CN1224446A - Detergent compositions comprising polyamine scavenger agents and enzymes - Google Patents
Detergent compositions comprising polyamine scavenger agents and enzymes Download PDFInfo
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- CN1224446A CN1224446A CN96180364A CN96180364A CN1224446A CN 1224446 A CN1224446 A CN 1224446A CN 96180364 A CN96180364 A CN 96180364A CN 96180364 A CN96180364 A CN 96180364A CN 1224446 A CN1224446 A CN 1224446A
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Classifications
-
- 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
-
- 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
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
Abstract
The present invention encompasses detergent compositions comprising lipase enzymes and polyamine scavenger agents. The lipase containing detergent composition has improved body soil and grease stain removal properties.
Description
FIELD OF THE INVENTION
The present invention relates to adopt polyamine scavenger agents and enzyme to strengthen cleaning performance, particularly remove the detergent composition of oil stain and health dirt.Fabric washing and hard-surface cleaning composition with improved removal health dirt and oil stain performance are provided.
The background of invention
The task that detergent manufacturers faces is to design to remove the product of wide spectrum dirt and spot from clean surface.Special hope can be removed body surface dirt and oil stain from clean surface, as butter, oleomargarine and meat oil.
The detergent composition that contains enzyme (comprising lipase) has been well-known.The detergent composition that contains lipase can make the triglyceride hydrolysis in health dirt and the grease effectively, thereby can remove body surface dirt and oil stain from clean surface effectively.Though without wishing to be bound by theory, people still think usually, in the triglyceride level of lipase in hydrolysis health grease and greasy dirt, understand inactivation owing to contacting with chlorine.In cleaning process, since cleaning liquid, for example effect of chlorine in the tap water, and lipase goes body fat and grease fouling performance just can reduce.
Chlorine scavenger such as S-WAT, peroxyboric acid and ammonium sulfate can remove or " removing " washings in chlorine.Yet in typical cleaning process, many scavenging agents only can remove dechlorination from cleaning liquid in initial cleaning process, and when rinse stage adds extra chloride cleaning liquid, just almost can't see what removing effect.
Have been found that now the composition that contains polyamine scavenger agents can be used to remove the chlorine in the cleaning liquid.In addition, polyamine is deposited on the clean surface, therefore can keep lipase to remove the usefulness of oil stain and health dirt at rinse stage.Though do not want to be limited by theory, thinking still that polyamine deposits on the clean surface and at rinse stage at wash phase continues to remain on this surface, thereby even still can remove chlorine effectively at rinse stage.Therefore, contain the detergent composition of this polyamine scavenger agents, can keep lipase to remove the usefulness of health dirt and oil stain from clean surface.
So, the purpose of this invention is to provide the composition that removal health dirt and oil stain performance are improved, said composition contains lipase and polyamine scavenger agents.By above these purposes or some other purpose that can see this patent in the following disclosure.
Background technology
Following document has disclosed various polymkeric substance or modified polyamine; United States Patent (USP) 4,548, No. 744, Connor, authorization date on October 22nd, 1985; United States Patent (USP) 4,597, No. 898, VanderMeer, authorization date on July 1st, 1986; United States Patent (USP) 4,877, No. 896, people such as Maldonado, authorization date on October 31st, 1989; United States Patent (USP) 4,891, No. 160, VanderMeer, 2 days January nineteen ninety of authorization date; United States Patent (USP) 4,976, No. 879, people such as Maldonado, 11 days December nineteen ninety of authorization date; United States Patent (USP) 5,415, No. 807, Gosselink, 16 days Mays nineteen ninety-five of authorization date; United States Patent (USP) 4,235, No. 735, people such as Marco, authorization date on November 25th, 1980; World patent WO 95/32272, open November 30 nineteen ninety-five on date; English Patent 1,537, No. 288, open December 29 1978 date; English Patent 1,498, No. 520, open January 18 1978 date; No. 2829022, German patent DE, authorization date on January 10th, 1980; Day disclosure JP 06313271, open April 27 1994 date.
In following patent, reported the detergent composition that contains lipase: United States Patent (USP) 3,950, No. 277; United States Patent (USP) 4,011, No. 169; No. 205,208, European patent; No. 206,390, European patent, No. 214,716, European patent and 258, No. 068 every piece of patents of European patent all have detailed description to lipase.
Brief summary of the invention
The present invention is around the detergent composition that contains lipase and polyamine scavenger agents.
The present invention is directed to the detergent composition that contains following ingredients: the A. detergent surfactant; B. lipase, its amount in every milligram of composition about 0.004 to about 6 steatolysis units; C. about 0.01% to about 15% scavenging agent, this scavenging agent contain the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n+1)W
mY
nZ or contain the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n-k+1)W
mY
nY '
kZ, wherein k is less than or equal to n, and the molecular weight of above-mentioned polyamine main chain before modification is greater than about 200 dalton, in the formula
ⅰ) the V unit is the end group unit of following formula:
ⅱ) the W unit is the backbone units of following formula:
ⅲ) the Y unit is a chain unit of following formula:
ⅳ) the Z unit is the end group unit of following formula:
Wherein be connected with the unitary main chain of R and be selected from following chain: C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Dihydroxyl-alkylidene group, C
8-C
12Two alkyl arylenes ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-, and mixed base; R wherein
1Be C
2-C
6Alkylidene group and mixed base thereof; R
2Be hydrogen ,-(R
1O)
xB and its mixed base; R
3Be C
1-C
18Alkyl, C
7-C
12Aralkyl, C
7-C
12The aryl that alkyl replaces, C
6-C
12Aryl, and mixed base; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkylene group, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and mixed base thereof; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Dihydroxyl-alkylidene group, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-, and mixed base, R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; E is selected from the following units: hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3, and mixed base; Oxide compound; B is a hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, and mixed base; M is hydrogen or water-soluble cationic, and its quantity is enough to satisfy charge balance; X is a water soluble anion; The numerical value of m from 4 to about 400; The numerical value of n from 0 to about 200; The numerical value of p from 1 to 6; The numerical value of q from 0 to 6; The numerical value of r is 0 or 1; The numerical value of w is 0 or 1; The numerical value of x from 1 to 100; The numerical value of y from 0 to 100; The numerical value of z is 0 or 1; And
D. all the other are adjunct ingredient.
The detailed description of invention
According to the present invention, discovery will make and contain the lipase cleaning composition and have fabulous degrease and remove the body surface fouling performance, can reach by the said composition that preparation contains the significant quantity polyamine scavenger agents.
Except as otherwise noted, all per-cents, ratio and ratio all are to be unit in weight herein.Except as otherwise noted, all temperature all with degree centigrade (℃) metering.All documents of quoting are listed in conjunction with its reference all at relevant portion.Tensio-active agent
Be applicable to that tensio-active agent of the present invention is positively charged ion, negatively charged ion, nonionic, both sexes, zwitter-ion and composition thereof, this paper will be further described below.Laundry detergent composition is any suitable form, for example outside particle-removing or the laundry strip, goes back concentrated solution, and thin liquid or other can pour into form.Can allocate polyamine scavenger agents of the present invention in the selected any washing matrix of manufacturers into.
According to the present invention, detergent for washing clothes can also contain in addition at least about 0.01%, preferably at least about 0.1%, more preferably at least about the following surfactant of 1% weight percent.Non-limiting tensio-active agent example useful in this article, typical amounts from about 1% to about 55% comprises conventional C
11-C
18Alkylbenzene sulfonate (" LAS ") and primary, side chain and random C
10-C
20Alkyl-sulphate (" AS "), C
10-C
18Secondary (2,3) alkyl-sulphate, its molecular formula is CH
3(CH
2)
x(CHOSO
3 -M
+) CH
3And CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3, x and (y+1) be to be approximately 7 integer at least in the formula preferably be approximately 9 at least, and M is water-soluble cationic, particularly sodium, undersaturated vitriol such as oleyl sulfate, C
10-C
18Alkyl alkoxy sulfate (" AE
xS ", EO1-7 ethoxy sulfate particularly), C
10-C
18Alkyl alkoxy carboxylate salt (particularly EO1-5 ethoxy carboxylate), C
10-C
18Glyceryl ether, C
10-C
18Alkyl polyglycoside and the corresponding many glycosides of sulfation thereof, and C
12-C
18α sulfonic acid fatty acid ester.Need, also can comprise the non-ionic type of routine and amphoteric tensio-active agent in the total composition, for example C
12-C
18Alkylethoxylate (" AE ") is comprising what is called narrow peak alkylethoxylate and C
6-C
12Alkane phenol alkoxy compound (particularly ethoxylate and blended oxyethyl group/propoxylated glycerine), C
12-C
18Trimethyl-glycine and sultaine (" Sultaines "), C
10-C
18Amine oxide etc.Also can use C
10-C
18N-alkyl polyhydroxy fatty amide.Typical example comprises C
12-C
18The N-methyl glucose amide.Referring to WO 9,206,154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, as C
10-C
18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C
12-C
18Glucamide can be used for low foam occasion.Also can use C
10-C
20Conventional soap class.If want high foam, can use side chain C
10-C
16The soap class.The mixing of negatively charged ion and nonionogenic tenside is particularly useful.Other conventional useful tensio-active agent is enumerated in standard textbook.Lipase
Suitable lipase is by the pseudomonas class, as GB 1,372, and the pseudomonas stutzeri ATCC 19.154 that discloses in 034, described microorganisms.Also can be referring to the lipase in No. 53,20487, the Japanese patent application book (on February 24th, 1978 is open).This lipase can be buied from the Amano Pharmaceutical Co.Ltd. of Japanese Nagoya, and its trade(brand)name is lipase P " Amano " or " Amano-P ".Other suitable commercialization lipase comprises Amano-CES, by viscosity pigment bacillus, and Toyo Jozo Co. for example, Tagata, the viscosity pigment bacillus of Japan is separated fat and belongs to the lipase that mutation NRRLB 3673 extracts; U.S. Biochemical Corp. and Dutch Disoynth Co., viscosity pigment bacillus lipase.The lipase that the gladiolus pseudomonas is extracted.Dredge cotton wool humic bacterium deutero-lipase (registered trademark LIPOLASE
) can be from Novo IndustriA/S, Denmark buys, also can be referring to EP 341,947, and it is the preferred lipase that this patent uses.Also can use the mixture of above-mentioned lipase.
