chemistry and physically stable, and it is applicable to the most economical mode that the human consumer uses in long-time.
In addition, find that acidic aqueous compositions of the present invention can be mixed with milk sap or microemulsion, does not need to change the rheology of composition in the preferred embodiment of the invention.In fact, found that described soil-suspending agent has reduced the viscosity that comprises the acidic aqueous compositions of peroxygen bleach of the present invention, no matter and before adding described soil-suspending agent viscosity why.
Background technology
EP-A-271312 discloses the laundry composition that comprises peroxyacid bleach and dirt release agent, wherein dirt release agent such as specific alkyl and hydroxyalkyl ether Mierocrystalline cellulose, comprise the polymkeric substance of ethylene terephthalate and terephthalic acid polyethylene oxide ester.Ethoxylation cationic diamine, ethoxylation cationic polyamine, ethoxylation cationic polymers are not disclosed.
US4659802 discloses and has comprised ethoxylation cationic diamine, ethoxylation cationic polyamine and/or ethoxylation cationic polymers as the detergent composition of removing great soil group dirt/anti redeposition agent.Peroxygen bleach is not disclosed.
EP-A-111965 disclose comprise the ethoxylation cation mono-or diamines, ethoxylation cationic polyamine and/or ethoxylation cationic polymers as the detergent composition (pH=6-8.5) of removing great soil group dirt/anti redeposition agent.Peroxygen bleach is not disclosed.
Summary of the invention
The present invention includes the pH that is applicable to pretreating fabrics and be lower than 6 and comprise the liquid aqueous composition of peroxygen bleach and soil-suspending agent, wherein said soil-suspending agent is selected from:
1) have the ethoxylation cationic diamine of following formula:
M wherein
1Be N+ or N group; Each M
2Be N+ or N group, at least one M
2It is the N+ group.
2) have the ethoxylation cationic polyamine of following formula:
3) ethoxylation cationic polymers, it comprises polymer backbone, at least 2 M groups and at least one L-X group, and wherein M is connected with skeleton or becomes holistic cation group with skeleton; X is a non-ionic group, is selected from H, C
1-C
4Alkyl or hydroxy alkyl ester or ether group and their mixture; Be linking group M and X or X be connected to hydrophilic chain on the polymer backbone with L,
4) their mixture; A wherein
1Be
R is H or C
1-C
4Alkyl or hydroxyalkyl, R
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene, or have the C of about 20 oxygen alkylidene units of 2-
2-C
3Oxyalkylene part, condition are not form the O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl ,-L-X part, or two R
2In conjunction with formation-(CH
2)
r-A
2-(CH
2)
s-part, wherein A
2Be-O-or-CH
2-, r is 1 or 2, and s is 1 or 2, and r+s is 3 or 4; Each R
3Be C
1-C
8Alkyl or hydroxyalkyl, benzyl, L-X part, or two R
3Or R
2With a R
3In conjunction with formation-(CH
2)
r-A
2-(CH
2)
s-part; R
4Be to have p C that replaces the replacement at position
3-C
12Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R
5Be C
1-C
12Alkenyl, hydroxy alkylidene, alkylene group, arylidene or alkarylene, or have the C of about 20 oxygen alkylidene units of 2-
2-C
3Oxyalkylene part, condition are not form O-O or O-N key; X is selected from H, C
1-C
4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and their mixture; L contains the poly (oxyalkylene) base section :-[(R
6O)
m(CH
2CH
2O)
n]-hydrophilic chain; R wherein
6Be C
3-C
4Alkylidene group or hydroxy alkylidene, m and n are feasible-(CH
2CH
2O)
n-part accounts for said poly (oxyalkylene) base section at least about 50% numerical value; Work as M
2When being N+, d is 1, works as M
2When being N, d is 0; For said cationic diamine, n is 6 and for said cationic polyamine and cationic polymers at least, and n is 3 at least; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1.
The present invention also comprise with as the method for the liquid acidic aqueous composition bleaching band dirt fabric of preamble definition, described method is included in washs before the described fabric, described composition is applied to the step at least a portion of described fabric with purified form.
The detailed Description Of The Invention composition
The present invention includes the liquid acidic aqueous composition that is applicable to pretreating fabrics, it comprises peroxygen bleach and is selected from the soil-suspending agent of ethoxylation cationic diamine, ethoxylation cationic polyamine, ethoxylation cationic amine polymkeric substance and its mixture of preamble definition.
In the liquid acidic aqueous composition that comprises peroxygen bleach, add this soil-suspending agent provide improve various spots are comprised the decontamination stain performance of oil stain, enzyme stain, soil/slurry stain, particularly under the pretreated condition of laundry, and the bleachability that improves, keep enough chemical stabilities simultaneously.
" decontamination stain performance " here look like be meant to various stain for example the decontamination of fats/oils spot and/or enzyme stain and/or mud/soil stain (particle spot) steep performance." fats/oils spot " here looks like is any dirt of butyrous and the spot that can find on fabric, as dirty machine oil, mineral oil, makeup, lipstick, vegetables oil, macaroni condiment, mayonnaise etc.The example of enzyme stain comprises grass, chocolate and bloodstain.
It is believed that to cause beyond thought benefit that promptly the decontamination stain and the bleachability of Gai Shaning has three kinds of mechanism.First kind of mechanism is, peroxygen bleach is surface-active for the surface of containing organic materials particularly, and it will migrate to fabric face thus, and it can be from the organic material of bleaching of surface removal then.Second kind of mechanism is, soil-suspending agent can with electronegative dirt digestion on the fabric face, thus in and fabric face.This will impel peroxygen bleach to migrate to fabric face.The third mechanism is, soil-suspending agent can be removed and suspend and be deposited on dirt on the fabric face, as grease, particulate fouling (mud/soil) and/or enzyme dirt, impels peroxygen bleach to be assigned on the stain that can bleach on the fabric thus.
Soil-suspending agent of the present invention is fully compatible with peroxygen bleach.Do not wish to accept keeping within bounds of opinion, the soil-suspending agent here and the consistency of SYNTHETIC OPTICAL WHITNER are soluble as follows.The quaternized dual purpose that is considered to have of the nitrogen groups of these molecules.It provides cationic charge to molecule, improved adsorption to spot/particle on the fabric face such as grogs, with oxidable lone electron pair on the nitrogen groups of having removed the albic material attack, make this molecule stable in containing the aqueous composition of peroxygen bleach thus.In addition, the soil-suspending agent of this paper and acidic medium are fully compatible.
Aqueous bleaching compositions of the present invention is chemically stable.Here " chemically stable " meaning is that the composition of the present invention that comprises peroxygen bleach does not lose the available oxygen more than 20% in 2 weeks under 50 ℃.The concentration of available oxygen can be measured by chemical titration well known in the art, for example iodimetry, permanganate titration and cerimetry.The standard to describe of described method and selection appropriate methodology is at for example " hydrogen peroxide ", W.C.Schumb, C.N.Satterfield and R.L.Wentworth, Reinhold publishing company, New York, 1955 and " organo-peroxide ", Daniel Swern, Wiley Int.Science edits, and 1970.In addition, the stability of described composition also can be evaluated by the bulging test method.
Bleaching composition of the present invention is a physically stable.Here " physically stable " meaning is the present composition when being exposed under the stress condition for example in 40 ℃ 2 weeks, without separating into two-phase or multiphase.
Composition of the present invention is aqueous, and they comprise by composition total weight thus, the water of 50%-98%, preferred 50%-95%, the more preferably water of 55%-90%.
The present composition comprises as the peroxygen bleach of necessary component or its mixture.
Being used for peroxygen bleach of the present invention is the known any peroxygen bleachs of those skilled in the art.This peroxygen bleach comprises hydrogen peroxide or its water-soluble sources, or their mixture.In fact, the existence of peroxygen bleach provides good cleaning and bleaching benefit to the composition of the present invention's use.Hydrogen peroxide cource described here is meant and produces the anionic any compound of perhydroxyl radical when contacting with water.
Be used for suitable water-soluble hydrogen peroxide cource of the present invention and comprise percarbonate; persilicate; persulphate is a persulphate for example; perborate, peroxy acid be diperoxy dodecanedioic acid (DPDA), mistake magnesium phthalate, mistake lauric acid, peroxybenzoic acid and alkyl peroxybenzoic acid, hydroperoxide, diacyl peroxide and its mixture for example.Being used for the preferred peroxygen bleach of the present invention is hydrogen peroxide, hydroperoxide and/or aliphatic diacyl peroxide.
Being used for the hydroperoxide that the present invention is fit to is tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-tri-methyl-amyl-2-hydroperoxide, diisopropyl benzene one hydroperoxide, t-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-dihydro-peroxidase.This hydroperoxide have fabric and the ultra-safe advantage of color, and good bleachability is provided simultaneously.
Being used for the aliphatic diacyl peroxide that the present invention is fit to is two bay acyl peroxides, didecyl acyl peroxide, two myristoyl superoxide or their mixture.This aliphatic diacyl peroxide has fabric and the ultra-safe advantage of color, and good bleachability is provided simultaneously.
The present composition comprises, by composition total weight, and this peroxygen bleach of 0.01%-15% or their mixture, preferred 0.1%-12%, more preferably 0.5%-10%, most preferably 2%-8%.
The present composition comprises the soil-suspending agent as necessary component, and it is selected from ethoxylation cationic diamine as defined above, ethoxylation cationic polyamine, ethoxylation cationic amine polymkeric substance and their mixtures.
In the formula of above-mentioned cationic amine, R
1Can be side chain (for example:
Ring-type (for example
Or most preferably straight chain (for example-CH
2CH
2-,-CH
2CH
2CH
2-) alkylidene group, hydroxy alkylidene, alkylene group, alkarylene or oxyalkylene.For ethoxylation cationic diamine, R
1C preferably
2-C
6Alkylidene group.Each R
2Preferably methyl or-the L-X part; Each R
3C preferably
1-C
4Alkyl or hydroxyalkyl, most preferable.
The positive charge of N+ group is offset by the counter anion of proper number.The counter anion that is fit to comprises Cl-, Br-, SO
3 -2, PO
4 -2, MeOSO
3 -Deng.Particularly preferred counter anion is Cl-and Br-.
