CN1238802A - Detergent composition comprising cationic amines and lipase enzymes - Google Patents
Detergent composition comprising cationic amines and lipase enzymes Download PDFInfo
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- CN1238802A CN1238802A CN 97199989 CN97199989A CN1238802A CN 1238802 A CN1238802 A CN 1238802A CN 97199989 CN97199989 CN 97199989 CN 97199989 A CN97199989 A CN 97199989A CN 1238802 A CN1238802 A CN 1238802A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
Abstract
Granular detergent compositions or components thereof containing a lipase enzyme and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal / anti-redeposition properties, for use in laundry and dish washing processes.
Description
Technical field
The present invention relates to be used to do washing and granular detergent composition or its component of wash up, wherein comprise and have particulate/cation compound and the lipase of dirt removal/antiredeposition performance.
Background of invention
The performance of a particularly important of detergent composition is its ability of removing granular dirt in washing process from various fabrics.Modal granular dirt may be an earth type dirt.The dirt particle generally comprises silico-aluminate negative electricity layer, and the positive electricity positively charged ion (as calcium) that is positioned at interlayer and combines with the negative electricity layer.
Remove the compound of performance for having particulate/dirt, can propose various patterns.A kind of pattern requires this compound to have two kinds of different characteristics.First compound is adsorbed onto the ability on the mud particles negative electricity layer, and it two is, in case absorption, this compound draws back the ability of (expansion) negative electricity layer, and mud particles just loses its bounding force like this, can remove in washing water then.
Except removing dirt, also need make the dirt of being removed keep suspending in the cycle in laundry (or wash up).The dirt of removing and being suspended in the washing water from fabric can deposit on the fabric face again.This dirt that deposits again can produce particularly noticeable delustring or " burnt hair " effect on white fabrics.In order to reduce this problem, can contain anti redeposition agent in the detergent composition.
For example, EP-B-111965 disclose have simultaneously that dirt is removed and the cation compound of antiredeposition performance in detergent application.
US4659802 and US4664848 have described having of can being used in combination with anion surfactant, and dirt is removed and the season amine of antiredeposition performance.
About the anti-redeposition of the positive electric compound of antiredeposition, a kind of pattern has been proposed below.In washing water, positively charged molecule can be given these granulin molecule dispersing propertys in the lip-deep adsorption of mud particles.Along with increasing this compound is adsorbed onto on the suspended state dirt particle, the latter just is enclosed in by connecting in the hydrophilic layer that ethoxy unit produced.Like this,, just can suppress hydrophilic coating dirt, especially deposit again on the hydrophobic fabric (as polyester) at fabric at laundry or wash up in the cycle.
Other detergent ingredients that often adopts in washing composition is a lipase.This enzyme becomes known for helping in the detergent composition to remove oil-dirt (containing triglyceride level or fatty ester).For example WO92/05249 discloses some and has improved Lipase variants of performance and preparation method thereof.
In general, it is directly related with its concentration in cleaning composition that lipase is removed the performance of spot, if therefore improve lipase content then improve the ability of removal spot.But find in extraordinary circumstances, for example adopt short machine washing circulation, or during cold washing heavily contaminated matrix, lipase can reach optimum performance under finite concentration, if surpass this level, increases lipase content again, can not reach the effect that improves decontamination stain performance.
The applicant finds that now this problem can add lipase and solves in the granular detergent composition (or its component) that contains cationic moiety season ethoxylation (gathering) amine (it has the dirt of removing/antiredeposition character).Both adopted positively charged ion season ethoxylation (gathering) amine, adopted the detergent composition (or its component) of lipase again, and, proved to produce unexpectedly better the cleaning and softening performance compared with the cleaning composition that adopts these two kinds of compositions separately separately.
Even further advantages of the invention are only to finish a cycles of washing also can find out cleaning effect afterwards.
All documents of quoting in this specification sheets, its relevant portion all is incorporated herein as reference.
Summary of the present invention
The present invention relates to granular detergent composition or its component, wherein comprise lipase and one or more have the cation compound of particulate/dirt removal/antiredeposition performance, be i.e. positively charged ion (part) season ethoxylation (gathering) amine compound.
In more detail, the present invention relates to granular detergent composition or its component, wherein comprise:
(a) lipase; With
(b) have the water-soluble cationic compound of dirt removal/antiredeposition performance, it is selected from:
1) has ethoxylation positively charged ion one amine of following structural formula
3) have the ethoxylation cationic diamine of following structural formula:
M wherein
1Be N+ or N group; Each M
2Be N+ or N group; And at least one M
2Be the N+ group;
3) have the ethoxylation cationic polyamine of following structural formula:
4) and composition thereof; A wherein
1Be
R is H or C
1-C
4Alkyl or hydroxyalkyl, R
1Be C
2-C
12Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2-
2-C
3The oxyalkylene part, but can not form any O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl ,-the L-X part, or two R
2Formation-(CH together
2)
r-A
2-(CH
2)
s-part, wherein A
2For-O-or-CH
2-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; Each R
3Be C
1-C
8Alkyl or hydroxyalkyl, benzyl ,-the L-X part, perhaps, two R
3Or R
2With a R
3Formation-(CH together
2)
r-A
2-(CH
2)
s-part; R
4For replacing C
3-C
12Alkyl, hydroxyalkyl, alkenyl, aryl or have the alkaryl of para-orientation position; R
5Be C
1-C
12Alkenyl, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2-
2-C
3The oxyalkylene part, but can not form any O-O or O-N key; X is for being selected from H, C
1-C
4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof; L is for containing polyoxyalkylene part-[(R
6O)
m(CH
2CH
2O)
n]-hydrophilic chain; R wherein
6Be C
3-C
4Alkylidene group or hydroxyl alkylidene group, and the number of m and n should make-(CH
2CH
2O)
n-part account for described polyoxyalkylene part at least about 50% weight; M
2During for N+, d is 1, M
2During for N, d is 0; For described positively charged ion one amine, n is at least about 16, for described cationic diamine at least about 6, for described cationic polyamine at least about 3; P is 3-8; Q is 1 or 0; T is 1 or 0, but q is 1 o'clock, and t is 1.
Wherein compound (a) and ratio (b) are 1: 100 to 100: 1
Detailed description of the present invention
An essential characteristic of the present invention is the water-soluble cationic compound with particulate/dirt removal/antiredeposition performance, and it is selected from positively charged ion one amine, diamines and polyamine.
Lipolytic enzyme is 1: 100 to 100: 1 with the ratio of water-soluble cationic compound, preferred 1: 10 to 10: 1, and most preferably 1: 5 to 5: 1.
In detergent composition, water-soluble cationic compound is preferably the 0.01-30% of detergent composition weight, more preferably 0.1-15%, most preferably 0.2-3.0%.
Cationic amine
According to the present invention, the water-soluble cationic compound of the present invention that can be used for granular detergent composition or its component comprises ethoxylation positively charged ion one amine defined above, ethoxylation cationic diamine and ethoxylation cationic polyamine.
In the aforementioned structural formula of cationic amine, R
1Can be side chain (as,
Cyclic (as,
Or most preferably straight chain (as-CH
2CH
2-,-CH
2CH
2CH
2-) alkylidene group, hydroxyl alkylidene group, alkenylene, alkarylene or oxyalkylene.For ethoxylation cationic diamine, R
1Preferred C
2-C
6Alkylidene group.Each R
2Preferable methyl or-the L-X part; Each R
3Preferred C
1-C
4Alkyl or hydroxyalkyl, most preferable.
The positive charge of N+ group is offset by the counter anion of suitable number.Suitable counter anion comprises Cl
-, Br
-, SO
3 -2, PO
4 -2, MeOSO
3-Deng.Particularly preferred counter anion is Cl
-And Br
-
X is selected from hydrogen (H), C
1-C
4A non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof.Preferred ester or ether are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.
In aforementioned structural formula, hydrophilic chain L is usually fully by polyoxyalkylene part [(R
6O)
m(CH
2CH
2O)
n]-form.In the polyoxyalkylene part-(R
6O)
m-and-(CH
2CH
2O)
n-can mix, or be preferably formed-(R
6O)
m-part and-(CH
2CH
2O)
nThe block of-part.R
6Preferred C
3H
6(propylidene); The preferred 0-of m is about 5, and most preferably 0, promptly this polyoxyalkylene part is fully by-(CH
2CH
2O)
n-form.-(CH
2CH
2O)
n-part preferably account for polyoxyalkylene part at least about 85% weight, most preferably account for 100% weight (m is 0).
In aforementioned structural formula, for cationic diamine and polyamine, M
1With each M
2Preferred N+ group.
Preferred ethoxylation positively charged ion one amine and diamines have following structural formula:
Wherein X and n define as above, and a is 0-20, preferred 0-4 (as, ethylidene, propylidene, hexylidene), b is 1 or 0.For preferred cation one amine (b=0), n is preferably at least about 16, and its representative value scope is about 20-35.For preferred cation diamines (b=1), n is at least about 12, and its representative value scope is about 12-42.
In the aforementioned structural formula of ethoxylation cationic polyamine, R
4(straight chain, side chain or cyclic) preferably replaces C
3-C
6Alkyl, hydroxyalkyl or aryl; A
1Preferably
N is preferably at least about 12, and its representative value scope is about 12-42; The preferred 3-6 of p.Work as R
4During for substituted aryl or alkaryl, q preferred 1 and R
5Preferred C
2-C
3Alkylidene group.Work as R
4Be substituted alkyl, hydroxyalkyl or alkenyl, and q is at 0 o'clock, R
5Preferred C
2-C
3The oxyalkylene part; When q is 1, R
5Preferred C
2-C
3Alkylidene group.
These ethoxylation cationic polyamines can be derived from the polyamino acid amides, as:
Or
These ethoxylation cationic polyamines also can be derived from polyamino propylene oxide derivative, as:
Wherein each c is 2-about 20.
Lipase
Another basal component of granular detergent composition of the present invention or its component is lipolytic enzyme or lipase.
Lipolytic enzyme is 1: 100 to 100: 1 with the ratio of water-soluble cationic compound, more preferably 1: 10 to 10: 1, and most preferably 1: 5 to 5: 1.
In the detergent composition, lipolytic enzyme or lipase preferably account for the 0.01%-3% of composition weight, more preferably 0.03%-1%, and 0.06%-0.5% most preferably is most preferably based on the 100KLU/g activity.
The lipase of suitable detergent use comprises the lipase of Rhodopseudomonas microorganisms, Pseudomonas stutzeri ATCC19.154 for example, and as English Patent 1,372,034 is introduced, also referring to the described lipase of disclosed Japanese patent application on February 24 in 1978.Described lipase can be available from Amano Pharm Pur GmbH (Japanese Nagoya), and its commodity are called lipase P " Amano ", are called " Amano-P " below.Other commercially available lipase comprises Amano-CES, come the lipase of autohension pigment bacillus, for example the steatolysis of viscosity pigment bacillus belongs to mutation NRRLB3673, can be available from the Toyo Jozo of Japanese Tagata, also can buy viscosity pigment bacillus lipase in addition from U.S. Biochemics Inc. and Dutch Disoynth company, and from the lipase of Tang Changpu pseudomonas.The LIPOLASE enzyme can be the preferred lipase of this paper available from Novo (seeing EPO 341,947) derived from thin cotton shape hair humic bacterium.
The lipase of particularly suitable is Ml Lipase
RAnd Lipomax
R(Gist-Brocades) and Lipolase
RWith Lipolase Ultra
R(Novo), when combining with the present composition, these lipase are very effective.The EP 258068 of Novo Nordisk, the WO94/03578 of WO 92/05249 and WO95/22615 and Unilever, the lipase that WO 95/35381 and WO 96/00292 are introduced also is suitable for the present invention.
The lipolytic enzyme of at [EC 3.1.1.50] and so on also is fit to, and they can think a kind of special lipase, promptly do not need the lipase of interface interaction.Relevant at adds cleaning composition, at WO-A-88/09367 (Genencor), among WO 90/09446 (Plant Genetic System) and WO 94/14963 and the WO 94/14964 (Unilever) introduction is arranged all.
Used another the preferred lipase of the present invention is the mutation of D96L lipolytic enzyme, and it is the mutation derived from the natural lipase of dredging cotton shape hair humic bacterium.Most preferably use and dredge cotton shape hair humic bacteria strain DSM4106.
Relevant D96L lipolytic enzyme mutation meaning is the described lipase mutation of WO 92/05249 patent application, wherein from the natural lipase of dredging cotton shape hair humic bacterium, the aspartic acid (D) at the 96th place has become leucine (L), according to relevant nomenclature, described 96 last aspartic acids are substituted by leucine and promptly are expressed as D96L.For measuring the activity of described D96L enzyme, use standard LU method of testing (analytical procedure, Novo Nordisk inside AF95/6-GB1991.02.07).Use gum arabic to make emulsifying agent, make tributyrin (Merck) emulsification prepare the substrate of D96L.Use static PH method to measure lipase activity in PH7.
Cationic polymers
Detergent composition and component thereof can comprise other cationic ethoxy amine polymer with particulate/dirt removal/antiredeposition performance that is selected from water-soluble cationic polymer.These polymkeric substance comprise main polymer chain, at least 2 M groups and at least one L-X group, wherein M be connected on the main chain or with main chain be the cation group of one; As non-ionic group, X is selected from H, C
1-C
4Alkyl or hydroxy alkyl ester or ether group and mixed group thereof; And L is for connecting M group and X group or X being connected to hydrophilic chain on the main polymer chain.
In detergent composition, the consumption of cationic ethoxy amine polymer is the 0.01-30% of detergent composition weight, more preferably 0.1-15%, most preferably 0.2-3%.
Herein, term " polymer " main chain " be meant the polymeric part that group M and L-X are connected or are combined as a whole.This term comprises oligopolymer main chain (2-4 unit) and true polymers main chain (5 or more multiple-unit).
In this article, term " is connected to " and is meant, the side group of this group for coming out from main polymer chain, and the example of this mode of connection can be represented by following general formula A and B:
In this article, term " is combined as a whole " and is meant that this group becomes the part of main polymer chain, and its example can be represented by following general formula C and D:
As long as formed cationic polymers is water miscible and has earth removal/antiredeposition performance, just can use any main polymer chain.The suitable polymers main chain can be derived from urethane, polyester, polyethers, polymeric amide, polyimide etc.; Polyacrylic ester, polyacrylamide, polyvingl ether, polyethylene, polypropylene and similarly polyalkenes, polystyrene and similarly poly-(alkarylene), polyalkyleneamines, polyalkylene imines, polyvinylamine, poly-alkylamine, polydiene propyl group amine, polyvinylpyridine, polyamino triazole, polyvinyl alcohol, amino poly-(ureylene), and composition thereof.
M contains N
+Any compatible cation group of (quaternary salt) positive center.The positive center of quaternary salt can be represented by following structure E and F:
Particularly preferred M group contains the quaternary salt center of being represented by general formula E.Cation group preferably is combined as a whole near main polymer chain or with it.
N
+The positive charge at center is offset by the counter anion of suitable number.Suitable counter anion comprises Cl
-, Br
-, SO
3 -2, SO
4 2-, PO
4 -2, MeOSO
3 -, or similar negatively charged ion.Particularly preferred counter anion is Cl
-And Br
-
X is selected from hydrogen (H), C
1-C
4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof.Preferred ester or ether are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.