The amount that contains lipase of the present invention in the detergent composition is to make final composition have lipolytic enzyme active 0.004 to about 6; Preferred about 0.007 to about 3; More preferably from about 0.01 to about 1 every milligram of composition is separated fat unit (LU/mg).
Detergent composition of the present invention contains 0.001% to about 5%; Preferred about 0.01% to about 2%; More preferably from about 0.1% to about 1% weight percent lipase.
Lipase unit (LU) is under the following conditions: 30 ℃ of temperature, pH=7.0, substrate is the tributyrin (Merck art.1958) of 4.8wt.%, the softening water of 78.5wt.% and the emulsion of 16.7wt.% emulsifying agent, and when pH was static, per minute can produce the lipase amount of the titratable lipid acid of 1 mmole.Described emulsifying agent is to prepare with the mixture of 17.9 gram sodium-chlor, 0.41 gram potassium primary phosphate (Merck art.4873), 400 milliliters of softening waters, 540 milliliters of glycerine (Merck art.4094) and 6.0 gram gum arabics (Sigma no.G-9752).Scavenging agent
Scavenging agent of the present invention relates to modified polyamine.These polyamine contain linear or the cyclic main chain.The polyamine main chain also can more or less contain some polyamine side chains.In general, polyamine main chain described herein is such modification: each nitrogen of polyamine chain below will be substituted with what is called, be described by quaternized, oxidized or its formed unit that combines.
With regard to purpose of the present invention, the definition of term " modification " is to substitute main chain NH hydrogen atom (replacement), make main chain nitrogen seasonization (by quaternized) or main chain nitrogen is oxidized to N-oxide compound (oxidized) with the E unit.When referring to when being adsorbed on hydrogen atom process on the main chain nitrogen with the E replacement unit, term " modification " and " replacement " are used interchangeably.Do not having to carry out quaternized or oxidizing reaction under some situation of substitution reaction, but the oxidation or the quaterisation of at least one main chain nitrogen are followed in preferred substitution reaction.
Linear or the acyclic polyamine main chain of forming scavenging agent of the present invention has following general molecular formula:
Above-mentioned main chain before modification subsequently, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.The cyclic polyamines main chain of forming scavenging agent of the present invention has following general molecular formula:
Above-mentioned main chain before modification subsequently, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.
With regard to the object of the invention, just be defined as V or Z " end group " unit in case constitute the primary amine nitrogen modification of main chain or side chain.For example, primary amine group is positioned at the end of polyamine main chain or side chain, and its structural formula is:
H
2N-R]-when it during according to modification of the present invention, after this just it is defined as V " end group " unit, or is called for short the V unit.Yet concerning the object of the invention, some or all primary amine groups can remain unmodified under the restricted condition that this paper below will further narrate.These unmodified primary amine groups remain " end group " unit because of its position in main chain.Equally, primary amine group is positioned at the end of polyamine main chain, and its structural formula is as follows:
-NH
2When it during according to modification of the present invention, after this just it is defined as Z " end group " unit, or is called for short the Z unit.It is unmodified that this unit can remain under the restricted condition that this paper below will further narrate.
Equally, just be defined as W " main chain " unit in case constitute the secondary amine nitrogen modification of main chain or side chain.For example, a secondary amine group (main component of main chain of the present invention and side chain) has the following formula structure:
When it during according to modification of the present invention, after this just it is defined as W " main chain " unit, or is called for short the W unit.Yet for the object of the invention, some or all secondary amine groups can remain unmodified.These unmodified secondary amine groups remain " main chain " unit because of its position in main chain.
Further analogize, constitute the tertiary amine nitrogen of main chain or side chain, in case modification just is defined as Y " side chain " unit.For example, a tertiary amine group (it is the chain component point of polyamine main chain or other side chain or ring) has the following formula structure
When it during according to modification of the present invention, after this just it is defined as Y " side chain " unit, or abbreviates the Y unit as.Yet for the object of the invention, some or all tertiary amine groups can remain unmodified.These unmodified tertiary amine groups remain " side chain " unit because of its position in main chain.Being used to be connected polyamine nitrogen with V, W with nitrogen bonded R unit, Y unit will introduce below.
So the final modified structure of polyamine of the present invention, linear polyamine polymer can be used following general formula
V
(n+1)W
mY
nZ can use following general formula for the cyclic polyamines polymkeric substance
V
(n-k+1)W
mY
nY '
kZ is for the polyamine that contains ring, the Y ' unit of following formula
Tapping point as a main chain or a chain link.For each Y ' unit, all there is the Y unit of a following formula
It will constitute the tie point that this ring is linked host polymer chain or side chain.At main chain is under the unique situation of unbroken loop, and the polyamine main chain is a following formula
So it does not contain Z end group unit and the following molecular formula of tool
V
N-kW
my
nY '
kWherein, k is the side chain unit number that constitutes ring.Preferred not cyclization of polyamine main chain of the present invention.
Under non-annularity polyamine situation, index n is relevant with the relative degree of branching with the ratio of exponent m.According to the present invention, branchiess linear modified polyamine has following chemical formula fully
VW
mZ promptly, n equals 0.The value of n big more (ratio of m and n is more little), the degree of branching is just big more in this molecule.Typical m value from minimum 4 to about 400, but also preferred bigger m value, particularly very little or when being almost 0 when index n value.
Each polyamine nitrogen (no matter be primary, the second month in a season or uncle) is in case according to modification of the present invention, always just can be defined as it one of following three kinds of classification: simply replacement, quaternized or oxidation.Unmodified those polyamine nitrogen unit look it is primary, the second month in a season or uncle's nitrogen and be included into V, W, Y or Z unit.With regard to the object of the invention, unmodified primary amine nitrogen is exactly V or Z unit, and unmodified secondary amine nitrogen is exactly the W unit, and unmodified tertiary amine nitrogen is exactly the Y unit.
The primary amine group of modification is defined as V " end group " unit, and it has one of following three kinds of forms:
A) have the simple replacement unit of following formula structure:
B) have the quaternized unit of following formula structure:
Wherein X provides the suitable counter of charge balance; With
C) have the oxidation unit of following formula structure:
The modification secondary amine group is defined as W " main chain " unit with one of following three kinds of forms:
A) have the simple replacement unit of following formula structure:
B) have the quaternized unit of following formula structure:
Wherein X provides the suitable counter of charge balance; With
C) have the oxidation unit of following formula structure:
The enhanced tertiary amine group definition is Y " side chain " unit with one of following three kinds of forms:
A) have the unmodified unit of following formula structure:
B) have the quaternized unit of following formula structure:
Wherein X provides the suitable counter of charge balance; With
C) have the oxidation unit of following formula structure:
Some modification primary amine group is defined as the Z end group unit of one of following three kinds of forms:
A) have the simple replacement unit of following formula structure:
B) have the quaternized unit of following formula structure:
Wherein X provides the suitable counter of charge balance; With
C) have the oxidation unit of following formula structure:
When arbitrary position on the nitrogen is not substituted or is unmodified, be interpreted as hydrogen and will replace E.For example, containing the unitary primary amine of a hydroxyethyl form E unit is V end group unit, and chemical formula is (HOCH
2CH
2) NH-.