X can be a non-ionic group, and it is selected from hydrogen (H), C
1-C
4Alkyl or hydroxy alkyl ester or ether group, or their mixture.Preferred ester or ether are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.
In above-mentioned formula, hydrophilic chain L is usually fully by poly (oxyalkylene) base section-[(R
6O)
m(CH
2CH
2O)
n-] form.This poly (oxyalkylene) base section-(R
6O)
m-and-(CH
2CH
2O)
n-part may be mixed together or is preferably formed-(R
6O) m-and-(CH
2CH
2O)
nThe block thing of-part.R
6C preferably
3H
6(propylidene); M most preferably is 0 preferably 0 to about 5, and promptly this poly (oxyalkylene) base section is fully by-(CH
2CH
2O)
n-part is formed.-(CH
2CH
2O)
n-part preferably account for the poly (oxyalkylene) base section at least about 85 weight %, 100 weight % (m is 0) most preferably.
In following formula, for cationic diamine and polyamines, M
1With each M
2N+ group preferably.
Preferred ethoxylation cationic diamine has following formula:
Wherein X and n definition is the same, and a is 0-4 (for example ethylidene, propylidene, a hexa-methylene), and b is 1.For the preferred cation diamines, n is at least about 12, generally in about 12-42 scope.
In the ethoxylation cationic polyamine of following formula, R
4The C that (straight chain, side chain or ring-type) preferably replaces
3-C
6Alkyl, hydroxyalkyl or aryl; A
1Preferably:
N is preferably at least about 12, generally in about 12-42 scope; P is 3-6 preferably.Work as R
4When being the aryl that replaces or alkaryl, q preferably 1, R
5C preferably
2-C
3Alkylidene group.Work as R
4Be the alkyl, hydroxyalkyl or the alkenyl that replace and when q is 0, R
5C preferably
2-C
3The oxyalkylene part; When q is 1, R
5C preferably
2-C
3Alkylidene group.
These ethoxylation cationic polyamines can be derived from polyaminoamide, for example:
These ethoxylation cationic polyamines amino propylene oxide derivative of autohemagglutination of also can deriving, for example:
Wherein the numerical value of each c is 2-about 20.
Water-soluble cationic polymer of the present invention comprises polymer backbone, at least 2 M groups and at least one L-X group, and wherein M is connected with skeleton or becomes holistic cation group with skeleton; X is a non-ionic group, is selected from H, C
1-C
4Alkyl or hydroxy alkyl ester or ether group and their mixture; Be linking group M and X or X is connected to hydrophilic chain on the polymer backbone with L.
Here said term " polymer " skeleton " be meant that group M is connected with L-X or becomes holistic polymeric part with it.In this term, comprise oligopolymer skeleton (2-4 unit) and real polymer backbone (5 or more a plurality of unit).
Here said term " connection " meaning is that this group hangs on the polymer backbone, and the example of this connection is represented by following general structural formula A and B:
Here said term " becomes an integral body ", and the meaning is the part that this group constitutes polymer backbone, and the example is represented by following general structural formula C and D:
Can use any polymer backbone, as long as the cationic polymers that forms is water miscible and has de-sludging/antiredeposition character.The polymer backbone that is fit to can derive from urethane, polyester, polyethers, polymeric amide, polyimide etc., polyacrylate, polyacrylamide, polyvingl ether, polyethylene, polypropylene and similarly polyalkylene, polystyrene and similarly poly-alkarylene, polyalkylene amine, polyalkyleneimine, polyvinylamine, PAH, polydiene propyl group amine, polyvinylpyridine, polyaminotriazole, polyvinyl alcohol, amino gather ureylene and their mixture.
M can be any compatible cation group, and it comprises the positively charged center of N+ (quaternary ammonium).This positively charged quaternary ammonium center can be represented by following general structural formula E and F:
Particularly preferred M group is those groups that contain the quaternary ammonium center of being represented by general structural formula E.This cation group is preferably placed at approaching or becomes an integral body with polymer backbone.
The positive charge at N+ center is offset by the counter anion of proper number.The counter anion that is fit to comprises Cl
-, Br
-, SO
3 2-, SO
4 2-, PO
4 2-, MeOSO
3 -Deng.Particularly preferred counter anion is Cl
-And Br
-
X can be a non-ionic group, is selected from hydrogen (H), C
1-C
4Alkyl or hydroxy alkyl ester or ether group and their mixture.Preferred ester or ether group are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.
The ratio that the cationic polymers that is applicable to the present composition generally has cation group M and non-ionic group X is about 1: 1-1: 2.But for example (promptly contain group L-X) and blended cationic/nonionic monomer, the ratio of cation group M and non-ionic group X can change by suitable copolymerization positively charged ion, nonionic.The ratio of M and X group can be usually about 2: 1-1: 10 scopes.In the preferred cation polymkeric substance, this ratio is about 1: 1-1: 5.The polymkeric substance that is obtained by this copolymerization generally is random, and promptly positively charged ion, nonionic and blended cationic/nonionic monomer are pressed the non repetitive sequence copolymerization.
The unit that contains M and L-X group can account for 100% of cationic polymers of the present invention.But, also allow in polymkeric substance, to comprise other unit (preferred nonionic).Other unitary example comprises acrylamide, vinyl ether and contains the tertiary amine group (M of on-quaternised
1) those unit of (containing the N center).These other unit can account for the 0%-about 90% of polymkeric substance, and (unit that accounts for the about 10%-100% of polymkeric substance is the unit that contains M and L-X group, comprises M
1-L-X group).Usually, these other unit about 50% (unit that accounts for about 50%-100% of polymkeric substance is the unit that contains M and L-X group) of 0%-that account for polymkeric substance.
The number of each M and L-X group is usually at about 2-200.Typically, the number of each M and L-X group is at about 3-100.The number of preferred each M and L-X group is at about 3-40.
Not that the hydrophilic chain L that is used for linking group M and X or is connected to polymer backbone part is usually fully by poly (oxyalkylene) base section-[(R ' O)
m(CH
2CH
2O)
n]-form.This poly (oxyalkylene) base section-(R ' O)
m-and-(CH
2CH
2O)
n-can mix, or be preferably formed-(R ' O)
m-and-(CH
2CH
2O)
nThe block thing of-part.R ' is C preferably
3H
6(propylidene); M is 0-5 preferably, most preferably is 0; Promptly this poly (oxyalkylene) base section is fully by-(CH
2CH
2O)
n-part is formed.-(CH
2CH
2O)
n-part preferably account for the poly (oxyalkylene) base section at least about 85%, 100 weight % (m is 0) most preferably.For-(CH
2CH
2O)
n-part, n is usually at 3-100.Preferred n is 12-42.
A plurality of (2 or more a plurality of)-L-X partly also can connect together and be connected on the group M or on the polymer backbone, the example is represented by following general structural formula G and H:
For example, by obtaining for example structure of G and H with Racemic glycidol and group M or with the hydroxyl of polymer backbone reaction and the follow-up formation of ethoxylation.
The representational type of cationic polymers of the present invention is as follows: A. urethane, polyester, polyethers, polymeric amide or similar polymkeric substance.
The cationic polymers that one class is fit to derives from urethane, polyester, polyethers, polymeric amide etc.These polymkeric substance comprise and are selected from the unit with formula I, II and III:
A wherein
1Be:
X is 0 or 1; R is H or C
1-C
4Alkyl or hydroxyalkyl; R
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkylene group, cycloalkylidene, arylidene or alkarylene or have the C of about 20 oxygen alkylidene units of 2-
2-C
3Oxyalkylene part, condition are and A
1Do not form O-O or O-N key; When x is 1, R
2Be-R
5-, except when A
1Be:
The time, or R
2Be-(OR
8)
y-or-OR
5-, condition is and A
1Do not form O-O or O-N key, and R
3Be-R
5-, except when A
1Be:
The time, or R
3Be-(R
8O)
y-or-R
5O-, condition is and A
1Do not form O-O or O-N key; When x is 0, R
2Be:
And R
3Be-R
5-; R
4Be C
1-C
4Alkyl or hydroxyalkyl, or-(R
5)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X part; R
5Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene; Each R
6Be C
1-C
4Alkyl or hydroxyalkyl, or-(CH
2)
r-A
2-(CH
2)
s-part, wherein A
2Be-O-or-CH
2-; R
7Be H or R
4R
8Be C
2-C
3Alkylidene group or hydroxy alkylidene; X is H,
-R
9Or its mixture, wherein R
9Be C
1-C
4Alkyl or hydroxyalkyl; K is 0 or 1; M and n are feasible-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
nThe numerical value at least about 85 weight % of]-part; M is 0-about 5; N is at least about 3; R is 1 or 2, s be 1 or 2 and r+s be 3 or 4; Y is 2-about 20; U, v and w numerical value make and have at least 2 N+ centers and at least 2 X groups.
In following formula, A
1Preferably:
A
2Preferably-O-; X preferably 1; R is H preferably.R
1Can be straight chain (for example-CH
2-CH
2-CH
2-,
Or side chain (for example
Alkylidene group, hydroxy alkylidene, alkylene group, cycloalkylidene, alkarylene or oxyalkylene; Work as R
1Be C
2-C
3During the oxyalkylene part, the preferably about 2-12 of the number of oxygen alkylidene unit; R
1C preferably
2-C
6Alkylidene group or phenylene most preferably are C
2-C
6Alkylidene group (for example ethylidene, propylidene, hexa-methylene).R
2Preferably-OR
5-or-(OR
8)
y-; R
3Preferably-R
5O-or-(OR
8)
y-; R
4And R
6Methyl preferably.With R
1Similar, R
5Can be straight or branched, preferably C
2-C
3Alkylidene group; R
7Preferably H or C
1-C
3Alkyl; R
8Ethylidene preferably; R
9Methyl preferably; X is H or methyl preferably; K preferably 0; M preferably 0, r and s each preferably 2; Y is 2-about 12 preferably.
In following formula, when the number of N+ center and X group was 2 or 3, n was preferably at least about 6; N most preferably is at least about 12, and all value ranges of u+v+w are generally in about 12-42 scope.For homopolymer (v and w are 0), the preferably about 3-20 of u.For random copolymers (u is at least 1 or is preferably 0), each preferably about 3-40 of v and w.