According to the present invention, in the cationic polymers that is applicable to detergent composition and component thereof, the ratio of cation group M and non-ionic group X is generally about 1: 1-1: 2.But,, can change the ratio of cation group M and non-ionic group X for example by suitable copolymerizable cationic monomers, non-ionic monomer (promptly containing the L-X group) and cationic/nonionic mix monomer.The ratio of group M and radicals X generally can be about 2: 1-1: 10.In the preferred cation polymkeric substance, this ratio is about 1: 1-1: 5.Normally random by the polymkeric substance that this copolyreaction forms, promptly cationic monomer, non-ionic monomer and cationic/nonionic mix monomer carry out copolymerization according to non-repetitive order.
The unit that contains group M and group L-X can comprise 100% cationic polymers of the present invention.But the unit (preferably non-ionic) that also can in polymkeric substance, comprise other.Other unitary example comprises acrylamide, vinyl ether and contains not season tertiary amine group (M
1) those groups (having the N center).These other unit can comprise the polymkeric substance of 0-about 90%, and (polymkeric substance of about 10-100% is for containing M and the L-X group (comprises M
1-L-X group) unit).Usually, these other unit can comprise the polymkeric substance (polymkeric substance of about 50-100% is the unit that contains M and L-X group) of 0-about 50%.
The group number of M and L-X is respectively about 2-200.Usually, the number of M and L-X group is respectively about 3-100.The number of preferred L and L-X group is respectively about 3-40.
Except being used to connect M group and X group or being used to be connected to part on the main polymer chain, hydrophilic chain L is usually fully by polyoxyalkylene part-[(R ' O)
m(CH
2CH
2O)
n]-form.In the polyoxyalkylene part-(R ' O)
m-and-(CH
2CH
2O)
n-part can mix, or be preferably formed-(R ' O)
m-with-(CH
2CH
2O)
nThe block of-part.The preferred C of R '
3H
6(propylidene); The preferred 0-of m is about 5, and most preferably 0, promptly this polyoxyalkylene part is fully by-(CH
2CH
2O)
n-form.-(CH
2CH
2O)
n-part preferably accounts for the polyoxyalkylene part at least about 85% weight, most preferably 100% weight (m is 0).For-(CH
2CH
2O)
n-part, n is generally about 3-100.N is preferably about 12-42.
A plurality of (2 or more) but-L-X part also hook connect together, be connected to then on M group or the main polymer chain, its example can be represented by following general formula G and H:
But the structure ethoxylation of G and H and so on is for example reacted by Racemic glycidol and M group or with main polymer chain, then formed hydroxyl-oxethylization is obtained.
The typical example of cationic polymers of the present invention is as follows:
A. urethane, polyester, polyethers, polymeric amide or similarly polymkeric substance.
One class suitable cationic polymers is derived from urethane, polyester, polyethers, polymeric amide or analogue.These polymkeric substance comprise and are selected from those unit with structural formula I, II and III:
A wherein
1For
X is 0 or 1; R is H or C
1-C
4Alkyl or hydroxyalkyl; R
1Be C
2-C
12Alkylidene group, hydroxyl alkylidene group, alkenylene, cycloalkylidene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2-
2-C
3The oxyalkylene part, but can not with A
1Form any O-O or O-N key; When x is 1, R
2For-R
5-, unless A
1For
Or be-(OR
8)
y-or-OR
5-, but can not with A
1Form any O-O or O-N key, and R
3For-R
5Unless, A
1For
Or be-(OR
8)
y-or-OR
5-, but can not with A
1Form any O-O or O-N key; When x is 0, R
2For:
And R
3For-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
2Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene; Each R
6Be C
1-C
4Alkyl or hydroxyalkyl or-(CH
2)
r-A
2-(CH
2)
s-, A wherein
2For-O-or-CH
2-; R
7Be H or R
4R
8Be C
2-C
3Alkylidene group or hydroxyl alkylidene group; X be H,
-R
9, or its mixed group, wherein R
9Be C
1-C
4Alkyl or hydroxyalkyl; K is 0 or 1; M and n should make-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; R is 1 or 2; S is 1 or 2, and r+s is 3 or 4; Y is 2-about 20; The numerical value of u, v and w should make it have at least 2 N
+Center and at least 2 X groups.
In above structural formula, A
1Preferably
A
2Preferably-O-; X preferred 1; And the preferred H of R.R
1Can be line style (as ,-CH
2-CH
2-CH
2-,
Or side chain (as
Alkylidene group, hydroxyl alkylidene group, alkenylene, cycloalkylidene, alkarylene or oxyalkylene; Work as R
1Be C
2-C
3During the oxyalkylene part, the preferably about 2-12 of the number of oxyalkylene units; R
1Preferred C
2-C
6Alkylidene group or phenylene, most preferably C
2-C
6Alkylidene group (as, ethylidene, propylidene, hexylidene).R
2Preferably-OR
5-or-(OR
8)
y-; R
3Preferably-R
5O-or-(OR
8)
y-; R
4And R
6Preferable methyl.As R
1The same, R
5Can be straight chain or side chain, preferred C
2-C
3Alkylidene group; R
7Preferred H or C
1-C
3Alkyl; R
8Preferred ethylidene; R
9Preferable methyl; Preferred H of X or methyl; K preferred 0; M preferred 0; R and s difference preferred 2; The preferably about 2-12 of y.
In above structural formula, n is preferably at least about 6, at this moment N
+The number of center and X group is 2 or 3; N is most preferably at least about 12, and for the u+v+w of all scopes, its representative value scope is about 12-42.For homopolymer (v and w are 0), the preferably about 3-20 of u.For random copolymers (u is at least 1 or preferred 0), v and w are preferably about 3-40 respectively.
B. polyacrylic ester, polyacrylamide, polyvingl ether or similarly polymkeric substance.
Another kind of suitable cationic polymers is derived from polyacrylic ester, polyacrylamide, polyvingl ether or similar polymkeric substance.These polymkeric substance comprise and are selected from those unit with structural formula IV, V and VI:
A wherein
1For
R is H or C
1-C
4Alkyl or hydroxyalkyl; R
1For replacing C
2-C
12Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C
2-C
3The oxyalkylene part; Each R
2Be C
1-C
12Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene; Each R
3Be C
1-C
4Alkyl or hydroxyalkyl ,-(R
2)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X part or common formation-(CH
2)
r-A
2-(CH
2)
s-part, wherein A
2For-O-or-CH
2-; Each R
4Be C
1-C
4Alkyl or hydroxyalkyl or two R
4Common formation-(CH
2)
r-A
2-(CH
2)
s-part; X be H,
-R
5, or its mixed group, wherein R
5Be C
1-C
4Alkyl or hydroxyalkyl; J is 1 or 0; K is 1 or 0; The numerical value of m and n should make-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; R is 1 or 2; S is 1 or 2, and r+s is 3 or 4; The numerical value of u, v and w should make it have at least 2 N
+Center and at least 2 X groups.
In above structural formula, A
1Preferably
Or
A
2Preferably-O-; The preferred H of R.R
1Can be straight chain (as,
) or side chain (as
Substituted alkylene, hydroxyl alkylidene group, alkenylene, alkarylene or oxyalkylene; R
1The preferred C that replaces
2-C
6Alkylidene group or replacement C
2-C
3Oxyalkylene, most preferably
Or
Each R
2Preferred C
2-C
3Alkylidene group; R
3And R
4The difference preferable methyl; R
5Preferable methyl; Preferred H of X or methyl; J preferred 1; K preferred 0; M preferred 0; R and s difference preferred 2.
In above structural formula, according to n, u, v and the w of urethane and similar polymkeric substance, can be with n, u, v and w change.
C. polyalkylene amine, polyalkyleneimine or similar polymkeric substance.
Another kind of suitable cationic polymers is derived from polyalkylene amine, polyalkyleneimine or similar polymkeric substance.These polymkeric substance comprise and are selected from those unit with structural formula VII, VIII and IX:
R wherein
1Be C
2-C
12Alkylidene group, hydroxyl alkylidene group, alkenylene, cycloalkylidene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2-
2-C
3The oxyalkylene part, but can not form any 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, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene; M ' is N
+Or N center; X be H,
-R
4, or its mixed group, wherein R
4Be C
1-C
4Alkyl or hydroxyalkyl; M ' is N
+The time, d is 1, when M ' was N, d was 0; M ' is N
+The time, e is 2, when M ' was N, e was 1; K is 1 or 0; The numerical value of m and n should make-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; The numerical value of x, y and z should make it have at least 2 M ' groups, at least 2 N
+Center and at least 2 X groups.
In above structural formula, R
1Can resemble the R in urethane and the similar polymkeric substance
1Change like that; Each R
2Preferable methyl or-(R
3)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X part; R
3Be C
2-C
3Alkylidene group; R
4Preferable methyl; The preferred H of X; K preferred 0; M preferred 0.
In above structural formula, n is preferably at least about 6, and at this moment the number of M ' and X group is 2 or 3; N is most preferably at least about 12, and for the x+y+z of all scopes, its representative value scope is about 12-42.Usually, x+y+z is that 2-is about 40, preferred 2-about 20.For short chain polymer, x+y+z is 2-9, has 2-9 N simultaneously
+Center and 2-11 X group.For long chain polymer, x+y+z is at least 10, preferred 10-about 42.For short chain and long chain polymer, M ' is generally the N of about 50-100%
+The mixed form at the N center of center and 0-about 50%.
Preferred this cationoid polymer-derived is from C
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 the poly-ethyleneamines of positively charged ion (PEA ' s) and polyethylene imines (PEI ' s).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 as above; A is 1 or 0.Before ethoxylation, the PEA that is used to prepare cationic polymers of the present invention has following general formula:
Wherein x+y+z is 2-9, and a is 0 or 1 (molecular weight of about 100-400).Each hydrogen atom that is connected on each nitrogen-atoms represents to be used for the reactive site of ethoxylation subsequently.For preferred PEA, x+y+z is about 3-7 (molecular weight of about 140-310).These PEA can obtain by fractionation then by comprising the reaction of ammonia and ethylene dichloride.Usually the PEA of gained is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).More than five amine, promptly hexamine, seven amine, eight amine and may nine amine, be difficult for fractionation by distillation owing to belong to deriving mixture together, therefore wherein can comprise other material, as cyclammonium, piperazine particularly.Also can there be cyclammonium, wherein contains nitrogen-atoms with side chain.Referring to, authorize the United States Patent (USP) № 2792372 of Dickson April 14 nineteen fifty-seven, wherein described the preparation process of PEA.
According to the unit number among the PEA, can change the required minimum ethoxylation degree of preferred dirt removal/antiredeposition performance.When y+z was 2 or 3, n was preferably at least about 6.If y+z is 4-9, then n can produce suitable effect at least about 3 o'clock.For preferred cation PEA, n is at least about 12, and its representative value scope is about 12-42.
At least about 440, this represents at least about 10 unit the molecular weight of PEI that is used to prepare polymkeric substance of the present invention before ethoxylation.The molecular weight that is used to prepare the preferred PEI of these polymkeric substance is about 600-1800.The main polymer chain of these PEI can be represented by following general formula:
Wherein the summation of x, y and z represents to obtain to have the number of the required enough sizes of the polymkeric substance of aforementioned molecular weight.Although can be the simple linear polymer main chain, also side chain can be arranged.According to preparation method, can change in the polymkeric substance primary, the relative proportion of the second month in a season and tertiary amine group.The distribution of amine groups is as follows usually :-CH
2CH
2-NH
230%-CH
2CH
2-NH-40%
Be connected among the PEI hydrogen atom on each nitrogen-atoms and represent to be used for the reactive site of ethoxylation subsequently.These PEI can,, have down polymerization ethylenimine and obtaining by at catalyzer as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, spirit of salt, acetate etc.The concrete grammar of preparation PEI is disclosed in, and the United States Patent (USP) № that the United States Patent (USP) № that authorizes people such as Ulrich December 5 nineteen thirty-nine March 8 in 2182306,1962 authorized people such as Mayle authorized people's such as Esselmann United States Patent (USP) № 2208095, the United States Patent (USP) № 2806839 that authorizes Crowther September 17 nineteen fifty-seven and authorizes the United States Patent (USP) № 2533696 (incorporating the present invention as a reference at this) of Wilson March 21 nineteen fifty-one on July 16 in 3033746,1940.
As defined in aforementioned structural formula, for positively charged ion PEI, n is at least about 3.But should be noted that the required minimum ethoxylation degree of suitable dirt removal/antiredeposition performance can increase along with the raising of PEI molecular weight, particularly far surpass about 1800 the time when the PEI molecular weight.In addition, the ethoxylation degree of preferred polymers also increases along with the raising of PEI molecular weight.At least about 600 PEI, n is preferably at least about 12 for molecular weight, and its representative value scope is about 12-42.Be at least 1800 PEI for molecular weight, n is preferably at least about 24, and its representative value scope is about 24-42.
D. diallyl amine polymer.
Another kind of suitable cationic polymers is derived from diallyl amine.These polymkeric substance comprise and are selected from the unit with structural 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, hydroxyl alkylidene group, alkylidene group, arylidene or alkarylene; Each R
3Be C
1-C
4Alkyl or hydroxyalkyl or common formation-(CH
2)
r-A-(CH
2)
s-part, wherein A be-O-or-CH
2-; X be H,
-R
4, or its mixed group, wherein R
4Be C
1-C
4Alkyl or hydroxyalkyl; K is 1 or 0; The numerical value of m and n should make-(CH
2CH
2O)
n-part accounts for-[(C
3H
6O)
m(CH
2CH
2O)
n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; R is 1 or 2; S is 1 or 2, and r+s is 3 or 4; X is 1 or 2; X is 0 o'clock, and y is 1, and x is 1 o'clock, and y is 0; The numerical value of u and v should make it have at least 2 N
+Center and at least 2 X groups.
In above structural formula, A is preferred-O-; R
1Preferable methyl; Each R
2Preferred C
2-C
3Alkylidene group; Each R
3Preferable methyl; R
4Preferable methyl; The preferred H of X; K preferred 0; M preferred 0; R and s difference preferred 2.
In above structural formula, n is preferably at least about 6, at this moment N
+The number of center and X group is 2 or 3; N is most preferably at least about 12, and for the u+v of all scopes, its representative value scope is about 12-42.Usually, v is 0, and u is that 2-is about 40, preferred 2-about 20.
Other detergent component
According to the present invention, detergent composition and component thereof also can comprise other detergent component.The exact nature of these other components and add-on thereof depend on the physical aspect of composition or component and the exact nature of used washing operation thereof.
Composition of the present invention and component thereof preferably comprise one or more other detergent component, and they are selected from additional surfactants, washing assistant, sequestrant, SYNTHETIC OPTICAL WHITNER, bleach precursor, bleaching catalyst, organic polymer, other enzyme, suds suppressor, lime soap dispersing agent, additional dirt suspension and anti redeposition agent, stain remover, spices and stopping agent.
Additional surfactants
According to the present invention, detergent composition and component thereof preferably comprise the additional surfactants that is selected from negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and composition thereof.
The United States Patent (USP) 3929678 that on December 30th, 1975 was authorized Laughlin and Heuring has been enumerated typical negatively charged ion, nonionic, both sexes and zwitterionic classes tensio-active agent.Other example provides in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch).The United States Patent (USP) 4259217 that on March 31st, 1981 was authorized Murphy has been enumerated suitable cationic surfactants.
As long as exist, both sexes and zwitterionics generally are used in combination with one or more negatively charged ion and/or nonionogenic tenside.
Anion surfactant
According to the present invention, detergent composition and component thereof preferably comprise additional anion surfactant.Basically can comprise any anion surfactant that is used to wash in this detergent composition.Comprising as the salt of anion sulfate acid, sulfonic acid, carboxylic acid and the sarkosine of tensio-active agent (for example, comprise sodium, potassium, ammonium and substituted ammonium salt, as single-, two and triethanolamine salt).Sulphate anion surface active agent is preferred.