With regard to the object of the invention, there are two class chain end group unit, V and Z unit.Z " end group " unit is to be-NH by structure
2End group primary amino group deutero-.According to the present invention, non-annularity polyamine main chain only contains a Z unit, and cyclic polyamines may not contain the Z unit.Form the N-oxide compound except the Z unit is modified, Z " end group " unit can be replaced by the E unit that this paper will be further described below.Be oxidized under the situation of N-oxide compound at Z unit nitrogen, nitrogen must be modified, so E can not be a hydrogen.
Polyamine of the present invention contains main chain R " connection " unit, to be used for connecting all nitrogen-atoms of this main chain.With regard to the object of the invention, the R unit comprises what is called " alkyl R " unit and " oxygen R " unit." alkyl " R unit is C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
3-C
12Hydroxy alkylidene (wherein oh group can be on the R cellular chain except that directly and on the arbitrary position the polyamine main chain nitrogen carbon atom that link); C
4-C
12Alkyl sub-dihydroxy (except that directly and polyamine main chain nitrogen join the carbon atom, hydroxyl groups can occupy wantonly two carbon atoms of R cellular chain); C
8-C
12(with regard to the object of the invention, it is the arylene group that has as two alkyl substituents of connection chain part to the dialkyl group arylidene.For example, two alkyl arylene tool following formulas:
This unit is 1,4 replacement not necessarily, also can be 1,2 or 1,3 C that replaces
2-C
12Alkylidene group, preferred ethylidene, propylene and composition thereof, more preferably ethylidene." oxygen " R contains-(R the unit
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-CH
2CH (OR
2) CH
2-,-(R
1O)
xR
1, and mixed cell, preferred cell is C
2-C
12Alkylidene group, C
3-C
12The hydroxyl alkylidene group, C
4-C
12The dihydroxy alkylidene group, C
8-C
12Two alkyl arylenes ,-(R
1O)
xR
1-,-(CH
2CH (OR
2) CH
2-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH-(OH) CH
2)
w-,-(R
1O)
xR
5(OR
1)
x-, preferred R unit is C
2-C
12Alkylidene group, C
3-C
12The hydroxyl alkylidene group, C
4-C
12The dihydroxy alkylidene group ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH-(OH) CH
2)
w-and its mixed cell, more preferred R unit is C
2-C
12Alkylidene group, C
3Hydroxy alkylidene and mixed cell thereof, most preferably C
2-C
6Alkylidene group.The most preferred main chain of the present invention contains at least 50% ethylidene R unit.
R
1The unit is C
2-C
6Alkylidene group and mixed cell thereof, preferred ethylidene.R
2Be hydrogen and-(R
1O)
xB, preferred hydrogen.
R
3Be C
1-C
18Alkyl, C
7-C
12Aryl alkylene, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and mixed cell thereof, preferred C
1-C
12Alkyl, C
7-C
12Aryl alkylene, more preferably C
1-C
12Alkyl, most preferable.R
3The unit is as the part of E unit described below.
R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkylene group, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, preferred C
1-C
10Alkylidene group, C
8-C
12Aryl alkylene, more preferably C
2-C
8Alkylidene group, most preferably ethylidene or butylidene.
R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-C (O) (R
4)
rC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-, R
5Ethene preferably ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH-(OH) CH
2-, more preferably-CH
2CH (OH) CH
2-.
R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene.
Preferably " oxygen " R unit is according to R
1, R
2And R
5The unit further defines.Preferably " oxygen " R unit contains preferred R
1, R
2And R
5The unit.Preferred scavenging agent of the present invention contains at least 50% ethylidene R
1The unit.Preferred R
1, R
2And R
5The unit combines with " oxygen " R unit and generates following preferred " oxygen " R unit.
ⅰ) with preferred R
5Substitution-(CH
2CH
2O)
xR
5(OCH
2CH
2)
x-, generation-(CH
2CH
2O)
xCH
2CHOHCH
2(OCH
2CH
2)
x-
ⅱ) with preferred R
1And R
2Substitution-(CH
2CH (OR
2) CH
2O)
z-(R
1O)
yR
1O (CH
2CH (OR
2) CH
2)
w-generation-(CH
2CH (OH) CH
2O)
z-(CH
2CH
2O)
yCH
2CH
2O (CH
2CH) (OH) CH
2)
w-
ⅲ) with preferred R
2Substitution-CH
2CH (OR
2) CH
2-generation-CH
2CH (OH) CH
2-
The E unit is selected from following groups: hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
mB ,-C (O) R
3, preferred hydrogen, C
2-C
22Hydroxy alkylidene, benzyl, C
1-C
22Alkylidene group ,-(R
1O)
mB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, more preferably C
1-C
22Alkylidene group ,-(R
1O)
xB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M, more preferably C
1-C
22Alkylidene group ,-(R
1O)
xB and-C (O) R
3When not in addition modification or when replacing, hydrogen atom will remain the group of representing E so on the nitrogen.
When V, W or the oxidation of Z unit, the E unit is hydrogen atoms not, and promptly nitrogen is the N-oxide compound.For example, main chain or side chain do not contain following structural unit:
In addition, when V, W or Z unit were oxidized, the E unit did not contain the carbonyl group that directly is keyed on the nitrogen-atoms, that is to say that nitrogen is the N-oxide compound.According to the present invention, E unit-C (O) R
3Group can not be keyed on the N-oxide modifying nitrogen, that is to say, does not have the N oxide compound acid amides and the integrated structure of following formula structure
B is a hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q-(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, preferred hydrogen ,-(CH
2)
qSO
3M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M, more preferably hydrogen or-(CH
2)
qSO
3M.
M is hydrogen or water-soluble cationic (presenting in an amount at least sufficient to satisfy charge balance).For example, sodium cation can satisfy-(CH equally
2)
pCO
2M and (CH
2)
qSO
3Therefore the requirement of M obtains-(CH
2)
pCO
2Na and-(CH
2)
qSO
3The Na group.More than one univalent cation (sodium, potassium or the like) can combine and satisfy required chemical charge balance.But an above anionic group can come charge balance by divalent cation, perhaps needs more than one univalent cation to satisfy the charge balance requirement of a plurality of anion-radicalss.For example, sodium atom replaces-(CH
2)
pPO
3The chemical formula of M is (CH
2)
pPO
3Na
3Divalent cation such as calcium (Ca
2+) or magnesium (Mg
2+) can be replaced or combination by other suitable unit price water-soluble cationic.Preferred cationic is sodium and potassium, more preferably sodium.
X is a water soluble anion, as chlorine (Cl
-), bromine (Br
-) and iodine (I
-), or X can be any electronegative group such as sulfate radical (SO
4 2-) and methyl-sulfuric acid root (CH
3SO
3 -).
The chemical formula index has following numerical value: p value from 1 to 6, q value from 0 to 6; The r value is 0 or 1; The w value is 0 or 1, x value from 1 to 100; Y value from 0 to 100; The z value is 0 or 1; M value from 4 to about 400; N value from 0 to about 200; The m+n value is at least 5.
Preferred scavenging agent of the present invention contains the polyamine main chain, and wherein about R group below 50% contains " oxygen " R unit, preferably is less than 20%, and more preferably less than 5%, most preferably the R unit does not contain " oxygen " R unit.
Do not contain the unitary most preferably scavenging agent of " oxygen " R and contain the polyamine main chain that 3 above carbon atoms are wherein arranged less than 50% R group.For example, ethylidene, propylene and trimethylene contain three or three following carbon atoms, therefore are preferred " alkyl " R unit.Working as main chain R unit in other words is C
2-C
12During alkylidene group, preferred C
2-C
3Alkylidene group, most preferably ethylidene.
Scavenging agent of the present invention contains the polyamine main chain of modification homopolymerization and non-homopolymerization, wherein 100% or be less than 100%-the NH unit is modified.With regard to the object of the invention, term " the polyamine main chain of homopolymerization " is defined as the have identical R unit polyamine main chain of (promptly being ethylidene entirely).But the definition of this homogeny is not got rid of and is contained other and add unitary polyamine, and this adds the unit and contains the superpolymer main chain that the artifact owing to selected chemical synthesis process exists.For example, this area the professional all know, thanomin can be used as the initiator of polymine in synthetic, so, with regard to the object of the invention, contain polymine sample from a hydroxyethyl groups of initiators for polymerization, can be regarded as the polyamine main chain that contains homopolymerization.Contain is that the polyamine main chain of ethylidene R unit (wherein not having ramose Y unit) is the homopolymerization main chain entirely.No matter how are the branch degree of the ring-type side chain that exists or quantity, are that the unitary polyamine main chain of ethylidene R all is the homopolymerization main chain entirely contain.
With regard to the object of the invention, term " main polymer chain of non-homopolymerization " is meant the polyamine main chain of the combination that contains different R element lengths and R cell type.For example, the R unit that contains of a kind of non-homopolymerization main chain is the unitary mixture of ethylidene and propylene.With regard to the object of the invention, the unitary mixture of " alkyl " and " oxygen " R not necessarily provides non-homopolymerization main chain.Appropriate control these " R unit chain lengths " to manufacturers provide the solubility of revising scavenging agent of the present invention and with the adaptive possibility of various fabrics.