B. polyacrylate, polyacrylamide, polyvingl ether or similarly polymkeric substance.
Another kind of suitable cationic polymers derives from polyacrylate, polyacrylamide, polyvingl ether etc.These polymkeric substance comprise and are selected from the unit with formula IV, V and VI:
A wherein
1Be:
R is H or C
1-C
4Alkyl or hydroxyalkyl; R
1Be the C that replaces
2-C
12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene or C
2-C
3Oxyalkylene; Each R
2Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene; Each R
3Be C
1-C
4Alkyl or hydroxyalkyl, or-(R
2)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X part, or combine formation-(CH
2)
r-A
2-(CH
2)
s-part, wherein A
2Be-O-or-CH
2-; Each R
4Be C
1-C
4Alkyl or hydroxyalkyl, or two R
4Combine formation-(CH
2)
r-A
2-(CH
2)
s-part; X is H,
-R
5Or its mixture, wherein R
5Be C
1-C
4Alkyl or hydroxyalkyl; J is 1 or 0; K is 1 or 0; M and n are feasible-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
nThe numerical value at least about 85 weight % of]-part; M is 0-about 5; N is at least about 3; R is 1 or 2, s be 1 or 2 and r+s be 3 or 4; U, v and w numerical value make and have at least 2 N+ centers and at least 2 X groups.
In following formula, A
1Preferably:
A
2Preferably-O-; R is H preferably.R
1Can be straight chain (for example
Or side chain (for example
The alkylidene group, hydroxy alkylidene, alkylene group, alkarylene or the oxyalkylene that replace; R
1The C of Qu Daiing preferably
2-C
6The C of alkylidene group or replacement
2-C
3Oxyalkylene most preferably is:
Each R
2C preferably
2-C
3Alkylidene group, each R
3And R
4Methyl preferably; R
5Methyl preferably; X is H or methyl preferably; J preferably 1; K preferably 0; M preferably 0; R and s each preferably 2.
In following formula, n, u, v and w can change according to n, u in urethane and the similar polymkeric substance, v and w.
C. polyalkylene amine, polyalkyleneimine or similarly polymkeric substance.
Another kind of suitable cationic polymers derives from polyalkylene amine, polyalkyleneimine etc.These polymkeric substance comprise and are selected from the unit with formula VII, VIII and IX:
R wherein
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkylene group, cycloalkylidene, arylidene or alkarylene or have the C of about 20 oxygen alkylidene units of 2-
2-C
3Oxyalkylene part, condition are not form the O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl, or-(R
3)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X part; R
3Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene; M ' is N+ or N center; X be H,
-R
4Or its mixture, wherein R
4Be C
1-C
4Alkyl or hydroxyalkyl; When M ' was N+, d was 1, and when M ' was N, d was 0; When M ' was N+, e was 2, and when M ' was N, e was 1; K is 1 or 0; M and n are feasible-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
nThe numerical value at least about 85 weight % of]-part; M is 0-about 5; N is at least about 3; X, y and z numerical value make and have at least 2 M ' groups, at least 2 N+ centers and at least 2 X groups.
In following formula, R
1Can be as the R in urethane and the similar polymkeric substance
1Equally change; Each R
2Preferably methyl or-(R
3)
k-[(C
3H
6O)
m(CH
2CH
2O) n]-the X part; R
3C preferably
2-C
3Alkylidene group; R
4Methyl preferably; X is H preferably; K preferably 0; M preferably 0.
In following formula, when the number of M ' and X group was 2 or 3, n was preferably at least about 6; N most preferably is at least about 12, and all value ranges of x+y+z are generally in about 12-42 scope.Generally, x+y+z is that 2-is about 40, preferred 2-about 20.For the polymkeric substance of short chain, x+y+z can be in the 2-9 scope, and has 2-9 N+ center and 2-11 X group.For long chain polymer, x+y+z is at least 10, preferably in about 42 scopes of 10-.For the polymkeric substance of short chain and long-chain, M ' group generally is the mixture with about 50-100%N+ center and the about 50%N of 0-center.
The preferred cation polymkeric substance derives from C in this class
2-C
3Polyalkylene amine (x+y+z is 2-9) and polyalkyleneimine (x+y+z is at least 10, preferred 10-about 42).Particularly preferred positively charged ion polyalkylene amine and polyalkyleneimine are cationic polyvinyl amine (PEA) and polymine (PEI).These preferred cation polymkeric substance comprise the unit with following general formula:
R wherein
2(preferable methyl), M ', X, d, x, y, z and n definition are the same; A is 1 or 0.
Before ethoxylation, the PEA that uses in preparation cationic polymers of the present invention has following general formula:
Wherein x+y+z is 2-9, and a is 0 or 1 (the about 100-400 of molecular weight).Each hydrogen atom that is connected with each nitrogen-atoms is represented the activity site of follow-up ethoxylation.For preferred PEA, x+y+z is about 3-7 (the about 140-310 of molecular weight).These PEA can obtain through fractionation then by ammonia and ethylene dichloride reaction.Resulting general PEA is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).More than five amine, i.e. hexamine, seven amine, eight amine and nine possible amine, they are the similar mixtures of deutero-, can not pass through fractionation by distillation, and the material that may comprise other for example cyclammonium and particularly piperazine.Also may there be the cyclammonium of being with side chain, wherein has nitrogen-atoms.Referring to the United States Patent (USP) 2792372 of the Dickson that authorizes May 14 nineteen fifty-seven, it has described the preparation of PEA.
The minimum level of preferred de-sludging/desired ethoxylation of antiredeposition performance can change according to the number of unit among the PEA.Be that n is preferably at least about 6 under 2 or 3 the situation at y+z.At y+z is under the situation of 4-9, when n is at least about 3 the time, can obtain suitable effect.For preferred cation PEA, n is at least about 12, generally in about 12-42 scope.
The PEI that uses in preparation polymkeric substance of the present invention had molecular weight at least about 440 before ethoxylation, its representative has at least about 10 unit.The preferred PEI that uses in these polymkeric substance of preparation has the about 600-1800 of molecular weight.The polymer backbone of these PEI can be represented by following general formula:
Wherein the summation of x, y and z is represented enough big numerical value, with the polymkeric substance of the molecular weight that obtains having afore mentioned rules.Although the straight-chain polymer skeleton is fine, also may there be side chain.In this polymkeric substance, exist primary, the relative proportion of the second month in a season and tertiary amine group can change, it depends on the preparation method.The distribution of amine groups is generally as follows:
-CH
2CH
2-NH
2 30％
-CH
2CH
2-NH- 40％
Define as following formula, for positively charged ion PEI, n is at least about 3.But it should be noted that the minimum level for the de-sludging/desired ethoxylation of antiredeposition performance that is fit to can increase with the increase of PEI molecular weight, when particularly a lot of above about 1800.In addition, the ethoxylation degree of preferred polymkeric substance is to increase along with the increase of PEI molecular weight.Be at least about 600 PEI for molecular weight, n is preferably at least about 12, generally in about 12-42 scope.For molecular weight is at least 1800 PEI, and n is preferably at least about 24, generally in about 24-42 scope.
D. diallyl amine polymer
Another kind of suitable cationic polymers is derived from those of diallyl amine.These polymkeric substance comprise and are selected from the unit with formula X and XI:
R wherein
1Be C
1-C
4Alkyl or hydroxyalkyl, or-(R
2)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X part; R
2Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene; Each R
3Be C
1-C
4Alkyl or hydroxyalkyl, or in conjunction with formation-(CH
2)
r-A
2-(CH
2)
s-part, wherein A be-O-or-CH
2-; X is H,
-R
4Or its mixture, wherein R
4Be C
1-C
4Alkyl or hydroxyalkyl; K is 1 or 0; M and n are feasible-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
nThe numerical value at least about 85 weight % of]-part; M is 0-about 5; N is at least about 3; R is 1 or 2, s be 1 or 2 and r+s be 3 or 4; X is 1 or 0; When x was 0, y was 1, and when x was 1, y was 0; The numerical value of u and v makes and has at least 2 N+ centers and at least 2 X groups.
In following formula, A preferably-O-; R
1Methyl preferably; Each R
2C preferably
2-C
3Alkylidene group; Each R
3Methyl preferably; R
4Methyl preferably; X is H preferably; K preferably 0; M preferably 0; R and s each preferably 2.
In following formula, when the number of N+ center and X group respectively was 2 or 3, n was preferably at least about 6, and n preferably at least 12, and u+v is generally in about 12-42 scope.Generally, v is 0, and u is that 2-is about 40, preferred 2-about 20.
According to composition of the present invention, by the gross weight of composition, comprise this soil-suspending agent of 0.01%-10% or its mixture, preferred 0.05%-5%, more preferably 0.1%-4%, most preferably 0.2%-2%.
Aqueous composition of the present invention is formulated in the acid pH scope.In fact, acidity described herein helps the decontamination/bleaching action of the present composition.The pH of present composition reality is lower than 6, more preferably less than 5, even more preferably 1-4.5, most preferably 2-4.5.
The present composition can comprise optional component, as tensio-active agent, bleach-activating agent, stablizer, sequestrant, radical scavenger, washing assistant, soil-suspending agent, dye-transfer, solvent, whitening agent, spices, suds suppressor, dyestuff or its mixture.The preferred optional component is made further more detailed description hereinafter.Laundry pretreatment process
In embodiment the most widely, the present invention relates to method with the above-mentioned liquid acidic aqueous composition pretreating fabrics of this paper.
" pretreating fabrics " should be understood to be in the method according to bleached woven fabric of the present invention, as hereinafter described, before the said fabric of washing, liquid aqueous composition of the present invention is applied at least a portion of band dirt fabric with its purified form, randomly is allowed to condition on the said fabric and acts on general 1 minute to several hours.
Therefore, the present invention includes method with liquid aqueous composition bleached woven fabric defined above, this method is included in before the described fabric of washing, said composition is applied to the step at least a portion of described fabric with its purified form, said composition and said fabric are kept in touch, and it is dry on said fabric that described composition is kept.
Described composition can keep contacting general 1 minute to several hours with said fabric, and preferred 1 minute to 1 hour, more preferably 1 minute to 30 minutes, most preferably 2-10 minute.Randomly, during the difficult relatively stain of removing on fabric pollutes/dirt, described composition can be by for example with sponge or brush or the mode that simply two fabrics rubbed toward each other, is rubbed stronger or more weakly and/or brushes.