Other anion surfactant comprises isethionate, as fatty amide, alkyl succinate and the sulfosuccinate of acyl-hydroxyethyl sulfonate, N-acyl taurine salt, methyl tauride, the monoesters of sulfosuccinate (especially saturated and unsaturated C
12-C
18Monoesters), the diester of sulfosuccinate (especially saturated and unsaturated C
6-C
14Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are suitable, as rosin, staybelite and be present in or derived from the resinous acid and the hydrogenated resin acid of butter.
Sulphate anion surface active agent
Be applicable to that sulphate anion surface active agent of the present invention comprises the uncle position and secondary position alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol ethylidene oxygen ether sulfate, C of straight or branched
1-C
17Acyl group-N-(C
1-C
4Alkyl) and-N-(C
1-C
4Hydroxyalkyl) glucosamine sulfate, and the vitriol of alkyl poly glucoside, for example vitriol of alkyl polyglucoside (nonionic non-sulfuric acid compound is introduced among this paper).
Alkyl sulfate surfactant is preferably selected from straight chain and side chain C
10-C
18Primary alkyl sulphates, more preferably C
11-C
15Branched-chain alkyl vitriol and C
12-C
14Straight-chain alkyl sulfate.
Alkyl ethoxy sulfate surfactant is preferably selected from the ethoxylation C that each molecule has 0.5 to 20 moles of ethylene oxide
10-C
18Alkyl-sulphate, more preferably C
11-C
18Alkyl, most preferably C
11-C
15Alkyl, per molecule be with 0.5 to 7, such tensio-active agent of preferred 1 to 5 moles of ethylene oxide ethoxylation.
The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl vitriol and alkyl ethoxy sulfate surfactant, and this type of mixture is disclosed in PCT patent application NO.WO9 3/,181 24.
The anion sulfoacid salt surfactant
Be suitable for anionic sulphonate tensio-active agent used herein and comprise C
5-C
20Linear alkylbenzene sulfonate, alkyl ester sulfonate, C
6-C
22Uncle or secondary alkyl sulfonate, C
6-C
24Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oleoyl glycerol sulfonate and their any mixture.
The anionic carboxylic acid salt surfactant
Suitable anionic carboxylate tensio-active agent comprises alkyl ethoxy carboxylate, alkyl ethoxy multi-carboxylate tensio-active agent and soap (' alkyl carboxyl '), the secondary soap of especially described herein some.
Suitable alkyl ethoxy carboxylate comprises having formula R O (CH
2CH
2O)
xCH
2COO
-M
+Those, wherein R is C
6-C
18Alkyl, x are 0-10, and ethoxylate distributes and should make, based on weight, wherein x be this amount of substance of 0 less than 20%, and M is a positively charged ion.Suitable alkyl polyethoxye polycarboxylate tensio-active agent comprises having formula R O-(CHR
1-CHR
2-O)-R
3Those, wherein R is C
6-C
18Alkyl, x are 1-25, R
1And R
2Be selected from hydrogen atom, methyl acid group, succsinic acid group, hydroxy succinic acid group and mixed group thereof, and R
3Be selected from hydrogen atom, have the replacement of 1-8 carbon atom or do not replace hydrocarbon, and composition thereof,
Suitable soap surfactant comprises and contains the unitary secondary soap surfactant of the carboxyl that is connected on the secondary carbon(atom).It is water miscible being used for preferred secondary soap surfactant of the present invention, is selected from 2-methyl isophthalic acid-undeeanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Also can comprise some soap as suds suppressor.
The basic metal sarcosinate surfactant
Other suitable anion tensio-active agent is for having formula R-CON (R
1) CH
2The basic metal sarcosinate surfactant of COOM, wherein R is C
5-C
17Straight or branched alkyl or alkenyl, R
1Be C
1-C
4Alkyl, and M is an alkalimetal ion.Its preference is the sodium-salt form of myristyl and oleoyl methyl sarcosinate.
Alkoxy-based non-ionic surface active agent
Basically any alkoxy-based non-ionic surface active agent all is applicable to the present invention.Preferred ethoxylation and propoxylation nonionogenic tenside.The preferred alkoxylated tensio-active agent can be selected from alkylphenol nonionic condenses, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, nonionic ethoxylate/propoxylated glycerine and propylene glycol condenses and the condensation product of nonionic ethoxylate and propylene oxide/ethylenediamine adduct.
The alcohol alcoxylates nonionogenic tenside
Fatty alcohol and 1-25 mole alkylene oxide, particularly ethylene oxide and/condensation product of propylene oxide is applicable to the present invention.The alkyl chain of fatty alcohol can be straight or branched, uncle position or secondary position, and generally comprises 6-22 carbon atom.Particularly preferably be, its alkyl contains the alcohol of 8-20 carbon atom and the condensation product of 2-10 mole ethylene oxide/every mol of alcohol.
The polyhydroxy fatty acid amide nonionogenic tenside
Be applicable to that polyhydroxy fatty acid amide of the present invention has formula R
2CONR
1Z, wherein R
1Be H, C
1-C
4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixed group, preferred C
1-C
4Alkyl, more preferably C
1Or C
2Alkyl, most preferably C
1Alkyl (that is methyl); R
2Be C
5-C
31Alkyl, preferred straight chain C
5-C
19Alkyl or alkenyl, more preferably straight chain C
9-C
17Alkyl or alkenyl, most preferably straight chain C
11-C
17Alkyl or alkenyl, or its mixed group; And Z is that at least 3 hydroxyls are directly connected to polyhydroxy alkyl or its alkoxylate deriveding group (preferred ethoxylation and propenoxylated) on its line style hydrocarbon chain.Z preferably in reduction amination derived from reducing sugar; Z is glycidyl more preferably.
The fatty amide nonionogenic tenside
Suitable fatty acid amide surfactants has formula R
6CON (R
7)
2, R wherein
6For containing 7-21 carbon atom, the alkyl of preferred 9-17 carbon atom, and each R
7Be selected from hydrogen atom, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl and-(C
2H
4O)
xH, wherein x is 1-3.
The alkyl polysaccharide nonionogenic tenside
Be applicable to that alkyl polysaccharide of the present invention is disclosed in the United States Patent (USP) 4565647 of authorizing Llenado on January 21st, 1986, wherein comprise hydrophobic group and polysaccharide, as the glycan glycosides, have the hydrophilic radical of 1.3-10 sugar unit with 6-30 carbon atom.
Preferred alkyl poly glucoside has structural formula:
R
2O (C
nH
2nO) t (glycosyl)
xWherein: R
2Be selected from alkyl, alkane phenyl, hydroxyalkyl, hydroxyalkyl phenyl and mixed group thereof, wherein alkyl group contains 10-18 carbon atom; N is 2 or 3; T is 0-10; And x is 1.3-8.Glycosyl is preferably derived from glucose.
Amphoterics
Be applicable to that amphoterics of the present invention comprises amine oxide surfactant and alkyl both sexes carboxylic acid.
Suitable amine oxide comprises having formula R
3(OR
4)
xN
0(R
5)
2Those compounds, R wherein
3Be selected from alkyl, hydroxyalkyl, amido propionyl and the alkane phenyl or its mixed group that contain 8-26 carbon atom; R
4Be alkylidene group or hydroxyl alkylidene group or its mixed group that contains 2-3 carbon atom; X is 0-5, preferred 0-3; And each R
5Be alkyl or hydroxyalkyl that contains 1-3 carbon atom or the polyoxyethylene group that contains 1-3 ethylene oxide group.Preferred C
10-C
18Alkyl dimethyl amine oxide and C
10-18Amidoalkyl dimethyl oxidation amine.
The suitable example of alkyl both sexes dicarboxylic acid is Miranol (TM) C2M Conc., by Miranol, and Inc., Dayton, NJ makes.
Zwitterionics
According to the present invention, zwitterionics also can add in detergent composition and the component thereof.These tensio-active agents can briefly be described as the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or the derivative of quaternary ammonium, quaternary phosphonium or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the examples that can be used for zwitterionics of the present invention.
Suitable trimethyl-glycine has formula R (R ')
2N
+R
2COO-, wherein R is C
6-C
18Alkyl, each R
1Be generally C
1-C
3Alkyl, and R
2Be C
1-C
5Alkyl.Preferred trimethyl-glycine is C
12-18Dimethyl caproic acid ammonium and C
10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.Mix beet alkali surface activator also applicable to the present invention.
Cats product
The cats product that is applicable to detergent composition of the present invention and component thereof comprises quaternary ammonium surfactant, is selected from C
6-C
16, preferred C
6-C
10N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.
The another kind of cats product that is applicable to detergent composition of the present invention and component thereof is the cationic ester tensio-active agent.
The cationic ester tensio-active agent is a kind of compound with surfactant properties of preferably water dispersiveness, wherein contains at least one ester (that is ,-COO-) key and at least one positive charge group.For example, United States Patent (USP) № 4228042,4239660 and 4260529 discloses suitable cationic ester tensio-active agent, comprising the cholinesterase tensio-active agent.
Ester bond in the preferred surfactants molecule and positive charge group are separated from each other by spacer groups, and the chain of described spacer groups comprises at least 3 atoms (i.e. the chain length of 3 atoms), preferred 3-8 atom, more preferably 3-5 atom, most preferably 3 atoms.The atom that forms the spacer groups chain can be selected from carbon, nitrogen and Sauerstoffatom and mixed form arbitrarily thereof, but any nitrogen on the described chain or Sauerstoffatom only are connected with carbon atom in the chain.Therefore, for example get rid of-O-O-(being superoxide) ,-N-N-and-N-O-key group uniformly-spaced, but for example comprise-CH
2-O-CH
2-and-CH
2-NH-CH
2The spacer groups of-key etc.The spacer groups chain preferably includes only carbon atom, most preferably hydrocarbon chain.
The water soluble detergency promoter compound
According to the present invention, detergent composition and component preferred package thereof contain water-soluble washing-aid compound, and its consumption in detergent composition is generally the 1-80% weight of composition, preferred 10-70% weight, most preferably 20-60% weight.
The water soluble detergency promoter compound comprises any mixture of water-soluble monomer multi-carboxylate or its sour form, homopolymerization and copolymerization poly carboxylic acid or its salt, borate, phosphoric acid salt and aforementioned substances, and wherein said poly carboxylic acid comprises and is separated from each other at least two carboxyls that are no more than two carbon atoms.Carboxylate salt and multi-carboxy acid salt washing agent can be monomer or oligomeric form, although because cost and performance cause and preferred monomers multi-carboxylate usually.
The suitable carboxylic salt that contains a carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and ether derivant thereof.The multi-carboxylate of containing 2 carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The multi-carboxylate of containing 3 carboxyls specifically comprises, water-soluble citrate, aconitate and citraconate and succinate derivative, as English Patent № 1379241 described carboxymethyl oxydisuccinic acid salt, English Patent № 1389732 described lactoyl oxydisuccinic acid salt and Netherlands patent applications 7205873 described aminosuccinic acid salt, and oxygen connection multi-carboxylate, as English Patent № 1387447 described 2-oxa-s-1,1,3-tricarballylic acid salt.
The multi-carboxylate of containing 4 carboxyls comprises, disclosed oxygen di-succinate, 1,1,2 among the English Patent № 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and comprise, English Patent № 1398421 and 1398422 and United States Patent (USP) № 3936448 in disclosed sulfonation pyrolysis Citrate trianion among disclosed sulfo-succinic acid salt derivative and the English Patent № 1439000.Preferred multi-carboxylate is for containing the hydroxycarboxylate, particularly Citrate trianion of maximum 3 carboxyls in each molecule.
As useful builder component, also can consider the mixture of the parent acid of monomer or oligomeric multi-carboxylate's sequestrant or itself and salt, as citric acid or Citrate trianion/citric acid mixture.In the present invention, borate washing assistant and the washing assistant that contains into borate substance are useful water soluble detergency promoters, described one-tenth borate substance washing composition store or wash conditions under can produce borate.
The suitable example of water-soluble phosphate washing assistant is the Sodium polymetaphosphate of alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, sodium orthophosphate potassium and ammonium, sodium-metaphosphate and potassium, the about 6-21 of the polymerization degree and the salt of phytic acid.
Be partly dissolved or insoluble washing-aid compound
According to the present invention, detergent composition and component thereof can comprise and be partly dissolved or insoluble washing-aid compound, and its consumption in detergent composition is generally the 1-80% weight of composition, preferred 10-70% weight, most preferably 20-60% weight.
The example of the insoluble washing assistant of most of water comprises sodium silicoaluminate.
Suitable aluminosilicate zeolite has single cell structure formula Na
z[(AlO
2)
z(SiO
2)
y] xH
2O, wherein z and y are at least 6; The mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.Silico-aluminate is a hydrated state, preferably contains 10-28%, more preferably the crystal form of 18-22% combination water.Aluminosilicate zeolite can be a crude substance, but preferred synthetic deriving.Synthetic crystallization silico-aluminate ion exchange material can be buied, and its commodity are called zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and composition thereof.Zeolite A has structural formula
Na
12[(AlO
2)
12(SiO
2)
12]·xH
2O
Wherein x is 20-30, especially 27.X zeolite has structural formula Na
86[(AlO
2)
86(SiO
2)
106] 276H
2O.
Another preferred aluminosilicate zeolite is a zeolite MAP builder.The amount of zeolite MAP is the 1-80% of composition weight, more preferably 15-40%.
EP384070A (Unilever) has described zeolite MAP builder.It is defined as the alkali metal aluminosilicate of zeolite P, and wherein the ratio of silicon and aluminium is no more than 1.33, preferred 0.9-1.33, more preferably 0.9-1.2.
Valuable especially is that wherein the ratio of silicon and aluminium is no more than 1.15, more special 1.07 the zeolite MAP that is no more than.
With d
50Value represents that the granularity of zeolite MAP detergent builders is preferably the 1.0-10.0 micron, more preferably 2.0-7.0 micron, most preferably 2.5-5.0 micron.
d
50The particulate diameter of value representation 50% weight is worth less than this.Granularity specifically can be by conventional method of analysis, as using scanning electronic microscope or utilizing laser particle size analyzer to measure.Determine d
50Other method of value is disclosed among the EP384070A.
Heavy metal ion chelating agent
Detergent composition of the present invention preferably comprises the heavy metal ion chelating agent as selectable components.In this article, " heavy metal ion chelating agent " be meant can with the component of heavy metal ion chelating.These components also can have calcium and magnesium sequestering power, but they preferably have and heavy metal, as iron, manganese and copper bonded selectivity.
The consumption of heavy metal chelant is generally the 0.005-20% of composition weight, preferred 0.1-10%, more preferably 0.25-7.5%, most preferably 0.5-5%.
Be applicable to that heavy metal ion chelating agent of the present invention includes organic phosphonates, as an alkali metal salt and the nitrilo trimethylene phosphonic salt of amino alkylidenyl many (alkylene phosphonic acids salt), ethane 1-hydroxyl di 2 ethylhexyl phosphonic acid.
In the above material, preferred diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexanediamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene-1,1-diphosphonate.Be applicable to that other heavy metal chelant of the present invention comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as the amino tetraacethyl of ethylene, ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two valeric acids, 2-hydroxy propylidene diamines disuccinic acid or its all salt.Particularly preferably be ethylene diamine-N, N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt or its mixture.