The preferred scavenging agent polymkeric substance of the present invention contains the polyamine main chain of homopolymerization, they wholly or in part by the polyoxyethylene group replace, quaternized, nitrogen is oxidized to the N-oxide compound wholly or in part wholly or in part, and above-mentioned effect combines.But, be not that all main chain amine nitrogen all must be used the same way as modification, the special requirement of manufacturers is waited until in the selection of method of modifying.The degree of ethoxylation is also decided by the particular requirement of manufacturers.
In general, the preferred polyamine that contains compound main chain of the present invention is polyene amine (PAA ' s), polyalkylene imine (PAI ' s), preferably polyethylene amine (PEA ' s), polymine (PEI ' s) or by PEA ' s or the PEI ' s that connects than the unitary group of the longer R of parent PAA ' s, PAI ' s, PEA ' s or PEI ' s arranged.Common polyene amine (PAA) is the tetrabutyl five amine.By ammonia and vinylchlorid reaction, and then fractionation obtains PEA ' s.Resulting common PE A ' s is three second tetramines (TETA) and tetraethylene-pentamine (TEPA).More than five amine, i.e. hexamine, seven amine, eight amine and nine possible amine, these belong to deriving mixture together and it seems and can not separate with fractionating process, and may comprise other material such as cyclammonium and particularly piperazine.Also may there be cyclammonium, nitrogen-atoms on side chain, occur with side chain.Referring to United States Patent (USP) 2,792, No. 372, Dickinson, 14 days Mays nineteen fifty-seven of authorization date, this patents state the preparation of PEA ' s.
The preferred amines main polymer chain contains the R unit, and [this unit is C
2Alkylidene group (ethylidene) unit], also be referred to as polymine (PEI ' s).Preferred PEI ' s has moderate at least branch, and promptly m and the ratio of n be less than 4: 1, but most preferably the ratio of the m of PEI ' s and n is about 2: 1.The preferred general formula of main chain before modification is as follows:
Wherein, m and n with such as above this paper definition.The preferred molecular weight of PEI ' s before modification is greater than about 200 dalton.
In the polyamine main chain, especially in the situation of PEI ' s, primary, will with preparation method different change with the unitary relative proportion of tertiary amine the second month in a season.Be connected to each hydrogen atom on each nitrogen-atoms of polyamine main chain representing subsequently replace, a potential site of quaternized or oxidizing reaction.
These polyamine for example can, in the presence of catalyzer such as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid etc., make the ethyleneimine polymerization and make.The special methods for preparing these polyamine main chains is disclosed in United States Patent (USP) 2,182, people such as No. 306, Ulrich, 5 days December nineteen thirty-nine of authorization date; United States Patent (USP) 3,033, No. 746, people such as Mayle, authorization date on May 8th, 1962; United States Patent (USP) 2,208, No. 095, people such as Esselmann, authorization date on July 16th, 1940; United States Patent (USP) 2,806, No. 839, Crowther, 17 days September nineteen fifty-seven of authorization date; With United States Patent (USP) 2,553, No. 693, Wilson, 21 days Mays nineteen fifty-one of authorization date; All documents are all listed in reference in this article.
The present invention contains example formula I-IV graphic extension of the modification scavenging agent polymkeric substance of PEI ' s.
What the formula I was described is the scavenging agent polymkeric substance that contains the PEI main chain, and wherein all commutable nitrogen all are with polyoxy alkylidene oxygen unit [(CH
2CH
2O)
7H] displacement hydrogen and modification, its chemical formula is as follows:
This is the example with the scavenging agent polymkeric substance of the complete modification of a kind of type group.
What the formula II was described is the scavenging agent polymkeric substance that contains the PEI main chain, and wherein all commutable primary amine nitrogen all are with polyoxy alkylidene oxygen unit [(CH
2CH
2O)
7H] displacement hydrogen and modification, then all oxidable primary and secondary nitrogen are oxidized to the N-oxide compound makes this molecule modification then, and above-mentioned scavenging agent polymer chemistry formula is as follows
The chemical formula II
What the formula III was described is the scavenging agent polymkeric substance that contains the PEI main chain, and wherein all main chain hydrogen atoms all are substituted, and some main chain amine unit is by quaternary ammoniated.Substituting group is polyoxy alkylidene oxygen unit [(CH
2CH
2O)
7H] or methyl group.The chemical formula of modified PE I scavenging agent polymkeric substance is as follows
The chemical formula III
What the formula IV was described is the scavenging agent polymkeric substance that contains the PEI main chain, and wherein main chain nitrogen (is promptly used-(CH with substitution reaction
2CH
2O)
7H or methyl substituted), quaternized, be oxidized to N-oxide compound or the modification in addition of its method that combines.The scavenging agent polymer chemistry formula that obtains is as follows
The chemical formula IV
In above-mentioned example, be not that unitary all nitrogen of classification all comprise identical modified-reaction.The present invention allows manufacturers to make the ethoxylation of part secondary amine nitrogen, and makes other secondary amine nitrogen be oxidized to the N-oxide compound.This also is applicable to primary amine nitrogen, and wherein manufacturers can select with one or more substituting groups all or part of primary amine nitrogen to be carried out modification before oxidation or quaternary ammonium reaction.Above this paper, the said restriction, can substitute onto any may combination of E group on the primary and secondary amine nitrogen.
Scavenging agent of the present invention is included in the detergent composition, its amount from about 0.01% to about 15%; Preferred about 0.05% to about 8%; More preferably from about 0.1% to about 3%.Adjunct ingredient
Stain remover
In this detergent composition, can select for use and know polymkeric substance stain remover (hereinafter claiming " SRA ").If you are using, the content of general SRA ' s is 0.01% to 10.0% of said composition weight, typical case 0.1% to 5%, preferred 0.2% to 3%.
Usually, preferred SRA ' s has hydrophilic fragments so that the surface hydrophilic of hydrophobic fabric such as polyester and nylon also has hydrophobic segment, be deposited on the hydrophobic fabric, clean and the rinsing whole process in adsorb on it always, thereby become " holdfast " of hydrophilic fragments.This spot that just can make appearance after handling with SRA in cleaning process thereafter easier disposing.
SRA ' s can comprise various electric charges (as negatively charged ion or even the positively charged ion thing, referring to United States Patent (USP) 4,956, No. 447, license to people such as Gosselink September 11 nineteen ninety) and uncharged monomeric unit, their structure can be linear, side chain or even star.They can comprise END CAPPED GROUP, and described END CAPPED GROUP can be controlled molecular weight especially effectively or change physics or surfactivity.For be used for dissimilar fibers or fabric with for different washing composition or detergent additives, its structure or charge distribution can design as the case may be.
Preferred SRA ' s comprises low polyterephthalate, and with following method preparation, this method relates to a kind of transesterify/oligomerization at least, usually also uses metal catalyst such as titanium alkoxide (IV) usually.This ester can make with additional monomer, this monomer can through 1,2,3,4 or more a plurality of position be incorporated in this ester structure, and surely not form intensive crosslinked one-piece construction.
Other SRA ' s comprises nonionic end capped 1,2-propylidene/polyoxyethylene terephthalic polyester is (referring to United States Patent (USP) 4,711, licensed to people such as Gosselink on December 8th, No. 730 1), for example carry out the material that transesterify/oligomerization makes by poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other example of SRA ' s comprises: part and the complete end capped oligomer ester of negatively charged ion (United States Patent (USP) 4,721, No. 580, licensed to Gosselink on January 26th, 1988) as by ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of the hot sodium sulfonate preparation of 6-dioxy-8-hydroxyl; And negatively charged ion; especially the end capped terephthalate of sulfo group aroyl (United States Patent (USP) 4; 877; 896; licensed to Maldonado on October 31st, 1989), the latter is the typical SRA that uses in laundry and fiber conbidioning product, an example is the ester composition that is made by m-sulfosalicylic acid list sodium salt, PG and DMT; optional (but preferred) further contains the PEG of interpolation, and for example PEG 3400.
SRA ' s also comprises: the simple segmented copolymer of terephthalic acid ethylene glycol polycondensate or terephthaldehyde's acid propylene glycol polycondensate and polyethylene oxide or poly-propylene oxide terephthaldehyde acid polymer is (referring to United States Patent (USP) 3,959,230, Hays, on May 25th, 1976 and United States Patent (USP) 3,893,929, Basadur, on July 8th, 1975); Derivatived cellulose is as hydroxyl ether cellulose polymer compound (can buy trade(brand)name METHOCEL from Dow); C
1-C
4Alkylcellulose and C
4Hydroxy alkyl cellulose (, being issued to people such as Nicol on December 28th, 093,1976) referring to United States Patent (USP) 4,000; And methyl cellulose ether, the average substitution degree of its each glucoside (methyl) is about 1.6 to about 2.3, recording 2% viscosity in aqueous solution at 20 ℃ is about 80 to about 120 centipoises.This kind material can be buied from market, and METOLOSE SM100 by name and METOLOSESM200 are the trade names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK manufacturing.