" washing " is interpreted as water rinse fabric simply at this paper, or with washing machine or simply with the conventional composition washing fabric that comprises at least a tensio-active agent of hand use.
" with its purified form " is interpreted as liquid aqueous composition and directly is not applied on the fabric of wanting pretreated through any dilution, and liquid aqueous composition for example of the present invention is applied by described herein.
The method of pre-treatment band dirt fabric according to the present invention, the liquid aqueous composition of Shi Yonging should preferably not remain to drying on fabric in the method.In fact, found that evaporation of water helps to increase the concentration of free radical on fabric face, increases chain reaction speed thus.Infer when liquid composition remains to drying on fabric that also when water evaporates automatic oxidation reaction can take place, this automatic oxidation reaction helps to produce peroxy radical, it can cause that color is damaged and/or fabric damages.Therefore, in the method according to bleached woven fabric of the present invention, the liquid aqueous bleaching compositions drying that the present invention is used is not on fabric, and this causes the safer pretreatment operation with liquid aqueous bleaching compositions of the present invention.Optional components
The present composition also can comprise optional component, as tensio-active agent, bleach-activating agent, stablizer, sequestrant, radical scavenger, washing assistant, soil-suspending agent, dye-transfer, solvent, whitening agent, spices, suds suppressor, dyestuff or its mixture.
Therefore, liquid aqueous composition of the present invention preferably comprises tensio-active agent or its mixture.Well known to a person skilled in the art any tensio-active agent all applicable to the present invention, comprise non-ionic type, anionic, cationic, amphoteric ion type and/or amphoterics, they account for the as many as 50% of composition total weight.Tensio-active agent can further improve the decontamination stain performance of the present composition.
Because performance, nonionogenic tenside is that the present invention is highly preferred.Liquid composition of the present invention can comprise nonionogenic tenside or its mixture of as many as 50%, preferred 0.3%-30%, more preferably 0.4%-25%.Being used for suitable nonionogenic tenside of the present invention is fatty alcohol ethoxylate and/or propoxylated glycerine, and they are commercially available and have multiple Fatty Alcohol(C12-C14 and C12-C18) chain length and multiple ethoxylation degree.In fact, the HLB value of this alkoxy-based non-ionic surface active agent depends primarily on the chain length of Fatty Alcohol(C12-C14 and C12-C18), oxyalkylated character and degree of alkoxylation.
The tensio-active agent catalogue is available, and it has listed the kinds of surface promoting agent, comprises nonionogenic tenside and their corresponding HLB values.
The chemical process that is fit to that preparation is used for nonionogenic tenside of the present invention comprises corresponding pure and mild oxyalkylene with required ratio condensation.This method is well known to a person skilled in the art, is described in detail in the prior art.In addition, be applicable to that multiple alcohol alcoxylates of the present invention can be buied by various suppliers commercial.
Being specially adapted to nonionogenic tenside of the present invention is that HLB value (hydrophile-lipophile balance value) is lower than 16, preferably is lower than 15, more preferably less than 12, most preferably is lower than 10 hydrophobicity nonionogenic tenside.Find that these hydrophobicity nonionogenic tensides have good degrease performance.
The hydrophobicity nonionogenic tenside that is preferred in the present composition is that the HLB value is lower than 16 tensio-active agent, and it has following formula RO-(C
2H
4O)
n(C
3H
6O)
mH, wherein R is C
6-C
22Alkyl chain, or C
6-C
28The alkylbenzene chain, n+m is 0-20, n is 0-15, m is 0-20, preferred n+m is 1-15, n and m are 0.5-15, more preferably n+m is 1-10, n and m are 0-10.R chain preferred for the present invention is C
8-C
22Alkyl chain.Therefore, being suitable for hydrophobicity nonionogenic tenside of the present invention is: Dobanol 91-2.5 (HLB=8.1; R is C
9And C
11The mixture of alkyl chain, n are 2.5, and m is 0), or Lutensol TO3 (HLB=8; R is C
13Alkyl chain, n are 3, and m is 0), or Lutensol AO3 (HLB=8; R is C
13And C
15The mixture of alkyl chain, n are 3, and m is 0), or Tergitol 25L3 (HLB=7.7; R is C
12-C
15Alkyl chain, n are 3, and m is 0), or Dobanol 23-3 (HLB=8.1; R is C
12And C
13The mixture of alkyl chain, n are 3, and m is 0), or Dobanol 23-2 (HLB=6.2; R is C
12And C
13The mixture of alkyl chain, n are 2, and m is 0), or Dobanol 45-7 (HLB=11.6; R is C
14And C
15The mixture of alkyl chain, n are 7, and m is 0), or Dobanol 23-6.5 (HLB=11.9; R is C
12And C
13The mixture of alkyl chain, n are 6.5, and m is 0), or Dobanol 25-7 (HLB=12; R is C
12And C
15The mixture of alkyl chain, n are 7, and m is 0), or Dobanol 91-5 (HLB=11.6; R is C
9And C
11The mixture of alkyl chain, n are 5, and m is 0), or Dobanol 91-6 (HLB=12.5; R is C
9And C
11The mixture of alkyl chain, n are 6, and m is 0), or Dobanol 91-8 (HLB=13.7; R is C
9And C
11The mixture of alkyl chain, n are 8, and m is 0), or Dobanol 91-10 (HLB=14.2; R is C
9-C
11The mixture of alkyl chain, n are 10, and m is 0), or its mixture.The preferred Dobanol of the present invention 91-2.5, Lutensol TO3, Lutensol AO3, Tergitol 25L3, Dobanol 23-3 or Dobanol 23-2, or its mixture.These Dobanol tensio-active agents can be purchased from SHELL.These Lutensol tensio-active agents can be purchased from BASF.These Tergitol tensio-active agents can be purchased from UNION CARBIDE.
Other ionic surfactant pack of the present invention that is used for that is fit to is drawn together according to the polyhydroxy fatty acid amide surfactant of following formula or their mixture:
R
2-C (O)-N (R
1)-Z is R wherein
1Be H, or C
1-C
4Alkyl, C
1-C
4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-31Alkyl, Z are the polyhydroxy alkyls with the straight-chain alkyl chain that is connected directly to few 3 hydroxyls, or its oxyalkylated derivative.
Preferred R
1Be C
1-C
4Alkyl, more preferably C
1Or C
2Alkyl most preferably is a methyl; R
2Be straight chain C
7-C
19Alkyl or alkenyl, preferred straight chain C
9-C
18Alkyl or alkenyl, more preferably straight chain C
11-C
18Alkyl or alkenyl, most preferably straight chain C
11-C
14Alkyl or alkenyl, or its mixture.Z is preferably derived by reducing sugar in reductive amination process and obtains; More preferably Z is a glycosyl part.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, the same with above listed single sugar, can use high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle.Can obtain being used for the mixing sugar component of Z by these maize treacle.Will be appreciated that absolute other suitable raw material of not planning to get rid of here.Z is preferably selected from-CH
2(CHOH)
n-CH
2OH ,-CH (CH
2OH) (CHOH)
N-1-CH
2OH ,-CH
2-(CHOH)
2(CHOR ') (CHOH)-CH
2OH and its alkoxy derivative, wherein n is 3 to 5 integer, comprises 3 and 5, R ' is single saccharides of H or cyclic or aliphatic series.Most preferably n is 4 glycosyl, specifically is-CH
2-(CHOH)
4-CH
2OH.
At formula R
2-C (O)-N (R
1Among the)-Z, R
1Can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.R
2-CO-N＜can be is Oleum Cocois acid amides, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc. for example.Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.
Be applicable to that polyhydroxy fatty acid amide surfactant of the present invention can be purchased by trade(brand)name HOE by Hoechst.
The method for preparing polyhydroxy fatty acid amide surfactant is that prior art is known.Generally, they can prepare by the following method: alkylamine and reducing sugar are reacted in reductive amination process, form the corresponding N-alkyl polyhydroxy amine, then in condensation/amidation step, with N-alkyl polyhydroxy amine and aliphatic ester or triglyceride level reaction formation N-alkyl, N-polyhydroxy fatty acid amide product.The method for compositions that preparation contains polyhydroxy fatty acid amide is disclosed in for example Thomas Hedley of promulgation on February 18 nineteen fifty-nine; Co., the british patent specification 809060 of Ltd.; The United States Patent (USP) 2965576 of the E.R.Wilson of promulgation on December 20 nineteen sixty, United States Patent (USP) 2703798 with the Anthony M.Schwartz of March 8 nineteen fifty-five promulgation etc., United States Patent (USP) 1985424 with the Piggott that issued on December 25th, 1934, in WO92/06070, they all quote for referencial use at this paper.
Liquid aqueous composition of the present invention also can comprise other tensio-active agent except comprising nonionogenic tenside, as anion surfactant or their mixture.Anion surfactant is preferred in the present invention as optional component, because they play wetting agent, promptly in laundry applications, their wet fabrics, the spot on the hydrophilic fabric particularly, help peroxygen bleach to finish its bleaching action thus, therefore help to improve scourability the spot that can bleach.In addition, anion surfactant makes it possible to obtain clear composition, even comprises hydrophobic components for example during hydrophobic surfactant when described composition.Composition of the present invention by composition total weight, can comprise the described anion surfactant of 0.1%-20%, or its mixture, preferred 0.2%-15%, more preferably 0.5%-13%.
Being specially adapted to of the present invention is sulfonate and sulfate surfactant.As anion surfactant is commonly known in the art, has found to be widely used in the merchant and has sold in the washing composition.These anion surfactants comprise C
8-C
22Alkylbenzene sulfonate (LAS), C
8-C
22Alkyl-sulphate (AS), unsaturated vitriol is oleyl sulfate, C10-C18 alkyl alkoxy sulfate (AES) and C10-C18 alkyl alkoxy carboxylate salt for example.The neutralizing cation that is used for negatively charged ion synthesising sulfonate and/or vitriol represented by the conventional positively charged ion that is widely used in the washing composition technology, for example sodium, potassium or alkanol ammonium.The present invention is alkyl-sulphate preferably, particularly has 6-18 carbon atom in alkyl chain, the Oleum Cocois alkyl-sulphate of preferred 8-15 carbon atom or their mixture.