Be applicable to that other heavy metal chelant of the present invention is an iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or the glyceryl iminodiethanoic acid described in EP-A-317542 and the EP-A-399133.Iminodiethanoic acid described in the EP-A-516102-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are applicable to the present invention.Beta-alanine-N described in the EP-A-509382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable for.
EP-A-476257 has described the suitable sequestrant based on amino.EP-A-510331 has described derived from collagen, Keratin sulfate or caseic suitable sequestrant.EP-A-528859 has described suitable alkyl imino oxalic acid sequestrant.Two pyridine carboxylic acids and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is suitable for.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxy propylidene diamines-N, N '-disuccinic acid (HPDDS) also is suitable for.
The organic peroxide acid bleach system
An essential characteristic according to detergent composition of the present invention and component thereof is the organic peroxide acid bleach system.The organic peroxide acid bleach system preferably comprises hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Organic peroxide acid can obtain by the real-world effectiveness of its precursor and hydrogen peroxide cource.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In another preference, preformed organic peroxide acid directly adds in the composition.Also comprise the composition that hydrogen peroxide cource and organic peroxide acid precursor mixture combine with preformed organic peroxide acid.
Inorganic perhydrate SYNTHETIC OPTICAL WHITNER
Inorganic perhydrate salt is preferred hydrogen peroxide cource.These salt are generally alkali metal form, and particular certain cancers, its add-on are the 1-40% weight of composition, more preferably 2-30% weight, most preferably 5-25% weight.
The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.These inorganic perhydrate salt are an alkali metal salt normally.Inorganic perhydrate salt can be used as the crystalline solid that does not have other protection and adds.But concerning some perhydrate salt, the preference of this particulate composition has adopted a kind of coating attitude material that perhydrate salt in the particulate product provides better stability in storage that can be.Suitable coating compounds comprises inorganic salt, as alkalimetal silicate, carbonate or borate or its mixture, or organic substance, as wax, oil or fatty soap.
Sodium peroxoborate is preferred perhydrate salt, can be to have nominal structural formula NaBO
2H
2O
2Monohydrate or tetrahydrate NaBO
2H
2O
23H
2O.
Alkali metal percarbonate, particularly SPC-D are the preferred perhydrate of the present invention.SPC-D is a kind of its structural formula and 2Na
2CO
33H
2O
2Corresponding addition compound, available its crystalline solid.
Potassium Persulphate is another the inorganic perhydrate salt that is used for detergent composition of the present invention.
Peroxyacid bleach precursor
Peroxyacid bleach precursor can form peroxy acid with hydroperoxidation in crossing hydrolysis reaction.In general, peroxyacid bleach precursor can be expressed as follows
Wherein L is a leavings group, and X can be any functionality basically, and the structure that needed only hydrolysis gained peroxy acid is
The add-on of peroxyacid bleach precursor compound is preferably the 0.5-20% weight of detergent composition, more preferably 1-15% weight, most preferably 1.5-10% weight.
Suitable peroxyacid bleach precursor compound comprises one or more N-or O-acyl group usually, and the selectable scope of this precursor is very wide.Suitable kind comprises the acylated derivatives of acid anhydrides, ester, imide, lactan or imidazoles and oxime.In these kinds, the example of useful matter is disclosed in GB-A-1586789.Suitable ester class is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386.
Leavings group
Leavings group (below be called the L group) should have enough activity to carry out hydrolysis reaction in optimal time scope (as, wash(ing)cycle).If but the L activity is too high, this activator just is difficult to stably be used for bleaching composition so.
Preferred L group is selected from:
With
With
And composition thereof, R wherein
1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R
3For containing the alkyl chain of 1-8 carbon atom, R
4Be H or R
3, R
5For containing the alkylidene chain of 1-8 carbon atom, and Y is H or solubilizing group.R
1, R
3And R
4All can be replaced, such as comprising alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides or ammonium or alkyl ammonium group by any functional group basically.
Preferred solubilizing group is-SO
3 -M
+,-CO
2 -M
+,-SO
4 -M
+,-N
+(R
3)
4X-and O＜-N (R
3)
3, most preferably-SO
3 -M
+With-CO
2 -M
+
R wherein
3For containing the alkyl chain of 1-4 carbon atom, M is for giving bleach-activating agent deliquescent positively charged ion, and X is a negatively charged ion of giving the bleach-activating agent solvency action.Preferred M is basic metal, ammonium or replaces ammonium cation, most preferably sodium and potassium, and X is halogenide, hydroxide radical, methylsulfate or acetic acid anion.
Alkyl percarboxylic acids bleach precursor
Alkyl percarboxylic acids bleach precursor can pass through hydrolysis and form percarboxylic acids, and preferably such precursor is crossed hydrolysis and formed peracetic acid.Preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, N
1N
1Tetrem acidylate Alkylenediamine, wherein alkylidene group comprises at least that 1-6 carbon atom, especially alkylidene group contain 1,2 and 6 carbon compound, preferred especially tetraacetyl ethylene diamine (TAED).
Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (different NOBS) nonanoyl oxygen benzene sulfonic acid sodium salt (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and five acetyl glucose.
The alkyl peroxy acids precursor that acid amides replaces
The alkyl peroxy acids precursor compound that acid amides replaces is suitable for the present invention, comprises those with following general formula:
Or
R wherein
1For containing the alkyl of 1-14 carbon atom, R
2For containing the alkylidene group of 1-14 carbon atom, R
5For H or contain the alkyl of 1-10 carbon atom, and L can be any leavings group basically.The bleaching activity immunomodulator compounds that this class acid amides replaces has introduction in EP-A-0170386.
Peroxybenzoic acid precursors
The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis, suitable O-acidylate peroxybenzoic acid precursors compound comprises and replacing and unsubstituted benzoyl oxygen Phenylsulfonic acid and Sorbitol Powder, glucose and all sugar and the benzoyl product of benzoylation reagent.And acid imide peroxybenzoic acid precursors compound, comprise the ureas that N-benzoyl succinimide, four benzoyl ethylene diamines and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzoglyoxaline, and other the peroxybenzoic acid precursors that contains the N-acyl group, comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.
The positively charged ion peroxyacid precursor
Positively charged ion peroxyacid precursor compound is crossed hydrolysis and is produced the positively charged ion peroxy acid.Described positively charged ion peroxyacid precursor generally passes through with positive charge functional group, and for example ammonium or alkyl ammonium group form because of (preferred ethyl ammonium or ammonium methyl) replaces its peroxy acid part.The positively charged ion peroxyacid precursor generally adds in the solid detergent composition with the salt that itself and suitable negatively charged ion (for example halogen ion) form.
The peroxyacid precursor compound that such positively charged ion replaces can be the derivative of peroxybenzoic acid or its replacement, precursor compound as previously described.In addition, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides replace, and will narrate as the back.
The positively charged ion peroxyacid precursor was introduced in following patent: U.S.4,904,406,4,751,015,4,988,451,4,397,757,5,269,962,5,127,852,5,093,022,5,106,528, U.K.1,382,594, EP475,512,458,396 and 284,292 and JP 87-318,332.Preferred this precursor is disclosed among UK patent application NO.9407944.9 and the US application NO.08/298903,08/298650,08/298904 and 08/298906.Suitable positively charged ion peroxyacid precursor comprises ammonium salt or alkylammonium salt, N-acidylate hexanolactam and the tetra-acetylated glucose benzoyl of the benzoyl peralcohol of all substituted alkyls or benzoyl oxygen Phenylsulfonic acid.N-acidylate hexanolactam class preferred cation peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam,
Benzoxazine organic peroxy acid precursor
As described in EP-A-332294 and EP-A-482807, another kind of suitable precursor compound is the benzoxazine type, particularly has those of following structural formula:
R wherein
1Be hydrogen, alkyl, alkaryl, aryl or aralkyl.
Preformed organic peroxide acid
Except organic peroxide acid bleach precursor compound, in other words for substituting organic peroxide acid bleach precursor compound, the organic peroxide acid bleach systems also can comprise preformed organic peroxide acid, and its consumption is generally the 1-15% weight of composition, more preferably 1-10% weight.
Preferred organic peroxy acid compound is the acid amides substitution compound with following general formula:
Or
R wherein
1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R
2Be alkylidene group, arylidene and the alkarylene that contains 1-14 carbon atom, and R
5For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy compound that these acid amides replace is disclosed in EP-A-0170386.
Other organic peroxide acid comprises diacyl and four acyl group peralcohol, especially diperoxy dodecanedioic acid, diperoxy tetradecane diacid, diperoxy Thapsic acid.List and diperoxyazelaic acid, list and two undecane dicarboxylic acid excessively and N-O-phthalic amido peroxide caproic acid also are suitable for the present invention.
Enzyme
Another preferred component that is used for detergent composition and component thereof is one or more other enzymes.
Preferred other enzyme comprises commercially available cellulase, endoenzyme, at, amylase, neutrality and Sumizyme MP, esterase, polygalacturonase, Sumylact L and the peroxidase in the common adding detergent composition.Suitable enzyme was introduced in United States Patent (USP) № 3519570 and 3533139.
Preferred commercially available proteolytic enzyme comprises, those that sell with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by the Novo Industries A/S of Denmark, those that sell with trade(brand)name Maxatase, Maxacal and Maxapem by Gist-Brocades, those that sell by Genencor International, and sell with trade(brand)name Opticlean and Optimase by Solvay Enzyme those.According to the present invention, the consumption of proteolytic enzyme in composition can be the 0.0001-4% organized enzyme of composition weight.
Preferred amylase comprises GB1, the α-Dian Fenmei of describing in detail among 296,839 (NoVo) that derives from the special bacterial strain of bacillus licheniformis.Preferred commercially available amylase comprises, those that sold with trade(brand)name Rapidase by Gist-Brocades, those that sold with trade(brand)name Termamyl and BAN by Novo Industries A/S.According to the present invention, the consumption of amylase in composition can be the 0.0001-2% organized enzyme of composition weight.
Organic polymer
According to the present invention, organic polymer is the preferred annexing ingredient of detergent composition and component thereof, therefore is preferably the component in any granular component, and wherein they can bond together granular component.In this article, " organic polymer " is meant, in detergent composition, be commonly used for any basically organic polymer of dispersion agent and antiredeposition and soil-suspending agent, according to the present invention, as any high molecular organic polymer of earth flocculation agent, but is not season ethoxylation (gathering) amine dirt removal/anti redeposition agent comprising in this article.
The consumption of organic polymer in detergent composition of the present invention is generally the 0.1-30% of composition weight, preferred 0.5-15%, most preferably 1-10%.
The example of organic polymer comprises water-soluble organic homopolymerization-or copolymerization-poly carboxylic acid or its salt, and wherein said poly carboxylic acid comprises and is separated from each other at least two carboxyls that are no more than two carbon atoms.Back one polymkeric substance is disclosed in GB-A-1596756.
The example of these salt be its MWt 1000-5000 the multi-carboxylate and with the multipolymer of maleic anhydride, the molecular weight of these multipolymers is 2000-100000, especially 40000-80000.The polyamino compound can be used for the present invention, comprising those compounds derived from aspartic acid, as disclosed among EP-A-3052282, EP-A-305283 and the EP-A-351629.
The terpolymer that contains the monomeric unit that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, especially molecular-weight average are that the terpolymer of 5000-10000 is also applicable to the present invention.
Other organic polymer that is applicable to detergent composition of the present invention comprises derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.
Other useful organic polymer is that polyoxyethylene glycol, especially molecular weight are 1000-10000, more particularly 2000-8000, most preferably from about 4000 polyoxyethylene glycol.
Press down foam system
When detergent composition of the present invention is used to machine-wash composition in allotment, preferably comprise the 0.01-15% that its consumption is a composition weight, preferred 0.05-10%, most preferably the foam that presses down of 0.1-5% is.
Be used for the suitable foam system that presses down of the present invention and can comprise any basically known anti-foam compound, for example comprise anti-foam compound of siloxanes and the anti-foam compound of 2-alkyl alcohol.
In this article, " anti-foam compound " be meant and can reduce by detergent composition solution, particularly the foaming that is produced when stirring this solution or any compound or its mixture of the degree of foaming.
Being particularly preferred for anti-foam compound of the present invention is the anti-foam compound of siloxanes, and it is defined as any anti-foam compound that comprises silicone components in this article.The anti-foam compound of these siloxanes also comprises silica component usually.In this paper and general industry field, term " siloxanes " comprises the polymkeric substance of the various higher molecular weights that contain siloxane unit and various alkyl.The anti-foam compound of preferred siloxanes is a siloxanes, the polydimethylsiloxane that especially has trimethyl silyl end-blocking block unit.
Other suitable anti-foam compound comprises fatty monocarboxylic acid and water-soluble salt thereof.Authorize the United States Patent (USP) 29543407 of Wayne St.John and described these materials December 27 nineteen sixty.Generally have 10-24 carbon atom as the mono carboxylic acid of aliphatic series of froth suppressor and the hydrocarbyl chain of water-soluble salt thereof, be preferably 12-18 carbon atom.Its suitable salt comprises an alkali metal salt, as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salt.
Other suitable anti-foam compound comprises, for example, and the fatty acid ester of high molecular fatty ester (as, fatty acid triglycercide), monohydroxy-alcohol, aliphatic C
18-C
40Ketone (as stearone), N-alkylation aminotriazine, as three-to six-alkyl melamine or two-to four-alkyl diamine chlorotriazine (cyanuryl chloride and two or three moles have the uncle of 1-24 carbon atom or reaction product, the propylene oxide of secondary amine), distearyl acid amides and single stearyl two-basic metal (as, sodium, potassium and lithium) phosphoric acid salt and phosphoric acid ester.
The preferred foam system that presses down comprises:
(a) anti-foam compound, the anti-foam compound of preferred siloxanes, the siloxanes that most preferably comprises following component is prevented the foam compound
(ⅰ) consumption is the 50-99% of the anti-foam compound weight of siloxanes, the polydimethylsiloxane of preferred 75-95%; With
(ⅱ) consumption is the 1-50% of the anti-foam compound weight of siloxanes/silicon-dioxide, the silicon-dioxide of preferred 5-25%;
The add-on of the anti-foam compound of wherein said silica/silicon oxygen alkane is a 5-50% weight, preferred 10-40% weight;
(b) consumption is a 0.5-10% weight, the compound dispersing agent of preferred 1-10% weight, most preferably comprise siloxane glycol rake formula (rake) multipolymer, wherein the content of polyoxyalkylene is 72-78%, and the ratio of ethylene oxide and propylene oxide is 1: 0.9-1: 1.1; Particularly preferred this siloxane glycol rake formula multipolymer is DC0544, can be buied by DOW Corning, and commodity are called DC0544;
(c) consumption is a 5-80% weight, and the inertia carrier fluid compound of preferred 10-70% weight most preferably comprises C
16-C
18Ethoxylated alcohol, wherein ethoxylation degree is 5-50, preferred 8-15.
EP-A-0210731 has described a kind of particulate very preferably and has pressed down foam system, wherein comprises siloxanes and prevents that foam compound and fusing point are 50-85 ℃ organic carrier, and wherein organic carrier comprises glycerine and the monoesters with lipid acid of 12-20 carbon atom.The preferred particulate that EP-A-0210721 discloses other presses down foam system, and wherein organic carrier is fusing point 45-80 ℃, and its carbochain has lipid acid or alcohol or its mixture of 12-20 carbon atom.
The dye transfer inhibitor polymkeric substance
Detergent composition of the present invention also can comprise 0.01-10% weight, the dye transfer inhibitor polymkeric substance of preferred 0.05-0.5% weight.