Suitable SRA ' the s that is feature with poly-(vinyl acetate) hydrophobic segment comprises poly-(vinyl acetate) graft copolymer, for example C
1-C
6The vinyl acetate graft copolymer preferably is grafted to poly-(vinyl-acetic ester) on the polyalkylene oxide main chain.Referring to european patent application 0 219 048, people such as Kud are disclosed on April 22nd, 1987.Commercial example on sale comprises SOKALAN SRA ' s such as SOKALAN HP-22, can be from BASF, and Germany buys.Other SRA ' s has the polyester that contains 10-15% (weight) terephthalic acid ethylene glycol polycondensate and 80-90% (weight) poly terephthalic acid polyoxyethylene glycol polycondensate (by molecular-weight average 300-5,000 polyoxyethylene glycol is derived and obtained) repeating unit.Commercial examples comprises the ZELCON 5126 of Dupont and the MILEASET of ICI.
Another preferred SRA is that the experience molecular formula is (CAP)
2(EG/PG)
5(T)
5(SIP)
1Oligopolymer; it contains terephthaloyl (T), sulfo group isophthaloyl (SIP), oxygen ethylidene oxygen and oxygen-1; 2-propylidene (EG/PG) unit is also preferred with END CAPPED GROUP (CAP) termination; preferred modification is to isethionate; make END CAPPED GROUP; for example following oligopolymer: the oxygen ethylidene oxygen and the oxygen 1 that contain a sulfo group isophthaloyl unit, 5 terephthaloyl unit, certain proportion (preferred about 0.5: 1 to about 10: 1); 2-propylidene oxygen unit, and band 2-(2-hydroxy ethoxy)-two END CAPPED GROUP unit of ethyl sulfonic acid sodium deutero-.Above-mentioned SRA preferably further contain account for this oligopolymer weight 0.5% to 20% subtract the degree of crystallinity stablizer, anion surfactant for example, as linear Sodium dodecylbenzene sulfonate or be selected from dimethylbenzene-, isopropyl benzene-and toluene-sulfonate or its mixture, these stablizers or properties-correcting agent are sent in the synthesising container, all these are at United States Patent (USP) 5, among 415,807 (Gosselink, Pan, Kellett and the Hall, authorize May 16 nineteen ninety-five) explanation is arranged all.The proper monomer of above-mentioned SRA comprises 2-(2 hydroxy ethoxy) ethyl sulfonic acid sodium, DMT, dimethyl-5-sulfoisophthalic acid sodium, EG and PG.
Other kind SRA ' s comprises: (I) utilizes the vulcabond coupler to connect the nonionic terephthalate of polyester construction, referring to United States Patent (USP) 4,201, and 824 people such as () Violland and United States Patent (USP) 4,240,918 people such as () Lagasse; (II) has the SRA ' s of carboxylate end group, by trimellitic acid 1,2-anhydride is joined among known SRA ' s, makes terminal hydroxy group be transformed into trimellitate and obtains.Suitable selecting catalyst, that carboxyl that separates by trimellitic acid 1,2-anhydride links to each other with polymer terminal group formation ester bond, rather than is connected with polymer ends by disconnecting the acid anhydride key.No matter be that nonionic or negatively charged ion SRA ' s can be used as raw material, if they have can esterification hydroxyl end groups.Referring to United States Patent (USP) 4,525,524 (people such as Tung).Other kind comprises: (III) connects the SRA mutation based on terephthaldehyde's acid anion of urethanum, referring to United States Patent (USP) 4,201, and 824 people such as () Violland; (IV) poly-(ethene hexanolactam) and have V-Pyrol RC and/or the monomeric related copolymers of dimethylaminoethyl acrylate methyl ammonia ethyl ester and so on comprises nonionic and cationic polymers, referring to United States Patent (USP) 4,579,681, people such as Ruppert; (V) comprises also that Acrylic Acid Monomer is grafted on the sulfonated polyester and the graft copolymer that obtains except that the SOKALAN type of BASF AG.These SRA ' s it is reported to have decontamination and antiredeposition activity, and this point is similar to the cellulose ester of knowing: referring to EP 279, and 134A, 1988, apply for by Rhone-Poulenc Chemie.Other type also comprises: (VI) vinyl monomer such as vinylformic acid and vinyl-acetic ester are grafted on the grafts on protein such as the casein: referring to EP 457, and 205A, BASF (1991) application; (VII) polyester-polyamide SRA ' s is formed by hexanodioic acid, hexanolactam and polyoxyethylene glycol condensation, is particularly suitable for being used for handling tynex, and referring to Bevan et al., DE 2,335,044 Unilever N.V., 1974 applications.Other useful SRA ' s is at United States Patent (USP) 4,240, introduction all arranged in 918,4,787,989 and 4,525,524.
Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach activator
The detergent composition of this paper can be chosen wantonly and contain SYNTHETIC OPTICAL WHITNER or bleaching composition, and said composition contains a kind of SYNTHETIC OPTICAL WHITNER and one or more bleach-activating agents.If any, the content of SYNTHETIC OPTICAL WHITNER account for detergent composition about 0.05% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to about 20%, especially for fabric detergent.If any, the amount of bleach-activating agent generally account for bleaching composition (adding bleach-activating agent by SYNTHETIC OPTICAL WHITNER forms) about 0.1% to about 60%, more preferably from about 0.5% to about 40%.
SYNTHETIC OPTICAL WHITNER used herein can be any SYNTHETIC OPTICAL WHITNER that is added on detergent composition in textiles cleaning, rigid surface cleaning or other known or just cognitive cleaning use.This comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.In this patent, can use perborate bleach, as Sodium peroxoborate (as one or tetrahydrate).
The another kind of SYNTHETIC OPTICAL WHITNER that can unrestrictedly use comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its esters.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises the magnesium salts of single peroxybenzoic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxygen Perbutyric Acid and diperoxy dodecanedioic acid.This SYNTHETIC OPTICAL WHITNER is disclosed in the following patent: United States Patent (USP) 4,483,781, Hartman, authorization date on November 20th, 1984, U.S. Patent application 740,446, Burns et al., June 3 1985 date of application, european patent application book 0,133,354, Banks et al.Open February 20 1985 date and United States Patent (USP) 4,412,934, Chung et al., 1 day November nineteen eighty-three of authorization date.Highly preferred SYNTHETIC OPTICAL WHITNER comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxygen crosses oxy hexanoic acid, and this licenses on January 6th, 1987 in people's such as Burns the United States Patent (USP) 4,634,551 introduction.
Also can use peroxygen bleach.Suitable peroxide bleaching chemical combination poplar comprises yellow soda ash peroxyhydrate and " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide of equal value.Also can use persulphate SYNTHETIC OPTICAL WHITNER (as the OXONE of Dupont commercial production).
Preferred percarbonate bleach contains average particle size and arrives about 1 for about 500 microns, 000 micron dried particle, the above-mentioned particle that wherein is no more than about 10% (weight) is less than about 200 microns, and the above-mentioned particle that is no more than about 10% (weight) is greater than about 1,250 micron.What can choose wantonly is, this percarbonate can the silicon-coating hydrochlorate, borate or water soluble surfactant active.Percarbonate can be buied from various commercial channel, as FMC, Solvay and Tokai Denka.
Also can use the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate or the like, preferably with the combination of following bleach-activating agent, this activator can be in the aqueous solution (promptly in cleaning process) original position produce peroxy acid corresponding to this bleach-activating agent.License in April 10 nineteen ninety in people's such as Mao United States Patent (USP) 4,915,854 and the United States Patent (USP) 4,412,934 and disclosed the various non-limitative example of these activators.Generally, also can use nonanoyl oxygen benzene sulfonate (NOBS) and EDTA (TAED) activator and composition thereof.Also can be for other the typical SYNTHETIC OPTICAL WHITNER used in this patent and activator referring to United States Patent (USP) 4,634,551.
Highly preferred amido derive bleach-activating agent as shown in the formula:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L is R wherein
1Be to contain 6 the alkyl of having an appointment, R to about 12 carbon atoms
2Be to contain 1 alkylidene group, R to about 6 carbon atoms
5Be H or alkyl, aryl or alkaryl (contain have an appointment 1 to about 10 carbon atoms), and the L suitable leavings group that is any.Leavings group is that bleach-activating agent is subjected to the anionic nucleophillic attack of all-hydrolytic and any group that can cement out from bleach-activating agent.Preferred leavings group is the phenylbenzimidazole sulfonic acid root.