Other anion surfactant that is used for the decontamination purpose also can be used for the present invention.These can comprise soap salt (comprise, for example, the ammonium salt of sodium, potassium, ammonium and replacement such as list, two and triethanolamine salt), C
8-C
22Uncle or secondary alkyl sulfonate, C
8-C
24Alkene sulfonate, by the sulfonation poly carboxylic acid that the pyrolysis product to alkaline earth metal citrate carries out sulfonation preparation, as GB patent 1,082,179 is described; C
8-C
24Alkyl polyglycol ether sulfate (comprising 10 moles oxyethane at the most); Alkyl ester sulfonate such as C
14-C
16Methyl ester sulfonate; Monoesters (the particularly saturated and unsaturated C of acylglycerol sulfonated ester, fatty oil base glycerol ester vitriol, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, isethionate such as acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinate
12-C
18Monoesters), the diester of sulfosuccinate (particularly saturated and unsaturated C
6-C
14Diester), the vitriol of the vitriol of alkyl polysaccharide such as the many polyglycosides of alkyl (nonionic non-sulfuric acid compound described below).Resinous acid and hydrogenated resin acid also suit, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in the butter or are obtained by butter.Other example can be referring to: " tensio-active agent and washing composition " (" Surface Active Agents and Detergents ") (I and II volume, Schwartz, Perry and Berch).Various these type of tensio-active agents also usually are disclosed in United States Patent (USP) 3,929,678 (1975.12.30 is issued to Laughlin etc.), and 23 hurdles, 58 walk to 29 hurdles, 23 row (it quotes for referencial use at this paper).
Other is applicable to that anion surfactant of the present invention also comprises with the acyl sarcosinate of acid and/or salt form or their mixture, preferably has the long acyl sarcosinate of following formula:
Wherein M is hydrogen or cationic moiety, and wherein R has 11-15 carbon atom, the alkyl of preferred 11-13 carbon atom.Preferred M is hydrogen and an alkali metal salt, particularly sodium and potassium.Described acyl sarcosinate tensio-active agent is obtained by natural acid and amino acid sarkosine (sarcosine).They are suitable as the aqueous solution use of powder with its salt or sour form.As the derivative of natural acid, described acyl sarcosinate can be fast and complete biodegradable, and have good and skin-friendliness.
Therefore, particularly preferredly be used for long acyl sarcosinate of the present invention and comprise C
12Acyl sarcosinate (promptly the wherein M according to following formula is a hydrogen, and R is the acyl sarcosinate with alkyl of 11 carbon atoms) and C
14Acyl sarcosinate (promptly the wherein M according to following formula is a hydrogen, and R is the acyl sarcosinate with alkyl of 13 carbon atoms).C
12Acyl sarcosinate is commercially available, for example the Hamposyl L-30 that is supplied by Hampshire
C
14Acyl sarcosinate is commercially available, for example the Hamposyl M-30 that is supplied by Hampshire
Also can comprise according to liquid aqueous composition of the present invention and well known to a person skilled in the art other tensio-active agent, as the amine oxide surfactant according to formula R1R2R3NO, wherein each R1, R2, R3 are C independently
1-C
30, preferred C
1-C
20, C most preferably
1-C
16Hydrocarbon chain.The content of amine oxide can be as many as 10%, the more preferably 1%-3% of composition total weight.
The present composition comprises bleach-activating agent or the conduct of its mixture is chosen wantonly but highly preferred component.The present composition that further comprises bleach-activating agent or its mixture provides more effective bleachability, situation at ambient temperature particularly, and pretreatment operation is carried out under this envrionment temperature.Here " bleach-activating agent " meaning is meant the compound that generates peracid with hydroperoxidation.The peracid of Xing Chenging has constituted the activatory SYNTHETIC OPTICAL WHITNER like this.Being specially adapted to bleach-activating agent of the present invention is hydrophobic bleach activator, promptly can not be basically and stably miscible with water activator.This hydrophobic bleach activator generally has and is lower than 11, preferably is lower than 10 the 2nd HLB value (hydrophile-lipophile balance value).The 2nd HLB well known to a person skilled in the art, and is defined in for example P.Becher, " the emulsification principle and put into practice " of Reinhold, and New York, 1957, or P.Sherman, " the emulsification science " of Academic Press, London, 1969.
Be applicable to that bleach-activating agent of the present invention comprises those that belong to ester, acid amides, imide or acid anhydride class.The example of this suitable compounds is disclosed among English Patent GB1586769 and the GB2143231, and its method that forms the pill form is described among European patent application EP-A-62523.The suitable example that is used for such compound herein is: tetra acetyl ethylene diamine (TAED), 3; 5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt, as for example at the diperoxy dodecylic acid described in the US4818425 with as for example at peroxide hexanodioic acid nonyl acid amides described in the US4259201 and positive nonanoly acyloxy benzene sulfonate (NOBS).Also suitable is the N-acyl caprolactam, and it is selected from: replace or unsubstituted benzoyl caprolactam, capryloyl hexanolactam, nonanoyl hexanolactam, caproyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, formyl radical hexanolactam, ethanoyl hexanolactam, propionyl hexanolactam, butyryl radicals hexanolactam, pentanoyl hexanolactam or its mixture.Special gang's bleach-activating agent of being concerned about is disclosed among the EP624154, particularly preferably is acetyl triethyl citrate (ATC) in this family.The advantage of acetyl triethyl citrate is because it is degraded into citric acid and alcohol at last, so favourable to environment.In addition, acetyl triethyl citrate has good stability to hydrolysis in product when storing, and be effective bleach-activating agent.At last, it is returned composition the good ability of washing that helps is provided.
According to composition of the present invention, in composition total weight, can contain 0.01-20%, preferred 1-10%, the more preferably described bleach-activating agent of 2-7% or its mixture.
According to each component that exists and its content, aqueous composition of the present invention can be mixed with solution, milk sap or microemulsion.As mentioned above, the present composition that generally comprises bleach-activating agent preferably is mixed with the aqueous emulsions of described bleach-activating agent in the matrix that contains water, peroxygen bleach, soil-suspending agent and emulsifying surfactant system, or is mixed with the microemulsion of described bleach-activating agent in the matrix that contains water, peroxygen bleach, soil-suspending agent and hydrophilic surfactant system.
The milk sap that the present invention preferably contains peroxygen bleach comprises the emulsifying surfactant system of at least two kinds of different tensio-active agents.In order to make stable milk sap, the preferred described two kinds of different tensio-active agents of this paper should have different HLB values (hydrophile-lipophile balance value), and preferably the difference of the HLB of these two kinds of tensio-active agents is at least 1, and preferably at least 2.In fact, can be made at 40 ℃ and placed at least two weeks down, basically without separating into the milk sap of different layers by suitably in water, mixing at least two kinds of said tensio-active agents with different HLB.
Milk sap according to the present invention can also contain other tensio-active agent except containing described emulsifying surfactant system, but they should change the weighted average HLB value of total milk sap not obviously.
In the embodiment preferred of milk sap of the present invention, wherein milk sap comprises the water-insoluble component of the above-mentioned bleach-activating agent of emulsification such as this paper, and this emulsification system satisfies formula:
And A% (weight)+B% (weight)=100%; HLB (X) HLB of emulsive component that indicates wherein, if there are several emulsive components of wanting, X represents its all (weighted mean based on the % of each component) in the formula so, the HLB of HLB (A) expression hydrophilic surfactant or its mixture, the HLB of HLB (B) expression hydrophobic surfactant or its mixture.
In the particularly preferred embodiment of milk sap of the present invention, wherein milk sap comprises acetyl triethyl citrate as bleach-activating agent, and it is 6 hydrophobic non ionic surfactants that suitable surfactant system comprises HLB for example, for example Dobanol
R23-2 and for example HLB are 15 hydrophilic nonionic tensio-active agent, for example Dobanol
R91-10.Other nonionic surfactant system that is fit to comprises for example Dobanol
R(23-6.5 HLB about 12) and Dobanol
R23 (HLB is lower than 6), or Dobanol
R45-7 (HLB=11.6) and Dobanol23-3 (HLB=8.1).
Be formulated in the preferred embodiment of the invention of milk sap at composition, described composition is opaque.In centrifugal check, observing milk sap of the present invention does not have demonstration to be separated under 6000rpm after 15 minutes.In the microscopic method check, described milk sap shows as the dispersion of drop in matrix.
In an embodiment of the present invention, wherein the present composition is formulated into microemulsion, and bleaching microemulsion of the present invention comprises the hydrophilic surfactant system that contains at least two kinds of different tensio-active agents such as nonionogenic tenside and anion surfactant.Being used for suitable hydrophilic surfactant of the present invention is those above-mentioned hydrophilic surfactants of this paper.Comprise in the embodiment of peroxygen bleach and bleach-activating agent at microemulsion of the present invention, in order stably to mix bleach-activating agent in described microemulsion, key factor is that at least a described tensio-active agent in the hydrophilic surfactant system must have the HLB value different with bleach-activating agent.In fact,, may form the single phase of successive, therefore reduce the chemical stability of bleach/bleach activator system if all said tensio-active agents have identical HLB value with activator.The HLB difference of preferred at least a said tensio-active agent and said bleach-activating agent is at least 1.0 HLB units, preferred 2.0 HLB units.
Be configured in embodiment of the present invention of microemulsion at composition, said composition is transparent on the macroscopic view not existing under opalizer and the dyestuff.In centrifugal check, observe the said microemulsion of the present invention and under 6000rpm, do not show after 15 minutes and be separated.Under the microscopic method check, this microemulsion shows as the dispersion of drop in matrix.We have observed this particle has general pact or is lower than 3 microns diameter dimension.
Being used for sequestrant that the present invention is fit to comprises and is selected from following sequestrant: the aromatic chelating agent of phosphine acid salt chelator, aminocarboxylate sequestrant, multifunctional replacement and the other sequestrant as glycine, Whitfield's ointment, aspartic acid, L-glutamic acid, propanedioic acid or its mixture.When using, sequestrant content in the present invention by composition total weight, is generally 0.001%-5%, preferred 0.05%-2%.