Preferably from multipolymer, Polyvinylpyrolidone (PVP) or its mixture of polyamine N-oxide, N-vinyl pyrrolidone and N-vinyl imidazole, wherein these polymkeric substance can be cross-linked polymers to dye transfer inhibitor.
A) polyamine N-oxide
Be applicable to that polyamine N-oxide of the present invention comprises the unit with following structural formula:
Wherein P is a polymerizable unit, and A is
-O-,-S-,-N-; X be 0 or 1R be aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle family or alicyclic group or its any mixed group, nitrogen-atoms can connect on it or becomes its part in the N-O group.
The N-O group can be represented by following general formula:
Or
R wherein
1, R
2, R
3Be aliphatic series, aromatics, heterocycle family or alicyclic group or its mixed group, x or/and y or/and z is 0 or 1, and the nitrogen of N-O group is former in connecting on it or becoming its part.The N-O group can become the part of polymerizable unit (P), maybe can be connected on the main polymer chain, or either way have.
Wherein the N-O group suitable polyamine N-oxide that becomes a polymerizable unit part comprises, wherein R be selected from aliphatic series, aromatics, alicyclic or heterocyclic group group polyamine N-oxide.A kind of described polyamine N-oxide comprises that wherein the nitrogen in the N-O group becomes those polyamine N-oxide of a R group part.Preferred polyamine N-oxide compound is a heterocyclic group for R wherein, as those of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.
Other suitable polyamine N-oxide is connected to polyamine oxide compound on the polymerizable unit for N-O group wherein.Preferred these polyamine N-oxide comprise that wherein nitrogen-atoms is the polyamine N-oxide with logical formula I of a described R group part in the N-O functional group, and wherein R is aromatics, heterocycle family or alicyclic group.Its example is that wherein R is a heterogeneous ring compound, as those polyamine N-oxide of pyridine, pyrroles, imidazoles and derivative thereof.
The polyamine N-oxide that can almost be had any polymerization degree.The polymerization degree is unimportant, as long as this material has required water-soluble and dye suspension performance.Its molecular-weight average is generally 500-1000000.
B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
Molecular weight is that the N-vinyl pyrrolidone of 5000-50000 and the multipolymer of N-vinyl imidazole also are applicable to the present invention.In preferred copolymer, the mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1-0.2.
C) Polyvinylpyrolidone (PVP)
Detergent composition of the present invention also can use the Polyvinylpyrolidone (PVP) (" PVP ") of molecular-weight average as 2500-400000.Suitable Polyvinylpyrolidone (PVP) can be available from ISPCorporation, New York, NY and Montreal, Canada, its name of product are PVP K-15 (viscosity-average molecular weight is 10000), PVP K-30 (molecular-weight average is 40000), PVP K-60 (molecular-weight average is 160000) and PVP K-90 (molecular-weight average is 360000).PVP K-15 also can be available from ISP Corporation.Other suitable Polyvinylpyrolidone (PVP) available from BASF Corporation comprises Sokalan HP 165 and Sokalan HP 12.
D) Ju Yi Xi oxazolidinone
Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the dye transfer inhibitor polymkeric substance.The molecular-weight average of described Ju Yi Xi oxazolidinone is 2500-400000.
E) polyvinyl imidazol
Detergent composition of the present invention also can use polyvinyl imidazol as the dye transfer inhibitor polymkeric substance.The preferred 2500-400000 of the molecular-weight average of described polyvinyl imidazol.
White dyes
In detergent composition of the present invention, also optional certain hydrophilic white dyes that contains the 0.005-5% weight of having an appointment.
Can be used for hydrophilic white dyes of the present invention and have following structural formula:
R wherein
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; And M is a salt-forming cation, as sodium or potassium.
In following formula, work as R
1Be anilino, R
2Be N-2-two-hydroxyethyl, and M is positively charged ion, during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 ' Stilbene disulfonic acid and disodium salts thereof.This specific whitening agent can have been bought from Ciba-geigy company, and its commodity are called Tinopal-UNPA-GX.In detergent composition of the present invention, Tinopal-UNPA-GX is the preferred hydrophilic white dyes that uses.
In following formula, work as R
1Be anilino, R
2Be N-2-hydroxyethyl-N-2-methylamino-, and M being positively charged ion, during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-s-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid disodium salt.This specific whitening agent can have been bought from Ciba-geigy company, and its commodity are called Tinopa1 5BM-GX.
In following formula, work as R
1Be anilino, R
2Be morpholino, and M being positively charged ion, during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid disodium salt.This specific whitening agent can have been bought from Ciba-geigy company, and its commodity are called Tinopal AMS-GX.
The polymkeric substance stain remover
In detergent composition of the present invention, the known polymkeric substance stain remover of optional use below is called " SRA ".If use, SRA generally accounts for the 0.01-10.0% of composition weight, is generally 0.1-5%, is preferably 0.2-3.0%.
Usually, preferred SRA contains hydrophilic segment and hydrophobic part, wherein: but described hydrophilic segment hydrophilicity-imparting treatment hydrophobic fiber, as the surface of polyester and nylon; Described hydrophobic part then deposits on the hydrophobic fiber, then by finishing washing and rinse cycle adheres on the hydrophobic fiber, thereby becomes the sticking agent of hydrophilic segment.This can guarantee that the spot that is produced is easier to be cleaned in washing step afterwards after SRA handles.
Preferred SRA comprises low polyterephthalate, and it, prepares by the method that comprises at least a transesterification/oligomerization under the existence as titanium (IV) alkoxide normally at metal catalyst.These esters can be made with other monomer, these monomers can via one, two, three, four or more the multi-section position introduce in the ester structure, and surely not form highly cross-linked overall structure.
Suitable SRA comprises the sulfonated products of substantial linear ester oligomer; it comprises terephthaloyl and the multiple unitary oligomer ester main chain of oxygen base alkylidene group oxygen basic weight; with covalently bound allyl group to this main chain the sulfonation terminal portions of deriving; for example; J.J.Scheibei and E.P.Gosselink are at the US4 in November 6 nineteen ninety; 968,451 are described this.This ester oligomer can make by following steps: (a) ethoxylation allyl alcohol, (b) in two-step approach transesterification/oligomerization, product and dimethyl terephthalate (DMT) (" DMT ") and 1 with (a), 2-propylene glycol (" PG ") reacts, and (c) product and the sodium metabisulfite of (b) is reacted in water.Other SRA comprises, people such as Gosselink are at the US4 on December 8th, 1987,711, nonionic end-blocking terephthalic acid 1 in 730,2-propylidene ester/terephthalic acid gathers (oxygen ethylidene) ester, as generating by transesterification/oligomerization of poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other example of SRA comprises; Gosselink is at the US4 on January 26th, 1988, disclosed part and the end capped oligomer ester of negatively charged ion fully in 721,580, and as ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of the hot sodium sulfonate of 6-two oxa-s-8-hydroxyl; Gosselink is at the US4 on October 27th, 1987, nonionic end-blocking block polyester oligopolymer in 702,857, as, by DMT, methyl (Me) end-blocking PEG and EG and/or PG, perhaps the mixture by DMT, EG and/or PG, Me end-blocking PEG and dimethyl-5-sulfoisophthalic acid sodium generates; And on October 31st, 1989 authorize Maldonado; people's such as Gosselink US4; 877; negatively charged ion in 896 (particularly sulphur aroyl) end-blocking terephthalate; the latter can be used for doing washing and the typical SRA of textile finishing product; between its example is served as reasons-and ester composition that sulfosalicylic acid list sodium salt, PG and DMT make, optional but also preferably comprise institute and add PEG (for example, PEG 3400).
SRA also comprises: the simple segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and terephthalic acid polyethylene oxide or terephthalic acid poly(propylene oxide), authorize the US3 of Hays referring on May 25th, 1976,959, authorized the US3 of Basadur on July 8th, 230 and 1975,893,929; Derivatived cellulose, as derive from the hydroxy ethers cellulose polymer compound METHOCEL of Dow; C
1-C
4Alkylcellulose and C
4Hydroxy alkyl cellulose is authorized people's such as Nico US4,000,093 referring on December 28th, 1976; And average (methyl) degree that replaces is the methyl cellulose ether of each about 1.6-2.3 in glucoside unit.Its viscosity (2% aqueous solution) under 20 ℃ is about 80-120 centipoise.These materials can METOLOSE SM100 and METOLOSE SM200 buy, they are trade(brand)names of the methyl cellulose ether made by Shinetsu Kagaku Kogyo KK..
Another kind of SRA comprises: (I) uses the vulcabond coupler to connect the nonionic terephthalate of polymer esters structure, referring to people's such as Violland US4, and 201,824 and people's such as Lagasse US4,240,918; (II) has the SRA of carboxylicesters end group, and it is by trimellitic acid 1,2-anhydride being added on the known SRA, changing terminal hydroxyl group into trimellitate and obtain.By suitable selecting catalyst, trimellitic acid 1,2-anhydride can be received on the end group of polymkeric substance by the ester bond of an isolated carboxylic acid of trimellitic acid 1,2-anhydride and not connect by opening anhydride bond.Nonionic or negatively charged ion SRA can be used as starting raw material, but as long as they contain the terminal hydroxy group of esterification.Referring to people's such as Tung US4,525,524.In addition, also comprise: (III) urethanum-keyed jointing type is based on the SRA of terephthalic acid anion salt, referring to people's such as Violland US4, and 201,824.
Other optional component
Other optional component that is applicable to the present composition comprises spices, tinting material and filling salt, and wherein sodium sulfate is preferred filling salt.
The detergent formulation of the nearly pH neutral of washing lotion
Although detergent composition of the present invention uses in broad washing lotion pH scope (as, about 5-12), to nearly neutral wash solution pH value, promptly in 20 ℃ of water, under the concentration of about 0.1-2% weight, when initial pH was about 7.0-10.5, they were with regard to particularly suitable in allotment.The nearly neutral pH prescription of washing lotion helps stabilized enzyme and prevents the dirt sedimentation.In these prescriptions, washing lotion pH value preferred about 7.0-10.5, more preferably from about 8.0-10.5, most preferably from about 8.0-9.0.
J.H.M.Wertz and P.C.E.Goffinet disclose the nearly neutral pH detergent formulation of preferred washing lotion in the european patent application 83.200688.6 of application on May 16 nineteen eighty-three.
This based composition very preferably also preferably comprise about 2-10% weight citric acid and a small amount of (as, less than about 20% weight) neutralizing agent, buffer reagent, phase modifier, hydrotropic solvent, enzyme, enzyme stabilizers, polyprotonic acid, foaming regulator, opacifying agent, antioxidant, sterilant, dyestuff, spices and whitening agent, authorize as on August 25th, 1981 described in people's such as Barrat the United States Patent (USP) 4285841.
The formation of composition
Detergent composition of the present invention can be made by the whole bag of tricks, comprising with all cpds dry mixed and gathering contained in the detergent component.Detergent component is preferably formed the part of detergent composition.
According to composition of the present invention can be various physical forms, comprising particle, tablet, thin slice, lozenge and strip.The partitioning device that utilization is arranged in washing machine drum adds that the composition of the washing machine that pollutes fabric is arranged is so-called concentrated granular detergent composition.
Also can be used for according to composition of the present invention, for example in the bleaching compositions of additives of chlorine bleaching agent, or be used in combination with it.
In general, can make by the whole bag of tricks, comprising dry mixed, sprinkling drying, gathering and granulation according to granular detergent composition of the present invention.Can add in other the detergent component by dry mixed, gathering (preferably combining) or as spraying dried ingredients according to season removal dirt/anti redeposition agent of the present invention with carrier substance.
In the particulate composition that comprises water-soluble cationic dirt removal/antiredeposition compound, the average particle size particle size of component should preferably be no more than 15% particle diameter greater than 1.8 millimeters, and is no more than 15% particle diameter less than 0.25 millimeter.Average particle size particle size should make preferably that the particulate diameter of 10-50% is the 0.2-0.7 millimeter.
Defined herein term " average particle size " be by with composition sample at a series of sieves, be filtered into many fractions (being generally 5 fractions) on the preferred Tyler sieve and calculate.With the relative sieve of the fraction weight aperture mapping of gained thus.Average particle size is thought in the aperture that the sample of 50% weight can pass through.
According to the present invention, the volume density of granular detergent composition is generally at least 600 grams per liters, more preferably 650 grams per liter to 1200 grams per liters.The measuring cup that volume density is utilized simple funnel and had plate valve in its lower end is measured, and wherein, the content in the funnel can all be poured into by plate valve and be arranged in the axially aligned cylindric measuring cup in funnel below.130 millimeters in this funnel is high, and the internal diameter of its top and bottom is respectively 130 millimeters and 40 millimeters.During installation, its lower end is positioned at the above 140 millimeters places of base-plates surface.The total height of measuring cup is 90 millimeters, and inner height is 87 millimeters, and internal diameter is 84 millimeters.Its nominal volume is 500 milliliters.
In order to measure, powder is poured in the funnel by hand, open plate valve, make powder be full of measuring cup then.The measuring cup of filling is removed from support, used the straight flange instrument then,, cross its upper limb, remove excessive powder as cutter.This measuring cup of filling of weighing is then doubly taken advantage of the powder weight value of gained, obtains volume density (grams per liter).As required, can carry out replicate measurement.
Clothes washing method
The present invention that machine washing method herein is usually included in dissolving or allotment significant quantity machine-washes in the washing machine of detergent composition, uses the washings processing pollution clothes." detergent composition of significant quantity " is meant, dissolving or allotment rise 10-300 gram product in the washing lotion, the common dosage of product and washing lotion volume commonly used in the conventional machine washing method at 5-65.
In washing methods, preferably adopt partitioning device.Partitioning device is equipped with Betengent product, before beginning washing, with it product is directly introduced in the washing machine drum then.Its volume should make it possible to comprise enough Betengent products that is usually used in the washing methods.
Before washing machine is equipped with clothing, among or afterwards, begin the washing before, the partitioning device that will comprise Betengent product is put into cylinder.When beginning to carry out wash(ing)cycle, in cylinder, add the machine water, cylinder carries out Periodic Rotating then.The design of partitioning device should be able to comprise dry Betengent product, when wash(ing)cycle, owing to cylinder rotates the agitaion that produces, and by contacting with washing water, this product is discharged then.
In order to discharge Betengent product when washing, this equipment can have many openings that this product can pass through.In addition, make the material liquid permeable of this equipment and impermeable solid phase prod, therefore can discharge dissolved product.Preferred Betengent product just discharges rapidly when begin wash(ing)cycle, in this washing stage, produces of short duration high local concentrations product in washing machine drum thus.
Preferred partitioning device is reusable, and through design, can keep the globality of container when drying regime and wash(ing)cycle.Following patent has been described the particularly preferred partitioning device that uses with the present composition: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.Be published in ManufacturingChemist by J.Bland, in November, 1989, the article on the 41-46 page or leaf has also been described, the special preferred allocation equipment that uses with the particle cleaning product of so-called " granula ".Another preferred allocation equipment that uses with the present composition is disclosed in PCT patent application № WO94/11562.
Special preferred allocation equipment is disclosed in european patent application № 0343069﹠amp; In 0343070.Back one patent application discloses a kind of bag shape flexible shroud equipment that is extended out by the support ring that surrounds a hole, its opening be suitable in bag, adding in the washing step one wash(ing)cycle required adequate prod.The part washing medium opening of flowing through enters in the bag, dissolved product, and solution outwards flows in the washing medium via this opening then.Support ring has a kind of screen type structure to prevent to enter wetting, undissolved product, and this structure generally includes the radial extension wall that is extended to form the spoked wheel configuration by the center shell, or has the similar structures of spirrillum wall.