The preferred example of following formula bleach activator comprises (6-decoyl amino-caproyl) oxygen benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate, (6-caprinoyl amino-caproyl) oxygen benzene sulfonate and composition thereof; as United States Patent (USP) 4; 634; introduced this paper and in 551 in conjunction with its reference of quoting.
Another kind of bleach-activating agent comprises benzoxazine type activator, at United States Patent (USP) 4,966, discloses this paper and in conjunction with its reference of quoting in 723 (mandates on October 30 nineteen ninety) as people such as Hodge.Particularly preferred benzoxazine type activator is:
Also have another kind of preferred bleach-activating agent to comprise acyl lactam activator, particularly acyl caprolactam and acyl group Valerolactim.Its chemical formula is as follows:
R wherein
6Be H or alkyl, aryl, alkoxy aromatic yl or alkaryl (containing 1) to about 12 carbon atoms.Particularly preferred lactan activator comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecanoyl hexanolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecanoyl Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl Valerolactim and composition thereof.Also can consult United States Patent (USP) 4,545,784 (licensing to Sanderson on October 8th, 1985) and in conjunction with its reference of quoting, this article has disclosed the acyl caprolactam that is absorbed in the Sodium peroxoborate into, comprises benzoyl caprolactam.
Other SYNTHETIC OPTICAL WHITNER outside the oxygen bleaching agent also is well-known in this professional domain and can be used for this patent.A useful especially class non-oxygen bleaching agent comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonic acid zinc and/or aluminium phthalocyanine.Referring to United States Patent (USP) 4,033, licensed to people such as Holcombe on July 5th, 718,1977.If you are using, generally contain this SYNTHETIC OPTICAL WHITNER (particularly sulfonic acid zinc phthalocyanine) about 0.025% to about 1.25% in the detergent composition.
If necessary, this SYNTHETIC OPTICAL WHITNER compound can be used manganic compound catalysis.This compound is well-known in this professional domain, for example comprises, is disclosed in United States Patent (USP) 5,246,621; United States Patent (USP) 5,244,594; United States Patent (USP) 5,194,416; United States Patent (USP) 5,114,606; With european patent application 549,271A1,549,272A1,544,440A2 and 544, the catalyzer of 490A1 based on manganese; This catalyzer preferred example comprises Mn
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
2, Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2-(1,4,7-trimethylammonium-1,4,7 7-triazacyclononanes)
2(ClO
4)
3, Mn
IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH
3)
3(PF
6) and composition thereof.Other bleaching catalyst based on metal comprises United States Patent (USP) 4,430,243 and United States Patent (USP) 5,114,611 in disclose those.In following United States Patent (USP), also reported and can use the manganese that have different cooperation ligands to strengthen bleaching action, as 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; With 5,227,084.
As a kind of practical application mode and not with this as restriction, can regulate its prescription and method among the present invention, to make it in solution washing liquid, can provide the active bleaching catalyst material of 1/10,000,000 order of magnitude.Preferably can provide about 0.1ppm to 700ppm in washing liquid, more preferably from about 1ppm is to the catalyst substance of about 500ppm.
Various other composition of available can be included in the composition of the present invention in the detergent composition, comprising other activeconstituents, carrier, solubility promoter, processing aid, dyestuff or pigment, liquid preparation with solid filler of solvent, bar compositions or the like.High if desired foam type can mix whipping agent such as C in composition
10-C
16Alkanolamide, typical content are 1%-10%.C
10-C
14Monoethanolamine and diglycollic amide are the typical species of this whipping agent.This kind whipping agent that use is added with high foaming cosurfactant amine oxide as mentioned above, trimethyl-glycine and sultaine also is good.If necessary, can add solubility magnesium salts such as MgCl
2, MgSO
4Deng, general consumption is 0.1%-2%, with auxiliary foaming and enhancing degrease performance.
The various detergent ingredients that use in the present composition can be chosen wantonly further by mentioned component being adsorbed onto in the porous hydrophobic matrix, then above-mentioned matrix are applied hydrophobic membrane again and are stablized.Before going in absorbing porous matrix, mixes with tensio-active agent earlier preferred described cleaning ingredients.During use, detergent ingredients is discharged into from matrix in the water washing solution, the washing function of performance expection.
Now illustrate this technology in more detail, (registered trademark SIPERNATD10 DeGussa) mixes mutually with proteolytic enzyme solution, and this solution contains the C of 3%-5% porous hydrophobic silicon-dioxide
13-15Ethoxylated alcohol (EO7) nonionogenic tenside.Typical enzyme/surfactant soln is 2.5 times of silica weight.The powder that obtains is put into silicone oil dispersed with stirring (can use viscosity at 500-12, the various silicone oil within 500).The silicone oil dispersion liquid that obtains is emulsified or join in the final washing composition matrix.In this way, all compositions such as above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, light activating agent, dyestuff, fluorescent agent, fabric conditioner and hydrolyzable tensio-active agent can obtain " protection " when (comprising the liquid laundry detergents composition) being used for washing composition.
Liquid detergent compositions can contain water and other solvent as carrier.Suitable is low-molecular-weight primary alconol or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol or Virahol.Preferably take surface of stability promoting agent, but also can use polyvalent alcohol as containing 2 to about 6 carbon atoms and 2 polyvalent alcohols (for example, 1, ammediol, ethylene glycol, glycerol and 1,2-propylene glycol) to about 6 hydroxyls with MHA.This combination can contain 5% to 90%, general 10% to 50% this carrier.
Detergent composition of the present invention is preparation in the requsst listed below preferably: when using with the water cleaning way, the pH that can make washing water is between about 6.5 to about 11, preferably between about 7.5 to 10.5.The preferred pH of dishwashing liquid product formulation is between about 6.8 to about 9.0.The typical pH of laundry product is 9-11.Desire is controlled at the pH value and recommends the usage level method therefor, comprises using damping fluid, alkali, acid or the like, and all be that this area professional is known.
Other enzyme
For various purposes, comprise from surfaces such as fabric or bowl dish and remove protein-based spot, carbohydrate-based spot, with dye transfer (for example when doing washing), and, also can comprise other enzyme except that esterase in this paper detergent composition for purposes such as fabric restoration in order to prevent to scatter.Suitable enzyme comprises proteolytic enzyme, amylase, cellulase, peroxidase and composition thereof, and these enzymes can be from any suitable source, as plant, animal, bacterium, fungi and yeast source etc.When being selected, the preferred Several Factors of selecting of influence is the active and/or stable optimizing of pH-, thermostability and to the stability of activated detergent, washing assistant etc.Consider these factors, preferred bacterium enzyme and fungal enzyme, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.
" detergent enzyme " used herein be meant in laundry, hard surface cleaning or personal care detergent composition, have cleaning, any enzyme of decontamination stain or other beneficial effect.Preferred detergent enzyme is lytic enzyme such as proteolytic enzyme and amylase.The preferred enzyme of purpose of being used to do washing includes, but is not limited to proteolytic enzyme, cellulase and peroxidase.The preferred enzyme that is used for automatic dishwasher is amylase and/or proteolytic enzyme, comprises current commercially available kind and improves kind, though more and more can be compatible through updating with SYNTHETIC OPTICAL WHITNER, but to a certain degree SYNTHETIC OPTICAL WHITNER inactivation susceptibility is arranged.
Usually mix the enzyme in washing composition or the washing composition additive composition, its amount will be enough to provide " cleaning significant quantity ".So-called " cleaning significant quantity " is meant can produce cleaning, decontamination, scale removal in matrix such as above fiber, the vessel etc., brighten, deodorizing or become the amount of new effect.In fact, for present commercial preparation, general consumption is to add maximum about 5mg in every gram cleaning composition, 0.01mg to 3mg organized enzyme more generally, in other words, the composition of this paper generally will contain 0.001% to 5%, the commercial enzyme preparation of preferred 0.01%-1% (weight).The common amount of proteolytic enzyme is the amount that is enough to provide every gram composition 0.005 to 0.1 Anson unit (AU) activity in above-mentioned commodity preparation.For some washing composition, the washing composition that for example uses in automatic dishwasher may wish to increase the organized enzyme content of commodity preparation, so that on-catalytic active substance total amount reduces to minimum, removes spot/film-forming properties or other final effect thereby improve.In the detergent formulation of high density, also need higher activity level.