Being used for the phosphine acid salt chelator that the present invention is fit to can comprise: ethydronic acid and aminophosphonic acid salt compound comprise that amino alkylidenyl gathers (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.These phosphonate compounds can its sour form or the different cationic salt existence of conduct on its part or all of acid functional group.Preferred amino phosphonates do sequestrant used herein be diethylenetriamine pentamethylenophosphonic acid(DTPP) salt (DTPMP), 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP) and amino three (methylene phosphonic acids) (ATMP).Such phosphine acid salt chelator can be from Monsanto with trade(brand)name DEQUEST
Buy.
The aromatic chelating agent of multifunctional replacement also can be used for the present composition.See the people's such as Connor of promulgation on May 21st, 1974 US3812044.The preferred compound of this class acid form is a dihydroxyl disulfobenzene for example 1,2-dihydroxyl-3,5-disulfobenzene.
The preferred biodegradable cheating agent that is used for herein is quadrol N, N '-disuccinic acid, or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.Quadrol N, N '-disuccinic acid, particularly (S, S) isomer has been described in detail among the US4704233 of the Hartman of on November 3rd, 1987 promulgation and Perkins.For example, quadrol N, N '-disuccinic acid are with trade(brand)name ssEDDS from Palmer Research Laboratories
RBuy.
Suitable aminocarboxylate used herein comprises: edetate, diethylentriamine pentacetate, diethylentriamine pentacetate (DTPA), N-Oxyethylethylenediaminetriacetic acid salt, triglycollamic acid salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, hydroxyethyl Diglycocol, trimethylenedinitrilo-tertraacetic acid (PDTA) and methylglycine oxalic acid (MGDA), the two is its sour form or with its basic metal, ammonium and substituted ammonium salt form.Be specially adapted to herein aminocarboxylate and be diethylentriamine pentacetate, for example from BASF with trade(brand)name Trilon FS
Trimethylenedinitrilo-tertraacetic acid of buying (PDTA) and methylglycine oxalic acid (MGDA).
Be used for the in addition preferred sequestrant of the present invention and have following formula:
R wherein
1, R
2, R
3And R
4Be independently 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; And R
5, R
6, R
7And R
8Be independently selected from-H and alkyl.
Be used for the particularly preferred sequestrant of the present invention and be 1-hydroxyl ethane diphosphonate (HEDP) and amino three (methylene phosphonic acids) (ATMP), diethylenetriamine methylene phosphonic acid salt (DTPMP), ethylidene N, N '-disuccinic acid, diethylentriamine pentacetate, glycine, Whitfield's ointment, aspartic acid, L-glutamic acid, propanedioic acid or its mixture.
Be used for list and dihydroxy-benzene and its analogue, alkyl and aryl carboxylic acid salt and its mixture that suitable free-radical scavengers of the present invention comprises known replacement.This free-radical scavengers that preferably is used for herein comprises: di-tert-butyl hydroxy toluene (BHT), quinhydrones, di-tert-butyl hydroquinone, a tertiary butylated hydroquinone, tertiary butyl hydroxybenzene methyl ether (anysole), phenylformic acid, toluic acid, pyrocatechol, tert-butyl catechol, benzylamine, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, grain gallate-based n-propyl or its mixture it is highly preferred that di-tert-butyl hydroxy toluene.When using free-radical scavengers, its content in the present invention by composition total weight, is generally 0.001%-2%, preferred 0.001%-0.5%.
The existence of sequestrant and/or free-radical scavengers made before the described fabric of washing, helped the present composition can be applicable to colored fabric through Long contact time pre-treatment band dirt safely.
Composition of the present invention can also comprise polyamines polymkeric substance or its mixture of soil suspension.The polyamines polymkeric substance that well known to a person skilled in the art any soil suspension also can be used among the present invention.Being used for the particularly suitable polyamines polymkeric substance of the present invention is the poly-alkoxylation polyamines.This material can be expressed as the molecule of the experience structural formula with following repeating unit usually:
The amine form and
Quaternary ammonium form wherein R is the alkyl that has 2-6 carbon atom usually; R
1Can be C
1-C
20Alkyl; Alkoxyl group is oxyethyl group, propoxy-etc., and y is 2-30, most preferably 10-20; N is at least 2 integer, preferred 2-20, most preferably 3-5; X
-Be the negatively charged ion that produces by quaterisation, for example halogen ion or methylsulfate.
Being used for the preferred polyamines of topnotch of the present invention is so-called ethoxylation polyvinylamine, i.e. the polymeric reaction product of oxyethane and ethylene imine, and it has following general formula:
Y=2-30 wherein.Be used for the present invention and particularly preferably be the ethoxylation polyvinylamine, particularly ethoxylation tetren and quaternised ethoxylation hexamethylene-diamine.
The present composition by composition total weight, generally comprises polyamines polymkeric substance or its mixture of this soil suspension of 0.01%-15%, preferred 0.1%-5%, more preferably 0.2%-3%.
The present composition also can comprise solvent or its mixture.More specifically, found in liquid composition according to the present invention, to add the effect that solvent system also helps described composition, promptly further improved to various types of spots comprise oil stain, enzyme stain and the spot that can bleach always go to steep performance, described solvent system comprises at least a hydrophobic solvent and at least a hydrophilic solvent.Usually, liquid aqueous composition of the present invention is by composition total weight, can comprise as many as 10% hydrophobic solvent or its mixture, preferred 0.1%-5%, more preferably 0.2%-2%, hydrophilic solvent or its mixture of as many as 20%, preferred 0.5%-15%, more preferably 1%-10%.
The hydrophobic solvent that is fit to that the present invention uses comprises terpenes as single-and those terpenes of double-ring monoterpene, particularly hydro carbons, and it comprises terpinene, terpinolene, limonene and firpene and its mixture.The preferred material of this class camber is d-limonene, kautschin, α-Pai Xi and/or beta-pinene.Other hydrophobic solvent comprises all types of paraffin, and they all are straight chain and non-straight chain, contains 2-20 carbon atom, preferred 4-10, more preferably 6-8 carbon atom.This paper is octane preferably.Be applicable to that other hydrophobic solvent of the present invention is a benzylalcohol.Be used for the particularly preferred hydrophobic solvent of the present invention and comprise d-limonene, kautschin, α-Pai Xi, beta-pinene, octane, benzylalcohol or its mixture.
Be used for the hydrophilic solvent that the present invention is fit to and comprise the alkoxylate fatty alcohol, as methoxypropanol, oxyethyl group propyl alcohol, propoxy-propyl alcohol, butoxy propyl alcohol and alkoxylated diols, as oxyethyl group-ethoxy ethanol, fatty alcohol such as ethanol, propyl alcohol and glycol such as propylene glycol or its mixture.
Well known to a person skilled in the art that any polymerization dirt release agent can randomly be used for the compositions and methods of the invention.The polymerization dirt release agent is characterised in that it contains hydrophilic segment and hydrophobic part simultaneously, and wherein hydrophilic segment makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; Hydrophobic part be deposited on the hydrophobic fiber surface and in whole washing, rinse cycle all the time attached to fiber surface on, therefore to hydrophilic segment tailor-made the using of weighing anchor.This feasible spot easier cleaning in washing process thereafter that after dirt release agent is handled, produces.
The polymerization dirt release agent that the present invention uses especially comprises those dirt release agents with following composition: (a) mainly by (i) or (ii) or one or more nonionic hydrophilic components of (iii) forming, wherein (i) is that the polymerization degree is at least 2 polyoxyethylene part, (ii) be that the propylene oxide or the polymerization degree are the polyoxypropylene part of 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless this unit is connected the two ends of adjacent part by ehter bond, the mixture that (iii) contains the oxyalkylene units of about 30 propylene oxide units of ethylene oxide and 1-, wherein said mixture contains abundant ethylene oxide unit, thereby make hydrophilic component that enough big wetting ability be arranged, when this dirt release agent is deposited on the surface of normal polyester synthon, can increase its surperficial wetting ability.Described hydrophilic segment preferably contains at least about 25% ethylene oxide unit, more preferably, and particularly for this component that contains 20-30 the propylene oxide unit of having an appointment, at least about 50% ethylene oxide unit; Or (b) comprise (i), and (ii), (iii) or (iv) one or more hydrophobic ingredients of part, wherein (i) is C
3Oxyalkylene terephthalic acid ester moiety, if wherein described hydrophobic ingredient also comprises the ethylene oxide terephthalate, then ethylene oxide terephthalate and C
3The ratio of oxyalkylene terephthalate units is about 2: 1 or is lower, (ii) is C
4-C
6Alkene or oxidation C
4-C
6Alkene part, or their mixture (iii) are poly-(vinyl ester) parts, and preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester), (iv) is C
1-4Alkyl oxide or C
4Hydroxyalkyl ether substituting group, or their mixture, substituting group wherein is with C
1-4Alkyl oxide or C
4Hydroxyalkyl ether derivatived cellulose or its form of mixtures exist, and this derivatived cellulose is amphipathic, therefore make them have the C of q.s
1-4Alkyl oxide and/or C
4The hydroxyalkyl ether unit to be being deposited on the conventional polyethylene terephthalate surface and keeping the hydroxyl of q.s, in case be adsorbed on these conventional synthon when surperficial when it, can increase the wetting ability of fiber surface; Or combination (a) and (b).
Although also can use the polymerization degree of higher degree, be generally about 1-200 in the polymerization degree of (a) polyoxyethylene part in (i), preferably 3-about 150; More preferably 6-about 100.The oxidation C that is fit to
4-6The alkene hydrophobic part is including, but not limited to polymerization dirt release agent end-blocking part, as MO
3S (CH
2)
nOCH
2CH
2O-, M is a sodium in the formula, n is the integer of 4-6, as in the United States Patent (USP) 4721580 of authorizing in 26 days January in 1988 of Gosselink disclosed those.
The polymerization dirt release agent that uses among the present invention also comprises derivatived cellulose, hydroxy ethers cellulose polymer compound for example, the copolymerization block thing of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide terephthalate or poly(propylene oxide) terephthalate etc.These reagent all have commercially available, comprising the Mierocrystalline cellulose hydroxy ethers as METHOCEL (Dow).The Mierocrystalline cellulose dirt release agent that the present invention uses also comprises and is selected from C
1-4Alkyl and C
4Those of hydroxy alkyl cellulose; United States Patent (USP) 4000093 referring to the people such as Nicol that authorized on December 28th, 1976.