In addition, partitioning device can be a flexible cell, as the bag shape.Bag can be to apply the impermeable protectiveness material of water to keep the fibrous texture of content here, as disclosed among the open № 0018678 of european patent application.As disclosed among the open № 0011500,0011501,0011502 and 0011968 of european patent application, it can also be made by the insoluble synthetic polymer of water, wherein has rupturable edge seal design in the water medium.A kind of easily broken simple seal of water of meeting comprises along the water-soluble binder of the edge sealing of bag, and described bag is made as polyethylene or polypropylene by water pressuretightness polymeric film.
Machine wash up method
It is contemplated that any machine wash up or cleaning pollution tableware of being suitable for, particularly clean the method for polluting silverware.
Preferred machine wash up method comprises, uses the liquid, aqueous processing of wherein dissolving or allotment significant quantity machine dishwashing compositions of the present invention to be selected from pottery, glassware, holloware, silverware and cutlery and the various pollution vessel of blended thereof." the machine dishwashing compositions of significant quantity " is meant that dissolving or allotment restrain product at the 8-60 that 3-10 rises in the washing lotion, and this is common dosage of product and the washing lotion volume that is usually used in the conventional machine wash up method.
The packing of composition
Actual commercially available bleaching composition can be packaged in any suitable containers, comprising the container that is made of paper, cardboard, plastics and any suitable laminate.European patent application № 94921505.7 has described preferred packing example.
The abbreviation that is used for embodiment
In detergent composition, the symbol that component is called for short has following connotation:
LAS: line style C
12Sodium alkyl benzene sulfonate
TAS: tallow alkyl sodium sulfate
C
XyAS:C
1x-C
1ySodium alkyl sulfate
C
46SAS:C
14-C
16Secondary position (2,3) sodium alkyl sulfate
C
XyEzS: with the C of z moles of ethylene oxide condensation
1x-C
1ySodium alkyl sulfate
C
XyE
z: with the C of average z moles of ethylene oxide condensation
1x-1y(being in the great majority)
The line style primary alconol
QAS?????R
2N
+(CH
3)
2(C
2H
4OH),R
2=C
12-C
14
Soap: the linear alkyl carboxylic acid sodium, derived from 80/20 of tallow and Oleum Cocois
Mixture C FAA:C
12-C
14(coconut) alkyl N-methyl glucose amide TFAA:C
16-C
18Alkyl N-methyl glucoside acid amides TPKFA:C
12-C
14Topping TEFA STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: have structural formula Na
12(AlO
2SiO
2)
1227H
2The hydration silicoaluminate of O
Sodium, its main particle size are 0.1-10 micron zeolite MAP: the ratio of silicon and aluminium is 1.07 hydrated sodium aluminosilicate zeolite MAP NaSKS-6: have structural formula δ-Na
2Si
2O
5The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder borate Sodium Tetraborate carbonate: anhydrous sodium carbonate, granularity is a 200-900 μ m supercarbonate: anhydrous sodium bicarbonate, distribution of particle sizes are 400-1200 μ m silicate: amorphous sodium silicate (SiO
2: Na
2O=2.0: 1) sodium sulfate: anhydrous slufuric acid na citrate: two hydration trisodium citrates, activity are 86.4%, distribution of particle sizes
Be 425-850 μ mMA/AA:1: 4 toxilic acids/acrylic acid multipolymer, the about 70000AA of molecular-weight average: sodium polyacrylate, molecular-weight average is 4500CMC: the plain ether of sodium carboxyme-thylcellulose fibre: the polymerization degree is 650 methyl cellulose ether, derives from Shin Etsu
Chemicals proteolytic enzyme: protease, active for 4KNP U/ gram, by NOVO
Trade(brand)name SayinaseAlcalase sells in Industries A/S company: protease, and active for the 3AU/ gram, by NOVO Industries
A/S sells cellulase: cellulolytic enzyme, and active for the 1000CEVU/ gram, by NOVO
Industries A/S sells, trade(brand)name Carezyme amylase: amylolytic enzyme, and active for the 120KNU/ gram, by NOVO
Industries A/S sells, trade(brand)name Termamyl 120T lipase: lipolytic enzyme, the active 100KLU/ of being restrains trade(brand)name
Lipolase, sell endoenzyme by NOVO Industries A/S: endo-dextranase, active for the 3000CEVU/ gram, by NOVO
Industries A/S sells PB4: four hydrated sodium perborates, nominal configuration formula NaBO
23H
2OH
2O
2PB1: anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, nominal configuration formula NaBO
2H
2O
2Percarbonate: SPC-D, nominal configuration formula 2Na
2CO
33H
2O
2NOBS: the ninth of the ten Heavenly Stems acyloxy Phenylsulfonic acid sodium salt TAED: tetraacetyl ethylene diamine Mn catalyzer: Mn
IV 2(m-0) 3 (1,4,7-trimethylammonium-1,4, three nitrogen heterocyclic ninth of the ten Heavenly Stems of 7-
Alkane)
2(PF
6)
2, in United States Patent (USP) № 5246621 and 5244594
Described DTPA: diethylene triaminepentaacetic acid(DTPA) DTPMP: diethylenetriamine five (methylene phosphonic acid salt), by Monsanto
Supply, commodity are called the DEQUEST2060 light activating agent: sulfonation zinc phthalocyanine phthalocyanine coats whitening agent 1:4 with bleaching dextrin water-soluble polymers, 4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2:4,4 '-two (4-anilinos-6-morpholino-1,3,5-triazines-2-yl)
Amino) Stilbene-2,2 '-disulfonic acid disodium HEDP:1,1-hydroxyl second di 2 ethylhexyl phosphonic acid EDDS: quadrol-N, N '-disuccinic acid QEA1: two ((C
2H
5O) (C
2H
4O)
n(CH
3)-N
+-C
6H
12-N
+-(CH
3) two
((C
2H
5O)-(C
2H
4O)
n), n=20-30QEA2 wherein: two ((C
2H
5O) (C
2H
4O)
n(CH
3)-N
+R
1, R wherein
1Be C
4-C
12
Base, and n=20-30QEA3: three { two ((C
2H
5O)-(C
2H
4O)
n(CH
3)-N
+)-(CONC
3H
6)-
C
3H
6O; n=20-26PEGX wherein: polyoxyethylene glycol; molecular weight is xPE0: polyoxyethylene; molecular weight is 50000TEPAE: the ethoxylate PVP of tetren: polyvinylpyrrolidonepolymers polymers PVNO: polyvinylpyridine N-oxide compound PVPVI: the multipolymer SRP1 of Polyvinylpyrolidone (PVP) and vinyl imidazole: the end capped ester of sulphur benzoyl group; have oxygen base ethyleneoxy group and terephthaloyl main chain SRP2: the short block of diethoxyization poly-(terephthalic acid 1,2-propylene glycol ester)
The polymer siloxane antifoams: the polydimethylsiloxane Foam Control, wherein use siloxanes-oxygen
Base alkylidene group multipolymer is as dispersion agent, described Foam Control and institute
The ratio of stating dispersion agent is 10: 1-100: 1 wax: in paraffinic waxes following examples, all content all are meant the weight percentage (%) of composition.
Embodiment 1
According to the present invention, prepare the following high density granular laundry detergent composition A-F that is particularly suitable for European machine washing condition.
| ???A | ???B | ???C | ???D | ???E | ???F | |
| ???LAS | ??8.0 | ??8.0 | ??8.0 | ??8.0 | ??8.0 | ??8.0 |
| ???C25E3 | ??3.4 | ??3.4 | ??3.4 | ??3.4 | ??3.4 | ??3.4 |
| ???C46AS | ??1.0 | ??2.0 | ??2.5 | ??- | ??3.0 | ??4.0 |
| ???C68AS | ??3.0 | ??2.0 | ??5.0 | ??7.0 | ??1.0 | ??0.5 |
| ???QAS | ??- | ??- | ??0.8 | ??- | ??- | ??0.8 |
| Zeolite A | ??18.1 | ??18.1 | ??16.1 | ??18.1 | ??18.1 | ??18.1 |
| Zeolite MAP | ??- | ??4.0 | ??3.5 | ??- | ??- | ??- |
| Carbonate | ??13.0 | ??13.0 | ??13.0 | ??27.0 | ??27.0 | ??27.0 |
| Silicate | ??1.4 | ??1.4 | ??1.4 | ??3.0 | ??3.0 | ??3.0 |
| Sodium sulfate | ??26.1 | ??26.1 | ??26.1 | ??26.1 | ??26.1 | ??26.1 |
| ???MA/AA | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| ???CMC | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| ???PB4 | ??9.0 | ??9.0 | ??9.0 | ??9.0 | ??9.0 | ??9.0 |
| ?TAED | ??1.5 | ??1.5 | ??1.0 | ??1.5 | ??- | ??1.5 |
| The Mn catalyzer | ??- | ??0.03 | ??0.07 | ??- | ??- | ??- |
| ?DTPMP | ??0.25 | ??0.25 | ??0.25 | ??0.25 | ??0.25 | ??0.25 |
| ?HEDP | ??0.3 | ??0.3 | ??0.2 | ??0.2 | ??0.3 | ??0.3 |
| ?EDDS | ??- | ??- | ??0.4 | ??0.2 | ??- | ??- |
| ?QEA1 | ??1.0 | ??0.8 | ??0.7 | ??1.2 | ??- | ??0.5 |
| ?QEA2 | ??- | ??- | ??- | ??- | ??1.0 | ??0.5 |
| Proteolytic enzyme | ??0.26 | ??0.26 | ??0.26 | ??0.26 | ??0.26 | ??0.26 |
| Amylase | ??0.1 | ??0.1 | ??0.4 | ??0.3 | ??0.1 | ??0.1 |
| Lipase | ??0.05 | ??0.6 | ??0.7 | ??0.1 | ??0.07 | ??0.1 |
| Photoactivation SYNTHETIC OPTICAL WHITNER (ppm) | ??15 ??ppm | ??15 ??ppm | ??15 ??ppm | ??15 ??ppm | ??15 ??ppm | ??15 ??ppm |
| Whitening agent 1 | ??0.09 | ??0.09 | ??0.09 | ??0.09 | ??0.09 | ??0.09 |
| Spices | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 | ??0.3 |
| The siloxanes antifoams | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 |
| Foreign material/a small amount of thing are to 100% | ||||||
| Density (grams per liter) | ??850 | ??850 | ??850 | ??850 | ??850 | ??850 |
Embodiment 2
According to the present invention, prepare the following granular laundry detergent compositions G-I that is particularly suitable for European machine washing condition.
| ?????G | ????H | ?????I | |
| ???LAS | ????5.25 | ???5.61 | ????4.76 |
| ???TAS | ????1.25 | ???1.86 | ????1.57 |
| ???C45AS | ????- | ???2.24 | ????3.89 |
| ????C25E3S | ????- | ????0.76 | ????1.18 |
| ????C45E7 | ????3.25 | ????- | ????5.0 |
| ????C25E3 | ????- | ????5.5 | ????- |
| ????QAS | ????0.8 | ????2.0 | ????2.0 |
| ????STPP | ????19.7 | ????- | ????- |
| Zeolite A | ????- | ????19.5 | ????19.5 |
| Zeolite MAP | ????2.0 | ????- | ????- |
| NaSKS-6/ citric acid (79: 21) | ????- | ????10.6 | ????10.6 |
| Carbonate | ????6.1 | ????21.4 | ????21.4 |
| Supercarbonate | ????- | ????2.0 | ????2.0 |
| Silicate | ????6.8 | ????- | ????- |
| Sodium sulfate | ????39.8 | ????- | ????14.3 |
| ????MA/AA | ????0.8 | ????1.6 | ????1.6 |
| ????CMC | ????0.2 | ????0.4 | ????0.4 |
| ????PB4 | ????5.0 | ????12.7 | ????- |
| Percarbonate | ????5.0 | ????- | ????12.7 |
| ????TAED | ????0.5 | ????3.1 | ????- |
| The Mn catalyzer | ????0.04 | ????- | ????- |
| ????DTPMP | ????0.25 | ????0.2 | ????0.2 |
| ????HEDP | ????- | ????0.3 | ????0.3 |
| ????QEA1 | ????0.9 | ????1.2 | ????- |
| ????QEA2 | ????- | ????- | ????1.0 |
| Proteolytic enzyme | ???0.26 | ????0.85 | ????0.85 |
| Lipase | ???0.15 | ????0.25 | ????0.15 |
| Cellulase | ???0.28 | ????0.28 | ????0.28 |
| Amylase | ???0.4 | ????0.1 | ????0.1 |
| ????PVP | ???0.9 | ????1.3 | ????0.8 |
| Photoactivation SYNTHETIC OPTICAL WHITNER (ppm) | ???15 ???ppm | ????27 ????ppm | ????27 ????ppm |
| Whitening agent 1 | ???0.08 | ????0.19 | ????0.19 |
| Whitening agent 2 | ???- | ????0.04 | ????0.04 |
| Spices | ???0.3 | ????0.3 | ????0.3 |
| The siloxanes antifoams | ???0.5 | ????2.4 | ????2.4 |
| Foreign material/a small amount of thing are to 100% |
Embodiment 3
According to the present invention, prepare the following detergent formulation that is particularly suitable for European machine washing condition.
| ????J | ????K | ????L | ????M | |
| The blowing powder | ????- | ????- | ????- | ????- |
| ????LAS | ????6.0 | ????5.0 | ????11.0 | ????6.0 |
| ????TAS | ????2.0 | ????- | ????- | ????2.0 |
| Zeolite A | ????- | ????27.0 | ????- | ????20.0 |
| ????STPP | ????24.0 | ????- | ????24.0 | ????- |
| Vitriol | ????9.0 | ????6.0 | ????13.0 | ????- |
| ????MA/AA | ????2.0 | ????4.0 | ????6.0 | ????4.0 |
| Silicate | ????7.0 | ????3.0 | ????3.0 | ????3.0 |
| ????CMC | ????1.0 | ????1.0 | ????0.5 | ????0.6 |
| ????QEA1 | ????0.8 | ????1.0 | ????1.4 | ????0.5 |
| ????QEA2 | ????- | ????- | ????- | ????0.5 |
| Whitening agent | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| The siloxanes antifoams | ????1.0 | ????1.0 | ????1.0 | ????0.3 |
| ????DTPMP | ????0.4 | ????0.4 | ????0.2 | ?????0.4 |
| Be sprayed onto | ||||
| ????C45E7 | ????- | ????- | ????- | ?????5.0 |
| ????C45E2 | ????2.5 | ????2.5 | ????2.0 | ?????- |
| ????C45E3 | ????2.6 | ????2.5 | ????2.0 | ?????- |
| Spices | ????0.3 | ????0.3 | ????0.3 | ?????0.2 |
| The siloxanes antifoams | ????0.3 | ????0.3 | ????0.3 | ?????- |
| Dried additive | ||||
| Vitriol | ????3.0 | ????3.0 | ????5.0 | ?????10.0 |
| Carbonate | ????6.0 | ????13.0 | ????15.0 | ?????14.0 |
| ????PB1 | ????- | ????- | ????- | ?????1.5 |
| ????PB4 | ????18.0 | ????18.0 | ????10.0 | ?????18.5 |
| ????TAED | ????3.0 | ????2.0 | ????- | ?????2.0 |
| ????EDDS | ????- | ????2.0 | ????2.4 | ?????- |
| Proteolytic enzyme | ????1.0 | ????1.0 | ????1.0 | ?????1.0 |
| Lipase | ????0.4 | ????0.5 | ????0.4 | ?????0.2 |
| Amylase | ????0.2 | ????0.2 | ????0.2 | ?????0.4 |
| The photoactivation SYNTHETIC OPTICAL WHITNER | ????- | ????- | ????- | ?????0.15 |
| Amount to | ????100.0 | ????100.0 | ????100.0 | ?????100.0 |
According to the present invention, prepare following granulated detergent prescription.Prescription N is particularly suitable for using under Japan's machine washing condition.Prescription O-S is particularly suitable for using under U.S.'s machine washing condition.