The suitable example of proteolytic enzyme is the subtilysin that obtains from specific subtilis and Bacillus licheniformis bacterial strain.A kind of suitable proteolytic enzyme obtains from bacillus strain, in the scope of pH8-12, have maximum activity, by Novo Industries A/S company (Denmark) (hereinafter to be referred as Novo) with registered trademark ESPERASE
Development is also sold.The preparation of this enzyme and similar enzyme has been described in the English Patent 1,243,784 of Novo.Other suitable example comprises the ALCALASE from Novo
And SAVINASE
And from International Bio-Synthetics, the MAXATASE of Inc. (Holland)
And protease A (on January 9th, 1985 disclosed European patent EP 130,756A) and proteolytic enzyme B (see the European patent EP 303 on April 28th, 1987, the 761A and the European patent EP 130 on January 9th, 1985,756A).Also can be referring to the high pH proteolytic enzyme of describing among the international monopoly WO 9318140 of Novo by Bacillaceae NCIMB 40338 extractions.The enzyme detergent that contains proteolytic enzyme, one or more other enzymes and reversible protease inhibitor has been described in the international monopoly WO of Novo 9203529A.Other preferred proteolytic enzyme comprises Procter ﹠amp; The proteolytic enzyme of introducing among the international monopoly WO 9510591A of Gamble.Need, also available adsorption reduction and hydrolytic action enhanced enzyme are as Procter ﹠amp; Those that introduce among the international monopoly WO 9507791 of Gamble.The recombinant trypsin sample proteolytic enzyme that is fit to this paper washing composition has introduction in the WO 9425583 of Novo.
More particularly, be referred to as the special preferred protease of " proteolytic enzyme D ", it is carbonylic hydrolase variant with aminoacid sequence of not finding at occurring in nature, it derives from the precursor carbonylic hydrolase by following manner: described carbonylic hydrolase, be equivalent to+76 on, come the substituted amino acid residue with different amino acid, also preferred this be equivalent to+76 be equivalent to be selected from the some residues of one or more amino acid of following radicals position together by different aminoacid replacement, described position is :+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+274, described numbering is according to the numbering of separating the amylobacter subtilysin, be entitled as the patent application (U.S. serial 08/322 of " containing the proteolytic enzyme cleaning combination " as people such as A.Baeck, 676) and people such as C.Ghosh in the patent application that is entitled as " bleaching composition that contains proteolytic enzyme " (U.S. serial 08/322,677), this two application all is to submit on October 13rd, 1994.
The amylase that the is applicable to this paper particularly amylase of (but being not limited to) automatic dishwasher purposes comprises, for example, and the α-Dian Fenmei of in the English Patent GB 1,296,839 of Novo, describing, RAPIDASE
(International Bio-Synthetics Inc.) is put TERMAMYL
(Novo).The FUNGAMYL that Novo produces
Particularly useful.Improve stability, for example the zymotechnic of oxidative stability is known.Referring to, J.Biological Chem. for example, Vol.260, No.11, June 1985, pp 6518-6521.Some preferred embodiment of the present composition, can use the amylase that has the stable amylase of improvement, particularly has the improvement oxidative stability in washing composition such as automatic bowl type washing composition, described improvement oxidative stability is the reference point TERMAMYL in commercial the use with respect to 1993
And measure.The preferred amylase of these this paper has the diastatic characteristic of " enhanced stability ", it is characterized in that at least a or multiple oxidative stability has the improvement that can determine: for example be the oxidative stability of the hydrogen peroxide/tetraacetyl ethylene diamine in the damping fluid of 9-11 to pH; For example in the common wash temperature thermostability under 60 ℃ according to appointment; Or be alkalescence stability under about 8 to about 11 at pH for example, all are measured all is at the reference point amylase comparative measurement of pointing out above.Can measure described stability with any now disclosed test method(s), referring to, for example, disclosed reference among the WO 9402597.Stability enhanced amylase can obtain from Novo or Genencor International.The particularly preferred kind of starch enzyme of this paper has from one or more bacillus amylases, especially bacillus amylase, use kunkel method Kunkel deutero-general character, with a kind of, two kinds or multiple amylase strain whether be that direct precursor is irrelevant.With reference to for the amylase, oxidative stability enhanced amylase is preferred for (particularly) bleaching, more preferably is used for (being different from chlorine bleaching) this paper detergent composition of oxygen bleaching with respect to above-mentioned.These preferred amylase comprise (a) according to above introduce February in 1994 disclosed Novo WO 9402597 on the 3rd amylase, further illustrate and be to use L-Ala or Threonine, preferably use Threonine, replace and be referred to as TERMAMYL
197 of Bacillus licheniformis α-Dian Fenmei on methionine residue gained mutant, or similar parent's amylase, for example bacillus amyloliquefaciens, subtilis or bacstearothermophilus diastatic corresponding position mutation; (b) the stable enhanced amylase of on the article of submitting to by the C.Mitchinson of Genencor International company in the 207th American Chemical Society whole nation meeting of 13-17 day in March, 1994 that is entitled as " anti-oxidant α-Dian Fenmei ", describing, wherein mention, SYNTHETIC OPTICAL WHITNER in the automatic dishwasher washing composition makes the α-Dian Fenmei inactivation, but the amylase that has improved oxidative stability is created with Bacillus licheniformis NCIB 8061 by Genecor.Methionine(Met) (Met) is considered to the residue that most probable is modified.On 8,15,197,256,304,366 and 438 positions, replace Met one at a time and produce specific mutant, particularly importantly M197L and M197T, M197T variant are the variants of stably express.At CASCADE
And SUNLIGHT
In measured stability; (c) the particularly preferred amylase of this paper is included in and adds the amylase mutation of modifying among the direct parent, has to introduce and can be from commission merchant, Novo with DURAMYL in WO 9510603A
The registrar name of an article is buied.Other particularly preferred oxidative stability enhanced amylase comprises those amylase of describing in WO 9418314 that licenses to Genencor International and the WO 9402597 that licenses to Novo.Also can use any other oxidative stability enhanced amylase, for example from available diastatic known chimeric, the hybridization or the parent's form of simply suddenling change, by site-directed mutagenesis deutero-amylase.Other preferred enzyme modification method is carried out easily, referring to the WO 9509909 of Novo.Diastatic enzyme concn should be about 0.0018% to about 0.06% a pure enzyme of total composition weight, preferred about 0.00024% to about 0.048% pure enzyme.
Can be used for cellulase of the present invention and comprise bacterium and the plain enzyme of fungi fiber type, preferably its best pH is between 5 and 9.5.U.S. Pat 4,435,307 (people such as Barbesgoard, authorized on March 6th, 1984) disclose and planted Pseudomonas insolens or corruption from corruption and plant enzyme and belong to DSM 1800 bacterial strains, or belong to suitable fungal cellulase of producing in the fungi of generation cellulase 212 of Aeromonas and the cellulase that from the liver pancreas of sea mollusk (Dolabella Auricual Solander), extracts.Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.CAREZYME
(Novo) be useful especially.Also can be referring to the WO 9117243 of Novo.
Be applicable to that at of the present invention has introduction in the WO of Genencor 8809367A.
Peroxidase can be used from " solution bleaching " with oxygen source (for example percarbonate, perborate, hydrogen peroxide etc.) one or the dyestuff that prevents to come off from matrix in when washing or pigment are transferred to and is in the washing soln other together and washed on the matrix.Known peroxidase comprises horseradish peroxidase, lignoenzyme, and haloperoxidase, for example the chlorine or bromine peroxidase.The detergent composition that contains peroxidase is disclosed in the WO 89099813A that licensed to Novo on October 19th, 1989 and licenses among the WO 8909813A of Novo.
The scope of enzyme material and the method that joins in the synthetic detergent composition thereof also are disclosed in WO 9307263A and the WO 9307260A that licenses to Genencor International, license to the WO 8908694A of Novo, license to people's such as McCarty US3 with on January 5th, 1971, in 553,139.Enzyme also is disclosed in US 4,101, among 457 (people such as Place, on July 18th, 1978 authorized) and the US 4,507,219 (Hughes, mandate on March 26th, 1985).Can be used for the enzyme material in the liquid detergent prescription, and join the method in this prescription, be disclosed in US 4,261, among 868 people such as (, on April 14th, 1981 authorized) Hora.The enzyme that is used for washing composition can make it stable with various technology.The enzyme stabilization technique is open and be illustrated in US 3,600, among 319 (licensing to people such as Gedge on August 17th, 1971), EP 199,405 and the EP 200,586 (licensing to Venegas on October 29th, 1986).The enzyme stabilising system also is disclosed in, and for example US 3,519, in 570.In licensing to the WO 9401532A of Novo, introduced the suitable bacillus AC13 that proteolytic enzyme, zytase and cellulase can be provided.
The enzyme stabilising system
The fluid composition (being limited to fluid composition but have more than) that contains enzyme among the present invention can contain has an appointment 0.001% to about 10%, and preferred about 0.005% to about 8%, and more preferably from about 0.01% to about 6% weight enzyme stabilising system.The enzyme stabilising system can be any stabilising system that can be compatible with detergent enzyme.This system can be provided by other active ingredient institute this function of inherent, or is for example added separately by the prescription teacher or the manufacturer of ready-made detergent enzyme.This stabilising system for example can contain calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid class and composition thereof, can design this stabilising system at different stable problems (type and the physical aspect that depend on detergent composition).