The dirt release agent that is characterised in that poly-(vinyl ester) hydrophobic part comprises poly-(vinyl ester), as C
1-6The graft copolymer of vinyl ester preferably grafts on poly-(vinyl-acetic ester) on polyoxyalkylene skeleton such as the polyethylene oxide skeleton.European patent application 0219048 referring to people such as disclosed Kud on the 22nd April in 1987.This commercially available class dirt release agent comprises SOKALAN type material, and for example SOKALAN HP-22 is obtained by BASF (West Germany).
The preferred dirt release agent of one class is the multipolymer with ethylene glycol terephthalate and the random block of polyethylene oxide (PEO) terephthalate.The molecular weight of this polymerization dirt release agent is about 25000-about 55000.United States Patent (USP) 3893929 referring to the United States Patent (USP) 3959230 of the Hays that authorized on May 25th, 1976 and the Basadur that authorized on July 8th, 1975.
Another kind of preferred polymerization dirt release agent is the polyester that has the ethylene glycol terephthalate repeating unit, it contains the ethylene glycol terephthalate unit of 10%-15% (weight) and the polyoxyethylene terephthalate unit of 90%-80% (weight), and it is that the polyoxyethylene glycol of 300-5000 obtains by molecular-weight average.The example of this polymkeric substance comprises commercially available material ZELCON5126 (Dupont production) and MILEASE T (ICI production).United States Patent (USP) 4702857 referring to the Gosselink that authorized on October 27th, 1987.
Also having a kind of preferred polymerization dirt release agent is the sulfonated products that is essentially the linear ester oligopolymer, and this oligopolymer contains terephthaloyl and the multiple unitary oligomer ester skeleton of oxyalkylene oxygen basic weight, and the terminal portions that links to each other with this skeleton covalency.In J.J.Scheibel that authorize November 6 nineteen ninety and the United States Patent (USP) 4968451 of E.P.Gosselink these dirt release agents there is complete description.Other polymerization dirt release agents that are suitable for comprise the terephthalate polyester in the people's such as Gosselink that on December 8th, 1987 authorized the United States Patent (USP) 4711730, the block polyester oligopolymer in the United States Patent (USP) 4702857 of the Gosselink that the end capped oligomer ester of negatively charged ion in the United States Patent (USP) 4721580 of the Gosselink that on January 26th, 1988 authorized and on October 27th, 1987 authorize.
Preferred polymerization dirt release agent also comprises the dirt release agent in the people's such as Maldonado that on October 31st, 1989 authorized the United States Patent (USP) 4877896, this patent disclosure negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl.
Preferred in addition dirt release agent is the oligopolymer with following repeating unit: terephthaloyl unit, sulfo group isophthaloyl base unit, oxygen ethyleneoxy group and oxygen-1; 2-propylidene unit, these repeating units have constituted the skeleton and the preferred isethionate end-blocking with modification of oligopolymer.Particularly preferred this type of dirt release agent comprises an about sulfo group isophthaloyl base unit, 5 terephthaloyl unit, ratios are oxygen ethylidene oxygen and the oxygen-1 of about 1.7-1.8; the end-blocking unit of 2-propylidene oxygen unit and 2 2-(2-hydroxy ethoxy) ethane sulfonic acid sodium.This dirt release agent also comprises by the about 0.5%-20% minimizing of the weight of oligopolymer crystalline stablizer, and this stablizer is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and its mixture.Referring to the United States Patent (USP) 5415807 that licenses to May 16 nineteen ninety-five such as Gosselink etc.
If the use dirt release agent, then to be generally about 0.01%-of detergent composition weight of the present invention about 10.0% for its consumption, and it is about 5% to be generally about 0.1%-, preferably about 0.2%-about 3.0%.
The present composition can comprise that also one or more effectively suppress the material that dyestuff shifts to another kind of fabric from a kind of fabric in cleaning process.Usually, this dye transfer inhibitor comprises polyvinylpyrrolidonepolymers polymers, polyamines N-oxide polymer, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, manganese phthalocyanine, peroxidase and their mixture.If you are using, the content of these reagent be generally composition weight about 0.01% to about 10%, preferred about 0.01% to about 5%, more preferably from about 0.05% to about 2%.
More particularly, being preferred for polyamines N-oxide polymer of the present invention contains and has following structural: R-A
xThe unit of-P; Wherein P is a polymerizable unit, and wherein a part or the N-O base that the N-O base can be connected with this unit or the N-O base can constitute this polymerizable unit can be connected with two unit; A be down one of array structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; With R be aliphatic group, the ethoxylation aliphatic group, aromatic group, heterocyclic radical or alicyclic radical or their any combinations, wherein the nitrogen-atoms in the N-O base can be connected with this group or the N-O group is the part of these groups.Preferred polyamines N-oxide compound is that wherein R is heterocyclic radical such as pyridine, pyrroles, imidazoles, tetramethyleneimine, those of piperidines and their derivative.
The N-O group can be represented with following formula:
R wherein
1, R
2, R
3Be aliphatic series, aromatics, heterocycle or alicyclic group or their combination; X, y and z are 0 or 1; Can be connected on any aforementioned group with the nitrogen of N-O group or constitute the part of any aforementioned group.The amine oxide unit of polyamines N-oxide compound has pK
a＜10, preferred pK
a＜7, more preferably pK
a＜6.
The present invention can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dye transfer rejection.The example of suitable polymeric skeleton comprises polyvinyls, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is an amine n-oxide, and other monomer type is the N-oxide compound.The amine n-oxide polymkeric substance generally has 10: 1 to 1: 1000000 the amine and the ratio of amine n-oxide.But the quantity that is present in the amine oxide in the polyamine oxidase thing polymkeric substance can change by suitable copolymerization or by suitable N-degree of oxidation.The polyamine oxidase thing can obtain with any polymerization degree almost.Typically, average molecular weight range is 500-1000000; More preferably 1000-500000; 50000-100000 most preferably.Such preferable material can be called " PVNO ".The most preferred polyamines N-oxide compound that can be used in the detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50000, and the ratio of amine and amine n-oxide is about 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being called " PVPVI ") also is preferred for the present invention.Preferred PVPVI has 5000-1000000, more preferably 5000-200000 and the most preferably molecular-weight average of 10000-20000.(average molecular weight range by as at " chemical analysis " of Barth etc., the 113rd volume, light scattering method of describing in " modernism of polymer characterization " determines that the disclosed content of the document is quoted as a reference at this paper).The PVPVI multipolymer generally has 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1 the N-vinyl imidazole and the molar ratio of N-vinyl pyrrolidone.These multipolymers can be straight chain or side chain.
The present composition also can use molecular-weight average for about 5000 to about 400000, preferred about 5000 to about 200000 and more preferably from about 5000 to about 50000 Polyvinylpyrolidone (PVP) (" PVP ").PVP is known to the skilled in the detergent applications; For example, referring to EP-A-262897 and EP-A-256696, these two pieces of patents are quoted as a reference by this paper.It is about 500 to about 100000 that the composition that contains PVP also can contain molecular-weight average, preferred about 1000 to about 10000 polyoxyethylene glycol (" PEG ").Preferably, what discharge in washing soln is about 2: 1 to about 50: 1 by the PEG of ppm and the ratio of PVP, more preferably from about 3: 1 to about 10: 1.
High if desired foam then can mix suds booster such as C in said composition
10-16Alkanolamide, its content is generally 1%-10%.C
10-C
14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.With this class suds booster and high bubble cosurfactant, as above-mentioned amine oxide, it also is favourable that trimethyl-glycine, sultaine use together.If necessary, also can add as MgCl
2, MgSO
4Deng the solubility magnesium salts obtaining more foam and strengthen to remove the grease performance, their usage quantity is generally 0.1%-2%.
When the present composition is designed to handle fabric or when washing, any white dyes well known in the art or other brightener or whitening agent generally can mix in the present composition by about 0.05% to about 1.2% content for detergent composition weight of the present invention.Can be used for commercially available white dyes of the present invention and can be divided into following group, it comprises, but needn't be subject to: stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophen-5, the 5-dioxide, the pyrroles, 5-and 6-unit heterocyclic whitening agent, listed is illustrative and nonrestrictive.The example of these whitening agent is disclosed in " production of white dyes and application (The Production andApplication of Fluorescent Brightening Agents) ", and M.Zahradnik is by JohnWiley ﹠amp; Sons, New York publishes (1982).
The specific examples of the white dyes that uses in the present composition is those that point out in the U.S. Pat 4790856 of the Wixon that authorized on December 13rd, 1988.These whitening agent comprise the PHORWHITE series of Verona.Disclosed other whitening agent comprises in this reference: the Tinopal UNPA that can buy from Ciba-Geigy, Tinopal CBS and Tinopal5BM; Artic White CC and Aric White CWD obtain by being positioned at gondola Hilton-Davis; 2-(4-styryl phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The specific examples of these whitening agent comprises: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho-[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.In addition referring to the U.S. Pat 3646015 of the Hamilton that authorized on February 29th, 1972.The negatively charged ion whitening agent generally is that the present invention is preferred.
The present composition that is fit to pretreating fabrics can be packaged in the various containers, comprises conventional bottle, the bottle of ball, sponge, brush or atomizer is housed.In addition, aqueous composition of the present invention is chemically stable, but they can be packaged in the container/bottle of given froth breaking, can not damage the stability that contains described composition through the described container/bottle of long storage time.Decontamination stain performance/bleachability test method
Under pretreatment condition, given composition can be by following test method evaluation to the decontamination stain and/or the bleachability of the fabric of band dirt.At first be applied in the band spot part of described fabric according to aqueous composition of the present invention, allow it act on about 1-10 minute, general 5 minutes, described pretreating fabrics washs the sufficiently long time down at 30 ℃-70 ℃ with conventional detergent composition according to common wash conditions then, to bleach described fabric.For example, the typical band dirt fabric that uses in this test method can be from EMC (Empirical Manufacturing Company) Cincinnati, Ohio, USA is purchased, for example the soil stain on two kinds of different substrate/fabrics for example cotton (CW120) and poly-cotton (PCW28), chocolate, macaroni condiment, dirty machine oil, makeup, tea, coffee, bloodstain.By will and using object of reference with the pretreated band dirt of present composition fabric, pretreated those fabrics of same combination that for example do not contain with good grounds soil-suspending agent of the present invention are relatively estimated decontamination stain/bleachability side by side then.By scoring unit (psu) of panel, determine difference with range estimation grading standard with the 0-4 value range.