| N | O | P | Q | R | S | |
| The blowing powder | - | - | ||||
| ??LAS | 22.0 | 5.0 | 4.0 | 9.0 | 8.0 | 7.0 |
| ??C45AS | 7.0 | 7.0 | 6.0 | - | - | - |
| ??C46AS | - | 4.0 | 3.0 | - | - | - |
| ??C45E35 | - | 3.0 | 2.0 | 8.0 | 5.0 | 4.0 |
| Zeolite A | 6.0 | 16.0 | 14.0 | 19.0 | 16.0 | 14.0 |
| ??MA/AA | 6.0 | 3.0 | 3.0 | - | - | - |
| ??AA | - | 3.0 | 3.0 | 2.0 | 3.0 | 3.0 |
| Sodium sulfate | 7.0 | 18.3 | 11.3 | 24.0 | 19.3 | 19.3 |
| Silicate | 5.0 | 1.0 | 1.0 | 2.0 | 1.0 | 1.0 |
| Carbonate | 28.3 | 9.0 | 7.0 | 25.7 | 8.0 | 6.0 |
| ??QEA1 | 0.9 | 0.9 | - | - | 0.5 | 1.1 |
| ????QEA2 | ???- | ???- | ????0.8 | ??1.0 | ??- | ?- |
| ????QEA3 | ???- | ???- | ????0.4 | ??- | ??- | ?- |
| ????PEG?4000 | ???0.5 | ???1.5 | ????1.5 | ??1.0 | ??1.5 | ?1.0 |
| Sodium oleate | ???2.0 | ???- | ????- | ??- | ??- | ?- |
| ????DTPA | ???0.4 | ???- | ????0.5 | ??- | ??- | ?0.5 |
| Whitening agent | ???0.2 | ???0.3 | ????0.3 | ??0.3 | ??0.3 | ?0.3 |
| Be sprayed onto | ||||||
| ????C25E9 | ???1.0 | ???- | ????- | ??- | ??- | ?- |
| ????C45E7 | ???- | ???2.0 | ????2.0 | ??0.5 | ??2.0 | ?2.0 |
| Spices | ???1.0 | ???0.3 | ????0.3 | ??1.0 | ??0.3 | ?0.3 |
| Gather | ||||||
| ????C45AS | ???- | ???5.0 | ????5.0 | ??- | ??5.0 | ?5.0 |
| ????LAS | ???- | ???2.0 | ????2.0 | ??- | ??2.0 | ?2.0 |
| Zeolite A | ???- | ???7.5 | ????7.5 | ??- | ??7.5 | ?7.5 |
| ????HEDP | ???- | ???1.0 | ????- | ??- | ??2.0 | ?- |
| Carbonate | ???- | ???4.0 | ????4.0 | ??- | ??4.0 | ?4.0 |
| ????PEG?4000 | ???- | ???0.5 | ????0.5 | ??- | ??0.5 | ?0.5 |
| Foreign material (water etc.) | ???- | ???2.0 | ????2.0 | ??- | ??2.0 | ?2.0 |
| Dried additive | ???- | ????- | ??- | ??- | ?- | |
| ????TAED | ???1.0 | ???2.0 | ????3.0 | ??1.0 | ??3.0 | ?2.0 |
| ????PB4 | ???- | ???1.0 | ????4.0 | ??- | ??5.0 | ?0.5 |
| ????PB1 | ???6.0 | ???- | ?????- | ??- | ??- | ?- |
| Percarbonate | ???- | ???5.0 | ????12.5 | ??- | ?- | |
| Carbonate | ???- | ???5.3 | ????1.8 | ??- | ??0.4 | ?0.4 |
| ????NOBS | ???4.5 | ???- | ????6.0 | ??- | ??- | ?0.6 |
| Isopropyl benzene sulfonic acid | ???- | ???2.0 | ????2.0 | ??- | ??0.2 | ?0.2 |
| Lipase | ???0.4 | ???0.4 | ????0.4 | ??0.06 | ??0.05 | ?0.2 |
| Cellulase | ???0.1 | ???0.2 | ????0.2 | ??- | ??0.2 | ?0.2 |
| Amylase | ???0.1 | ???0.3 | ????0.3 | ??- | ??- | ?- |
| Proteolytic enzyme | ???1.0 | ???0.5 | ????0.5 | ??0.5 | ??0.5 | ?0.5 |
| ????PVPVI | ???- | ???0.5 | ????0.5 | ??- | ??- | ?- |
| ????PVP | ???0.5 | ???0.5 | ????0.5 | ??- | ??- | ?- |
| ????PVNO | ???- | ???0.5 | ????0.5 | ??- | ??- | ?- |
| ????SRP1 | ???- | ???0.5 | ????0.5 | ??- | ??- | ?- |
| The siloxanes antifoams | ???- | ???0.2 | ????0.2 | ??- | ??0.2 | ?0.2 |
| Amount to | ???100.0 | ???100.0 | ????100.0 | ??100.0 | ??100.0 | ?100.0 |
Embodiment 5
According to the present invention, prepare following granulated detergent prescription.Prescription W and X are particularly suitable for using under U.S.'s machine washing condition.Y is particularly suitable for using under Japan's machine washing condition.
Embodiment 6
| ?????T | ??????U | ??????V | |
| The blowing powder | |||
| Zeolite A | ????30.0 | ?????22.0 | ?????6.0 |
| Sodium sulfate | ????19.0 | ?????5.0 | ?????7.0 |
| ??MA/AA | ????3.0 | ?????3.0 | ?????6.0 |
| ??LAS | ????14.0 | ?????12.0 | ?????22.0 |
| ??C45AS | ????8.0 | ?????7.0 | ?????7.0 |
| Silicate | ????- | ?????1.0 | ?????5.0 |
| Soap | ????- | ?????- | ?????2.0 |
| Whitening agent 1 | ????0.2 | ?????0.2 | ?????0.2 |
| ??QEA1 | ????0.6 | ?????2.0 | ?????1.0 |
| Carbonate | ????0.8 | ?????16.0 | ?????20.0 |
| ??DTPMP | ????- | ?????0.4 | ?????0.4 |
| Be sprayed onto | ????- | ?????1.0 | ?????5.0 |
| ??C45E7 | ????1.0 | ?????1.0 | ?????1.0 |
| Dried additive | |||
| ??HEDP | ????1.0 | ?????- | ?????- |
| ??PVPVI/PVNO | ????0.5 | ?????0.5 | ?????0.5 |
| Proteolytic enzyme | ????1.0 | ?????1.0 | ?????1.0 |
| Lipase | ????0.4 | ?????0.1 | ?????0.2 |
| Amylase | ????0.1 | ?????0.1 | ?????0.1 |
| Cellulase | ????0.1 | ?????0.1 | ?????0.1 |
| ??TAED | ????- | ?????6.1 | ?????4.5 |
| ??PB | ????11.0 | ?????5.0 | ?????6.0 |
| Sodium sulfate | ????- | ?????6.0 | ?????- |
| Surplus (moisture and foreign material) |
According to the present invention, prepare the following granulated detergent that is particularly suitable under the machine washing condition of Europe, using and make up.
| ??W | ??X | |
| The blowing powder |
| Zeolite A | ?????20.0 | ?????- |
| ????STPP | ?????- | ?????20.0 |
| ????LAS | ?????6.0 | ?????6.0 |
| ????C68AS | ?????2.0 | ?????2.0 |
| Silicate | ?????3.0 | ?????8.0 |
| ????MA/AA | ?????4.0 | ?????2.0 |
| ????CMC | ?????0.6 | ?????0.6 |
| ????QEA1 | ?????0.9 | ?????0.6 |
| ????QEA3 | ?????0.1 | ?????- |
| Whitening agent 1 | ?????0.2 | ?????0.2 |
| ????DTPMP | ?????0.4 | ?????0.4 |
| Be sprayed onto | ||
| ????C45E7 | ?????5.0 | ?????5.0 |
| The siloxanes antifoams | ?????0.3 | ?????0.3 |
| Spices | ?????0.2 | ?????0.2 |
| Dried additive | ||
| Carbonate | ?????14.0 | ?????9.0 |
| ????PB1 | ?????1.5 | ?????2.0 |
| ????PB4 | ?????18.5 | ?????13.0 |
| ????TAED | ?????2.0 | ?????2.0 |
| The photoactivation SYNTHETIC OPTICAL WHITNER | ?????15ppm | ?????15ppm |
| Proteolytic enzyme | ?????1.0 | ?????1.0 |
| Lipase | ?????0.2 | ?????0.08 |
| Amylase | ?????0.4 | ?????0.4 |
| Cellulase | ?????0.1 | ?????0.1 |
| Vitriol | ?????10.0 | ?????20.0 |
| Surplus (moisture and foreign material) | ||
| Density (grams per liter) | ?????700 | ?????700 |
Embodiment 7
According to the present invention, prepare following detergent composition.
| ??????Y | ??????Z | ????AA | |
| The blowing powder | |||
| Zeolite A | ????15.0 | ????15.0 | ????15.0 |
| Sodium sulfate | ????0.0 | ????5.0 | ????0.0 |
| ??LAS | ????3.0 | ????3.0 | ????3.0 |
| ??OAS | ????- | ????1.5 | ????1.5 |
| ????DTPMP | ?????0.4 | ?????0.2 | ?????0.4 |
| ????CMC | ?????0.4 | ?????0.4 | ?????0.4 |
| ????MA/AA | ?????4.0 | ?????2.0 | ?????2.0 |
| Gather | |||
| ????LAS | ?????5.0 | ?????5.0 | ?????5.0 |
| ????TAS | ?????2.0 | ?????2.0 | ?????1.0 |
| Silicate | ?????3.0 | ?????3.0 | ?????4.0 |
| ????QEA1 | ?????1.0 | ?????2.5 | ?????0.6 |
| The Mn catalyzer | ?????0.03 | ?????- | ?????- |
| Zeolite A | ?????8.0 | ?????8.0 | ?????8.0 |
| Carbonate | ?????8.0 | ?????8.0 | ?????4.0 |
| Be sprayed onto | |||
| Spices | ?????0.3 | ?????0.3 | ?????0.3 |
| ????C45E7 | ?????2.0 | ?????2.0 | ?????2.0 |
| ????C25E3 | ?????2.0 | ?????- | ?????- |
| Dried additive | |||
| Citrate trianion | ?????5.0 | ?????- | ?????2.0 |
| Supercarbonate | ?????- | ?????3.0 | ?????- |
| Carbonate | ?????8.0 | ?????15.0 | ?????10.0 |
| Percarbonate | ?????- | ?????7.0 | ?????10.0 |
| ????TAED | ?????6.0 | ?????2.0 | ?????5.0 |
| ????PB1 | ?????14.0 | ?????7.0 | ?????10.0 |
| ????EDDS | ?????- | ?????2.0 | ?????- |
| MW is 5000000 polyethylene oxide | ?????- | ?????0.2 | |
| Wilkinite | ?????- | ?????- | ?????10.0 |
| Proteolytic enzyme | ?????1.0 | ?????1.0 | ?????1.0 |
| Lipase | ?????0.4 | ?????0.1 | ?????0.3 |
| Amylase | ?????0.6 | ?????0.6 | ?????0.6 |
| Cellulase | ?????0.6 | ?????0.6 | ?????0.6 |
| The siloxanes antifoams | ?????5.0 | ?????5.0 | ?????5.0 |
| Dried additive | |||
| Sodium sulfate | ?????0.0 | ?????3.0 | ?????0.0 |
| Surplus (moisture and foreign material) | ?????100.0 | ?????100.0 | ?????100.0 |
| Density (grams per liter) | ?????850 | ?????850 | ?????850 |
Embodiment 8
According to the present invention, prepare following detergent composition.
| ????BB | ????CC | ????DD | ????EE | |
| ????LAS | ????20.0 | ????14.0 | ????24.0 | ????22.0 |
| ????QAS | ????0.7 | ????1.0 | ????- | ????0.7 |
| ????TFAA | ????- | ????1.0 | ????- | ????- |
| ????C25E5/C45E7 | ????- | ????2.0 | ????- | ????0.5 |
| ????C45E3S | ????- | ????2.5 | ????- | ????- |
| ????STPP | ????30.0 | ????18.0 | ????30.0 | ????22.0 |
| Silicate | ????9.0 | ????5.0 | ????10.0 | ????8.0 |
| Carbonate | ????13.0 | ????7.5 | ????- | ????5.0 |
| Supercarbonate | ????- | ????7.5 | ????- | ????- |
| Percarbonate | ????- | ????5.0 | ????9.0 | ????15.0 |
| ????DTPMP | ????0.7 | ????1.0 | ????- | ????- |
| ????QEA1 | ????0.4 | ????1.2 | ????0.5 | ????2.0 |
| ????QEA2 | ????0.4 | ????- | ????- | ????- |
| ????SRP1 | ????0.3 | ????0.2 | ????- | ????0.1 |
| ????MA/AA | ????2.0 | ????1.5 | ????2.0 | ????1.0 |
| ????CMC | ????0.8 | ????0.4 | ????0.4 | ????0.2 |
| Proteolytic enzyme | ????0.8 | ????1.0 | ????0.5 | ????0.5 |
| Amylase | ????0.8 | ????0.4 | ????- | ????0.25 |
| Lipase | ????0.2 | ????0.06 | ????0.25 | ????0.1 |
| Cellulase | ????0.15 | ????0.05 | ????- | ????- |
| Photoactivation SYNTHETIC OPTICAL WHITNER (ppm) | ????70 ????ppm | ????45 ????ppm | ????- | ????10 ????ppm |
| Whitening agent 1 | ????0.2 | ????0.2 | ????0.08 | ????0.2 |
| ????PB1 | ????6.0 | ????2.0 | ????- | ????- |
| ????HEDP | ????- | ????- | ????2.3 | ????- |
| ????TAED | ????2.0 | ????1.0 | ????- | ????- |
| Surplus (moisture and foreign material) |
Embodiment 9
Following laundry detergent bar composition produced according to the present invention.