Further specify the present invention by following examples.Embodiment
By the listed component of listed mixed prepare following composition (weight %, unless otherwise indicated). composition I II III IV V VI VII VIIIDobanol 45-7 6.4 6.4 6.4 1.5 12.0 6.0-1.5Dobanol 23-3 8.6 8.6 8.6--6.0 1.5 1.5Dobanol 23-6.5---1.5----Dobanol 91-10------1.5-C25-AE-2.5-S 4.0 4.0 4.0 1.5 12.0 6.0--C10 alkyl sulfates------1.7 1.7 alkyl grape sugar acid amides 2.0 2.0 2.0-----ATC*3.5 3.5 3.5-3.5---H
2O
24.0 4.0 4.0-6.0 4.0 7.0 7.0 2 bay acyl peroxides 0.5--1.0-2.0--EHDQ
*0.5 0.5 0.5 0.2 1.0 0.7 0.5 0.5 limonene D (+)--0.5 0.1 0.5 1.0--benzylalcohol--2.0 1.0----1-methoxyl group-2-propyl alcohol--5.0-2.0 3.0--ATMP
* *0.2 0.1--0.16---HEDP
* * *-------0.16DTPMP
* * * *------0.18-water and minor component is to 100%H
2SO
4To pH4ATC
*Be that acetyl triethyl citrate Dobanol 23-3 is that HLB is 8.1 C12-C13 nonionic ethoxylated surfactant.Dobanol 23-6.5 is that HLB is 11.9 C12-C13 nonionic ethoxylated surfactant.Dobanol 45-7 is that HLB is 11.6 C14-C15 nonionic ethoxylated surfactant.Dobanol 91-10 is that HLB is 14.7 C9-C11 nonionic ethoxylated surfactant.ATMP
* *Be amino three (methylene phosphonic acids).DTPMP
* * * *Be diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.HEDP
* * *It is 1-hydroxyl ethane diphosphonate.EHDQ
* *Be with the quaternised 24-ethoxylation of methyl chloride hexamethylene-diamine
At the usefulness described fabric of water rinse or before the U.S. or the washing of European wash conditions according to standard, when with the fabric of above-mentioned any composition I-VIII pre-treatment band dirt, for example, keep this composition and act on fabric, when contacting about 5 minutes, various spots have been obtained fabulous decontamination stain performance, described spot comprises the spot such as the macaroni condiment of fats/oils spot such as soil stain, dirty machine oil, makeup, lipstick, carotenoid type, the spot that can bleach such as tea steep and enzyme steeps as grass steeps, bloodstain.
Claims (14)
1. the liquid aqueous composition of a suitable pretreating fabrics, its pH are lower than 6 and comprise peroxygen bleach and be selected from the soil-suspending agent of following material:
1) have the ethoxylation cationic diamine of following formula:
M wherein
1Be N+ or N group; Each M
2Be N+ or N group, at least one M
2It is the N+ group;
2) have the ethoxylation cationic polyamine of following formula:
3) ethoxylation cationic polymers, it comprises polymer backbone, at least 2 M groups and at least one L-X group, and wherein M is connected with skeleton or becomes holistic cation group with skeleton; X is a non-ionic group, is selected from H, C
1-C
4Alkyl or hydroxy alkyl ester or ether group and their mixture; Be linking group M and X or X is connected to hydrophilic chain on the polymer backbone with L;
4) their mixture; A wherein
1Be
R is H or C
1-C
4Alkyl or hydroxyalkyl, R
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene, or have the C of about 20 oxygen alkylidene units of 2-
2-C
3Oxyalkylene part, condition are not form the O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl ,-L-X part; Or two R
2In conjunction with formation-(CH
2)
r-A
2-(CH
2)
s-part, wherein A
2Be-O-or-CH
2-, r is 1 or 2, and s is 1 or 2, and r+s is 3 or 4; Each R
3Be C
1-C
8Alkyl or hydroxyalkyl, benzyl, L-X part, or two R
3Or R
2With a R
3In conjunction with formation-(CH
2)
r-A
2-(CH
2)
s-part; R
4Be to have p C that replaces the replacement at position
3-C
12Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R
5Be C
1-C
12Alkenyl, hydroxy alkylidene, alkylene group, arylidene or alkarylene, or have the C of about 20 oxygen alkylidene units of 2-
2-C
3Oxyalkylene part, condition are not form O-O or O-N key; X is selected from H, C
1-C
4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and their mixture; L contains the poly (oxyalkylene) base section :-[(R
6O)
m(CH
2CH
2O)
n]-hydrophilic chain; R wherein
6Be C
3-C
4Alkylidene group or hydroxy alkylidene, m and n are feasible-(CH
2CH
2O)
n-part accounts for the numerical value at least about 50 weight % of said poly (oxyalkylene) base section; Work as M
2When being N+, d is 1, works as M
2When being N, d is 0; For said cationic diamine, n is about 6 and for said cationic polyamine and cationic polymers at least, and n is 3 at least; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1.
2. according to the composition of claim 1; wherein said peroxygen bleach is hydrogen peroxide or its water-soluble sources; the water-soluble source of described hydrogen peroxide is preferably selected from percarbonate; persilicate; persulphate; perborate; peroxy acid; hydroperoxide; diacyl peroxide and its mixture; be more preferably hydrogen peroxide; tert-butyl hydroperoxide; the cumyl hydroperoxide; 2; 4; 4-tri-methyl-amyl-2-hydroperoxide; diisopropyl benzene one hydroperoxide; t-amyl hydroperoxide; 2; 5-dimethyl-hexane-2, the 5-dihydro-peroxidase; two bay acyl peroxides; the didecyl acyl peroxide; two myristoyl superoxide or their mixture.
3. according to the composition of arbitrary aforesaid right requirement, it comprises by composition total weight, 0.01%-15%, preferred 0.1%-12%, more preferably 0.5%-10%, most preferably described peroxygen bleach of 2%-8% or their mixture.
4. require among the 1-3 each composition according to aforesaid right, wherein said soil-suspending agent is ethoxylation cationic diamine, wherein R
1Be C
2-C
6Alkylidene group, preferred hexa-methylene.
5. require among the 1-3 each composition according to aforesaid right, wherein said soil-suspending agent is the ethoxylation cationic polyamine, and wherein R4 is the C that replaces
3-C
6Alkyl, hydroxyalkyl or aryl; A
1Be:
With p be 3-6.
6. require among the 1-3 each composition according to aforesaid right, wherein said soil-suspending agent is an ethoxylation cationic amine polymkeric substance, it has and is selected from following skeleton: urethane, polyester, polyethers, polymeric amide, polyimide, polyacrylate, polyacrylamide, polyvingl ether, polyalkylene, polystyrene, poly-alkarylene, polyalkylene amine, polyalkyleneimine, polyvinylamine, PAH, polydiene propyl group amine, polyvinylpyridine, polyaminotriazole, polyvinyl alcohol, amino poly-ureylene and their mixture.
7. according to the composition of arbitrary aforesaid right requirement, it comprises by composition total weight, 0.01%-10%, preferred 0.05%-5%, more preferably 0.1%-4%, the most preferably described soil-suspending agent of 0.2%-2% or its mixture.
8. according to the composition of arbitrary aforesaid right requirement, it also comprises by composition total weight, preferred 0.01-20%, more preferably 1-10%, most preferably 2-7% bleach-activating agent.
9. composition according to Claim 8; wherein said bleach-activating agent is selected from acetyl triethyl citrate; tetra acetyl ethylene diamine; 3; 5; 5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt; the diperoxy dodecylic acid; peroxide hexanodioic acid nonyl acid amides; positive nonanoly acyloxy benzene sulfonate; the N-acyl caprolactam; replace and unsubstituted benzoyl caprolactam; the capryloyl hexanolactam; the nonanoyl hexanolactam; the caproyl hexanolactam; the decanoyl hexanolactam; the undecylene acyl caprolactam; the formyl radical hexanolactam; the ethanoyl hexanolactam; the propionyl hexanolactam; the butyryl radicals hexanolactam; pentanoyl hexanolactam and composition thereof, preferably acetyl triethyl citrate.
10. according to the composition of arbitrary aforesaid right requirement, its pH is lower than 5, and more preferably 1-4.5 most preferably is 2-4.5.
11. according to the composition that arbitrary aforesaid right requires, it also comprises at least a optional components that is selected from tensio-active agent, stablizer, sequestrant, radical scavenger, washing assistant, soil-suspending agent, dye-transfer, solvent, whitening agent, spices, suds suppressor, dyestuff and its mixture.
12. according to the composition that arbitrary aforesaid right requires, it is the form of milk sap or microemulsion.
13. method with the liquid acidic aqueous composition bleaching band dirt fabric that requires according to arbitrary aforesaid right, described method is included in before the described fabric of washing, described composition is applied to the step at least a portion of described fabric with its purified form.
14. according to the method for claim 13, wherein before the described fabric of washing, described composition and described fabric were kept in touch 1 minute to 1 hour, preferred 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97181136 CN1242798A (en) | 1996-10-31 | 1997-10-30 | Liquid aqueous bleaching compositions and pretreatment process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96870137.5 | 1996-10-31 | ||
| CN 97181136 CN1242798A (en) | 1996-10-31 | 1997-10-30 | Liquid aqueous bleaching compositions and pretreatment process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1242798A true CN1242798A (en) | 2000-01-26 |
Family
ID=5178108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97181136 Pending CN1242798A (en) | 1996-10-31 | 1997-10-30 | Liquid aqueous bleaching compositions and pretreatment process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1242798A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106232796A (en) * | 2014-02-28 | 2016-12-14 | 雷克特本克斯尔(品牌)有限公司 | Compositions |
-
1997
- 1997-10-30 CN CN 97181136 patent/CN1242798A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106232796A (en) * | 2014-02-28 | 2016-12-14 | 雷克特本克斯尔(品牌)有限公司 | Compositions |
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