| ???FF | ???GG | ?????HH | ????II | ????JJ | ????KK | ????LL | ????MM | |
| ??LAS | ???- | ???- | ????19.0 | ???15.0 | ???21.0 | ????6.75 | ????8.8 | ????- |
| ??C28AS | ???30.0 | ???13.5 | ????- | ???- | ???- | ????15.75 | ????11.2 | ????22.5 |
| Sodium laurate | ???2.5 | ???9.0 | ????- | ???- | ???- | ????- | ????- | ????- |
| Zeolite A | ???2.0 | ???1.25 | ????- | ???- | ???- | ????1.25 | ????1.25 | ????1.25 |
| Carbonate | ???20.0 | ???3.0 | ????13.0 | ???8.0 | ???10.0 | ????15.0 | ????15.0 | ????10.0 |
| Lime carbonate | ???21.5 | ???- | ????- | ???- | ???- | ????- | ????- | ????- |
| Vitriol | ???5.0 | ???- | ????- | ???- | ???- | ????- | ????- | ????- |
| ??TSPP | ???5.0 | ???- | ????5.0 | ???- | ???5.0 | ????5.0 | ????2.5 | ????5.0 |
| ??STPP | ???5.0 | ???15.0 | ????- | ???- | ???- | ????5.0 | ????8.0 | ????10.0 |
| Wilkinite | ???- | ???10.0 | ????- | ???- | ???5.0 | ????- | ????- | ????- |
| ??DTPMP | ???- | ???0.7 | ????0.6 | ???- | ???0.6 | ????0.7 | ????0.7 | ????0.7 |
| ??MA/AA | ???0.4 | ???1.0 | ????- | ???- | ???0.2 | ????0.4 | ????0.5 | ????0.4 |
| ??SRP1 | ???0.3 | ???0.3 | ????0.3 | ???0.3 | ???0.3 | ????0.3 | ????0.3 | ????0.3 |
| Proteolytic enzyme | ???- | ???0.12 | ????- | ???0.08 | ???0.08 | ????- | ????- | ????0.1 |
| Lipase | ???0.07 | ???0.1 | ????0.15 | ???0.1 | ???0.2 | ????0.5 | ????0.1 | ????0.1 |
| Amylase | ???- | ???- | ????0.8 | ???- | ???- | ????- | ????0.1 | ????- |
| Cellulase | ???- | ???0.15 | ????- | ???- | ???0.15 | ????- | ????- | ????- |
| ??PEO | ???- | ???0.2 | ????- | ???0.2 | ???0.3 | ????- | ????- | ????0.3 |
| Spices | ???1.6 | ???- | ????- | ???- | ???- | ????- | ????- | ????- |
Following compacting high-density produced according to the present invention (0.96kg/l) dishwashing detergent composition F F to KK, and its meaning of the symbol of used composition is as follows in this washing composition: metasilicate: metasilicate sodium (SiO
2: Na
2O=1.0) non-ionic type: sell with trade(brand)name Plurafac LF404 by BASF GmbH,
Average degree of ethoxylation 3.8, and average propoxylation degree 4.5
C
13-C
15Mixed ethoxylated/propoxylated fatty alcohol (low bubble) PAAC: five amine cobaltous acetate (III) salt BzP: benzoyl peroxide paraffin: the paraffin oil BTA that sells with trade(brand)name Winog70 by Wintershall: benzotriazole Bismuth trinitrate: Bismuth trinitrate salt trimer: contain vinylformic acid: toxilic acid: ethylacrylic acid monomeric unit, its weight
Than being 60: 20: 20, the trimer 480N:3 of molecular-weight average about 7000: vinylformic acid/methacrylic acid of 7, molecular-weight average about 3500
Random copolymers
| ????FF | ?????GG | ?????HH | ?????II | ????JJ | ????KK | |
| ????STPP | ???24.80 | ????24.80 | ????25.00 | ????28.39 | ???28.50 | ???20.00 |
| Citrate trianion | ???- | ????- | ????- | ????- | ???10.00 | ???10.00 |
| Carbonate | ???- | ????- | ????17.50 | ????17.50 | ???- | ???- |
| ????QEA1 | ???0.5 | ????1.5 | ????2.0 | ????1.0 | ???0.3 | ???0.8 |
| Silicate | ???20.36 | ????20.36 | ????14.81 | ????14.81 | ???14.81 | ???- |
| Metasilicate | ???2.50 | ????2.50 | ????2.50 | ????- | ???- | ???- |
| ????PB1 | ???7.79 | ????7.79 | ????9.74 | ????14.28 | ???9.74 | ???- |
| ????PB4 | ????- | ????- | ????- | ???- | ???- | |
| Percarbonate | ???- | ????- | ????- | ????- | ???- | ???6.70 |
| Non-ionic type | ???1.50 | ????1.50 | ????2.00 | ????1.50 | ???2.00 | ???2.60 |
| ????TAED | ???2.39 | ????2.39 | ????2.39 | ????- | ???- | ???4.00 |
| ????HEDP | ???0.46 | ????0.46 | ????1.00 | ????- | ???0.83 | ???- |
| ????DETPMP | ???- | ????- | ????0.65 | ????- | ???- | ???- |
| ????PAAC | ???- | ????- | ????- | ????0.20 | ???- | ???- |
| ????B,P | ???- | ????- | ????- | ????4.44 | ???- | ???- |
| Paraffin | ???0.50 | ????0.50 | ????0.50 | ????0.50 | ???- | ???0.20 |
| Proteolytic enzyme | ???2.20 | ????2.20 | ????2.20 | ????2.20 | ???2.00 | ???0.50 |
| Amylase | ???1.50 | ????1.50 | ????1.20 | ????1.50 | ???1.00 | ???1.10 |
| ????BTA | ????0.30 | ??0.30 | ????0.30 | ???0.30 | ????- | ????- |
| Bismuth trinitrate | ????- | ??- | ????0.30 | ???- | ????- | ????- |
| Lipase | ????0.5 | ??0.3 | ????1.0 | ???1.4 | ????0.8 | ????0.6 |
| Trimer | ????- | ??- | ????- | ???4.00 | ????- | ????- |
| ????480N | ????2.77 | ??2.77 | ????6.00 | ???- | ????6.67 | ????- |
| Vitriol | ????8.44 | ??8.44 | ????20.77 | ???- | ????23.24 | ????1.00 |
| Foreign material and water surplus | ||||||
| PH (1% solution) | ????10.90 | ??10.90 | ????11.00 | ???10.80 | ????10.90 | ????9.60 |
Claims (21)
1. a granular detergent composition or its component wherein comprise: (a) lipolytic enzyme; (b) have the water-soluble cationic compound of dirt removal/antiredeposition performance, it is selected from:
1) have ethoxylation positively charged ion one amine of following structural formula:
2) have the ethoxylation cationic diamine of following structural formula:
M wherein
1Be N+ or N group; Each M
2Be N+ or N group; And at least one M
2Be the N+ group;
3) have the ethoxylation cationic polyamine of following structural formula:
4) and composition thereof; A wherein
1Be
And R is H or C
1-C
4Alkyl or hydroxyalkyl, R
1Be C
2-C
12Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2-
2-C
3The oxyalkylene part, but can not form any O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl ,-the L-X part, or two R
2Formation-(CH together
2)
r-A
2-(CH
2)
s-part, wherein A
2For-O-or-CH
2-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; Each R
3Be C
1-C
8Alkyl or hydroxyalkyl, benzyl ,-the L-X part, perhaps, two R
3Or R
2With a R
3Formation-(CH together
2)
r-A
2-(CH
2)
5-part; R
4For replacing C
3-C
12Alkyl, hydroxyalkyl, alkenyl, aryl or have the alkaryl of para-orientation position; R
5Be C
1-C
12Alkenyl, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2-
2-C
3The oxyalkylene part, but can not form any O-O or O-N key; X is for being selected from H, C
1-C
4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof; L is for containing polyoxyalkylene part-[(R
6O)
m(CH
2CH
2O)
n]-hydrophilic chain; R wherein
6Be C
3-C
4Alkylidene group or hydroxyl alkylidene group, and the number of m and n should make-(CH
2CH
2O)
n-part account for described polyoxyalkylene part at least about 50% weight; M
2During for N+, d is 1, M
2During for N, d is 0; For described positively charged ion one amine, n is at least about 16, for described cationic diamine at least about 6, for described cationic polyamine at least about 3; P is 3-8; Q is 1 or 0; T is 1 or 0, but q is 1 o'clock, and t is 1, and wherein compound (a) and ratio (b) are 1: 100 to 100: 1.
2. according to granular detergent composition or its component of claim 1, wherein said ratio is 1: 10 to 10: 1.
3. according to the granular detergent composition of claim 1 or 2, the consumption of wherein said cation compound is 0.01% to 30% of a detergent composition weight.。
4. according to any one granular detergent composition among the claim 1-3, wherein said cation compound is that 0.2% to 3% amount with detergent composition weight adds.
5. according to any one granular detergent composition or its component among the claim 1-4, wherein said cation compound is ethoxylation positively charged ion one amine, it is characterized in that a R
2Be methyl, two R
2Be the L-X part, m be 0 and n be at least about 20.
6. according to any one granular detergent composition or its component among the claim 1-4, wherein said cation compound is the ethoxylation cationic diamine, it is characterized in that R
1Be C
2-C
6Alkylidene group.
7. according to granular detergent composition or its component of claim 6, wherein said ethoxylation cationic diamine is characterised in that R
1Be hexylidene.
8. according to any one detergent composition or its component among the claim 1-4, wherein said cation compound is the ethoxylation cationic polyamine, it is characterized in that R
4For replacing C
3-C
6Alkyl, hydroxyalkyl or aryl; A1 is
And p is 3-6.
9. according to any one granular detergent composition or its component among the claim 6-8, wherein said cation compound is characterised in that: R
2Be methyl or L-X part, each R
3Be methyl, and M
1With each M
2Be N
+Group.
10. according to any one granular detergent composition or its component among the claim 6-9, wherein m be 0 and n be at least 12.
11. according to the granular detergent composition in claim 6 or 7 or its component, wherein m be 0 and n be at least about 20.
12. according to any one granular detergent composition of claim 1-11, wherein said lipolytic enzyme adds with the amount of composition weight 0.01% to 3%, press the active calculating of 100KLU/g.
13. according to any one granular detergent composition of claim 1-12, wherein said lipolytic enzyme adds with the amount of composition weight 0.03% to 1%, press the active calculating of 100KLU/g.
14. according to any one granular detergent composition or its component among the claim 1-13, the cationic polymers that wherein has dirt removal/antiredeposition performance be characterised in that have main chain, at least 2 M groups and at least 1 L-X group, wherein M is for being connected on the main chain, or the cation group that is connected as a single entity with major key, and comprise N
+Center of positive charge; L connects M group and X group or X is connected on the main polymer chain; X is for being selected from H, C
1-C
4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof; And L is for containing polyoxyalkylene part-[(R
6O)
m(CH
2CH
2O)
n]-hydrophilic chain.
15. according to granular detergent composition or its component of claim 14, wherein said cationic polymers is the ethoxylation cationic polymers that a kind of main chain is selected from urethane, polyester, polyethers, polyimide, polyalkyleneimine and composition thereof.
16. according to any one granular detergent composition among the claim 1-15, it is 8.0-10.5 that wherein said composition makes washing lotion pH value through allotment.
17. according to any one granular detergent composition among the claim 1-16, wherein the consumption of heavy metal ion chelating agent is the 0.1-10% of described detergent composition weight.
18. wherein have organic peroxyacid bleaching system according to detergent composition or its component of any one among the claim 1-17, comprise hydrogen peroxide cource and organic peroxy acid blanching precursor compound.
19., wherein contain the tensio-active agent that is selected from anion surfactant, nonionogenic tenside, cats product, amphoterics and zwitterionics and composition thereof according to any one granular detergent composition or its component among the claim 1-18.
20. method of washing clothes in the family expenses washing machine, wherein, before beginning washing, the preferred partitioning device that uses, with introducing in the washing machine drum according to the granular detergent composition of any one among the claim 1-19 of significant quantity, described partitioning device can make granular detergent composition be discharged in the washing lotion gradually during washing.
21. according to any one granular detergent composition or its component of claim 1-20, the application in the dishwashing detergent process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9619927.8 | 1996-09-24 | ||
| GB9619927A GB2317393A (en) | 1996-09-24 | 1996-09-24 | Detergent compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1238802A true CN1238802A (en) | 1999-12-15 |
Family
ID=10800426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97199989 Pending CN1238802A (en) | 1996-09-24 | 1997-09-22 | Detergent composition comprising cationic amines and lipase enzymes |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0929637A4 (en) |
| JP (1) | JP2000503712A (en) |
| CN (1) | CN1238802A (en) |
| AR (1) | AR010475A1 (en) |
| AU (1) | AU4356597A (en) |
| BR (1) | BR9713217A (en) |
| CA (1) | CA2265803A1 (en) |
| GB (1) | GB2317393A (en) |
| WO (1) | WO1998013463A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104955930A (en) * | 2013-02-19 | 2015-09-30 | 宝洁公司 | Method of laundering a fabric |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6906022B1 (en) | 1998-09-25 | 2005-06-14 | The Procter & Gamble Company | Granular detergent compositions having homogenous particles and process for producing same |
| WO2000018877A1 (en) * | 1998-09-25 | 2000-04-06 | The Procter & Gamble Company | Granular detergent compositions having homogenous particles and process for producing same |
| GB0810881D0 (en) * | 2008-06-16 | 2008-07-23 | Unilever Plc | Improvements relating to fabric cleaning |
| WO2009153184A1 (en) * | 2008-06-16 | 2009-12-23 | Unilever Plc | Improvements relating to fabric cleaning |
| WO2016004617A1 (en) * | 2014-07-11 | 2016-01-14 | The Procter & Gamble Company | Structured particles comprising alkoxylated polyalkyleleimine, and granular laundry detergent comprising particles |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101457A (en) * | 1975-11-28 | 1978-07-18 | The Procter & Gamble Company | Enzyme-containing automatic dishwashing composition |
| US4659802A (en) * | 1982-12-23 | 1987-04-21 | The Procter & Gamble Company | Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions |
| DE3380259D1 (en) * | 1982-12-23 | 1989-08-31 | Procter & Gamble | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
| US4664848A (en) * | 1982-12-23 | 1987-05-12 | The Procter & Gamble Company | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
| US4861512A (en) * | 1984-12-21 | 1989-08-29 | The Procter & Gamble Company | Sulfonated block polyesters useful as soil release agents in detergent compositions |
| US4711730A (en) * | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
| US4713194A (en) * | 1986-04-15 | 1987-12-15 | The Procter & Gamble Company | Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions |
| US4861502A (en) * | 1988-02-08 | 1989-08-29 | The Procter & Gamble Company | Conditioning agent containing amine ion-pair complexes and composiitons thereof |
| CA2191314C (en) * | 1994-06-01 | 2000-06-27 | Ronald A. Ii Swift | Detergent composition containing oleoyl sarcosinate and anionic surfactants in optimum ratios |
| EP0906382A4 (en) * | 1996-05-17 | 1999-11-24 | Procter & Gamble | Detergent composition |
-
1996
- 1996-09-24 GB GB9619927A patent/GB2317393A/en not_active Withdrawn
-
1997
- 1997-09-22 CA CA002265803A patent/CA2265803A1/en not_active Abandoned
- 1997-09-22 AU AU43565/97A patent/AU4356597A/en not_active Abandoned
- 1997-09-22 JP JP10515748A patent/JP2000503712A/en active Pending
- 1997-09-22 CN CN 97199989 patent/CN1238802A/en active Pending
- 1997-09-22 BR BR9713217-9A patent/BR9713217A/en unknown
- 1997-09-22 WO PCT/US1997/016716 patent/WO1998013463A1/en not_active Application Discontinuation
- 1997-09-22 EP EP97941712A patent/EP0929637A4/en not_active Withdrawn
- 1997-09-24 AR ARP970104402 patent/AR010475A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104955930A (en) * | 2013-02-19 | 2015-09-30 | 宝洁公司 | Method of laundering a fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0929637A1 (en) | 1999-07-21 |
| GB9619927D0 (en) | 1996-11-06 |
| EP0929637A4 (en) | 2000-01-05 |
| GB2317393A (en) | 1998-03-25 |
| AU4356597A (en) | 1998-04-17 |
| AR010475A1 (en) | 2000-06-28 |
| CA2265803A1 (en) | 1998-04-02 |
| WO1998013463A1 (en) | 1998-04-02 |
| JP2000503712A (en) | 2000-03-28 |
| BR9713217A (en) | 2000-12-05 |
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