A kind of stabilising method are to utilize water-soluble calcium and/or magnesium ion source in the final product composition having, provide this ion to this enzyme.Generally, calcium ion is more effective than magnesium ion, so if can only use the just preferred calcium ion of a kind of cationic words.Typical detergent composition, especially liquid should contain in every liter of finished product cleaning composition and have an appointment 1 to about 30, preferred about 2 to about 20, and more preferably from about 8 to about 12 mmole calcium ions, according to the diversity of mixing enzyme, type is different with factors such as consumption, also can change to some extent.Preferred water-soluble calcium or the magnesium salts of adopting comprises for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate and lime acetate; More generally use calcium sulfate or with the corresponding magnesium salts of the calcium salt of being given an example.Certainly the consumption that further increases calcium and/or magnesium is good, and for example strengthens the effect of degreasing of some type list surface-active agent.
Another kind of stabilising method are to use borate substance.U.S. Pat 4,537,706 referring to Severson.When the borate stablizer uses can up to this combination 10% or more than, but be boric acid or other borate compound of about 3% (weight) at most more in general, as borax or ortho-borate for the suitable consumption of liquid detergent.Substituted boracic acid can be used for substituting boric acid as phenyl-boron dihydroxide, butane boric acid, p-bromobenzene boric acid etc., and utilizes this replacement boron derivative can reduce the total amount of boron in the detergent composition.
The stabilising system of some cleaning combination can further contain 0 to about 10%, and the preferred about 0.01% chlorine bleaching scavenging agent to about 6% (weight) can prevent the chlorine bleaching material damage and the fermentoid that exist in many water sources, especially under alkaline condition.Though cl content may be very little in the water, generally be about 0.5ppm to 1.75ppm, with the chlorine in the contacted Total Water of enzyme,, just may be quite a large amount of for example washing the dishes or washing in the fabric process; Therefore, the chlorine that runs in the use brings problem sometimes to the stability of enzyme.Because can appear in the present composition with perborate or the percarbonate that chlorine bleach reacts, its amount is not calculated in stable system, therefore generally speaking, because use them can obtain improvement effect, to tackle chlorine may not be necessary with adding stablizer.Suitable chlorine scavenger negatively charged ion is well-known and buys easily that if you are using, they can be the salt that contains ammonium cation, as ammonium sulphite, ammonium bisulfite, hyposulfurous acid ammonium, ammonium thiosulfate, ammonium iodide etc.Antioxidant, as carbamate, xitix etc., organic amine, as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and its mixture also can use equally.Equally, also can add specific enzyme inhibition system, make different enzymes have maximum consistency.Scavenging agent that other is commonly used such as hydrosulfate, nitrate, muriate, hydrogen peroxide cource, as four hydrated sodium perborates, single hydrated sodium perborate and SPC-D, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc. and composition thereof, also can use if desired.In general, because mentioned the effect that all compositions (for example hydrogen peroxide cource) of better generally acknowledging effect also can play chlorine scavenger respectively, add chlorine scavenger separately so there is no imperative, unless in the enzyme embodiment of the present invention, lack its function and can make chlorine remove the compound that effect reaches required degree; Even so, add scavenging agent just to reaching best effect.And the prescription teacher will avoid using adding back and extremely inconsistent any enzyme scavenging agent of other activeconstituents or stablizer when preparation, and teacher of the prescription can therefrom train a chemist's general skill thus.About the use of ammonium salt is simply it and detergent composition to be mixed, but it is easy to absorb the water and/or the ammonia that dissociates when storing.Therefore, if there is this material, as US 4,652,392 (people such as Baginski) are described in particle for better preserved.
Washing assistant
Detergent builders can be chosen wantonly in the composition that is included in this paper, so that help to control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition and helps to remove particulate fouling.
The content of washing assistant can have the variation of broad according to the physical form of the end-use of composition and its needs.When it existed, composition generally contained the washing assistant at least about 1%.Liquid formulations generally contains the 5-50% that has an appointment (weight), the detergent builders of more general about 5-30% (weight).Granular recipe generally contains the 10-80% that has an appointment (weight), the detergent builders of more general about 15-50% (weight).Yet, and do not mean that the lower or high-content more of eliminating.
Inorganic or phosphorus-containing detergent washing assistant includes, but is not limited to: poly-phosphate (illustrating with tri-polyphosphate, pyrophosphate salt and glassy polymetaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), the basic metal of vitriol and silico-aluminate, ammonium and alkanol ammonium salts.Yet, need non-phosphorus builder in certain areas.Importantly, composition herein even under what is called " weak " washing assistant (comparing) that exists such as Citrate trianion with phosphoric acid salt, or with zeolite or layered silicate washing assistant the time under the situation of what is called " composite deficiency ", it is unexpectedly good that function is also made us.
The example of silicate-like builder is an alkalimetal silicate, especially SiO
2: Na
2O is 1.6: 1-3.2: those silicate and the layered silicate of 1 scope, and for example at the lamina sodium silicate described in the US 4664839 (H.P.Rieck, on May 12nd, 1987 authorized).NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " herein usually) by the crystalline layered silicate of Hoechst sale.Different with zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has the δ-Na of layered silicate
2SiO
5Morphological form.It can pass through such as preparing in those methods described in DE-A-3417649 and the DE-A-3742043.SKS-6 is the layered silicate that is preferred for very much herein, but other such layered silicate for example has general formula NaMSi
xO
2x+1YH
2O (wherein M is sodium or hydrogen, and x is the number of 1.9-4, preferred 2 and y be the number of 0-20, preferred 0) those also can be used for herein.Various other layered silicates that derive from Hoechst comprise: as NaSKS-5, NaSKS-7 and the NaSKS-11 of α, β and γ form.As mentioned above, δ-Na
2SiO
5(NaSKS-6 form) is most preferably to be used for herein.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be as crisp (crispening) agent in granular recipe, as the oxygen bleaching stablizer with as the component of foam control system.
The example of carbonate builders is as disclosed alkaline-earth metal and alkaline carbonate in German patent application number 2321001 (on November 15th, 1973 is open).
The silico-aluminate washing assistant is useful in the present invention.The silico-aluminate washing assistant is very important in most popular commercially available heavy dirty granular detergent composition, and also is the important builder component in the liquid detergent formula.The silico-aluminate washing assistant comprises the formula M that sees service
z[(zAlO
2)
y] xH
2Those of O, wherein z and y are at least 6 integer, and the mol ratio of z and y is that about 1.0-0.5 and x are the integers of about 15-264.
Useful aluminosilicate ion exchange material can buy from the market.These silico-aluminates structurally can be crystalline or unbodied, and can naturally occurring silico-aluminate or synthetic obtaining.A kind of method of producing aluminosilicate ion exchange material is disclosed in US 3985669 (people such as Krummel, on October 12nd, 1976 authorized).Useful herein preferred synthetic crystallization aluminosilicate ion exchange material can zeolite A, and the title of zeolite P (B), zeolite MAP and X zeolite is bought.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has molecular formula Na
12[(AlO
2)
12(SiO
2)
12] xH
2O, wherein x is about 20-30, particularly about 27.This material is called as zeolite A.The zeolite (x=0-10) of dehydration also can be used for herein.The particle diameter of preferably aluminosilicate salt is about 0.1-10 micron.
The organic detergent washing assistant that is applicable to the object of the invention includes, but is not limited to various many carboxylate cpds.As used in this article, " many carboxylates " representative has a plurality of carboxylate group, the compound of preferred at least 3 carboxylate group.Many carboxylates washing assistant generally joins in the composition with sour form, but form that also can neutral salt adds.When using with salt form, basic metal, for example sodium, potassium and lithium or alkanol ammonium salts are preferred.
In many carboxylates washing assistant, comprise various types of useful matteies.The important many carboxylates washing assistant of one class comprises many carboxylates, and it comprises as disclosed oxygen di-succinate in US 3128287 (Berg, on April 7th, 1964 authorized) and US 3635830 people such as (, mandate on January 18th, 1972) Lamberti.Referring to " TMS/TDS " washing assistant among the US 4663071 (people such as Bush, on May 5th, 1987 authorized).Suitable many carboxylates ether also comprises ring compound, especially alicyclic compound, for example those disclosed in US 3923679, US 3835163, US4158635, US 4120874 and US 4102903.
Other useful detergent builder compound comprises many carboxylates of hydroxyl ether, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene 2,4, the 6-trisulfonic acid, and carboxy methoxy-succinic acid, the ammonium salt of various basic metal, ammonium and the replacement of polyacetic acid, for example ethylenediamine tetraacetic acid (EDTA) and triglycollamic acid, and many carboxylates, for example mellitic acid, succsinic acid, oxygen di-succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.
Lemon acids washing assistant, for example citric acid and its water-soluble salt (especially sodium salt), because its recyclability and biological degradability, so counterweight dirt detergent agent prescription is many carboxylates washing assistant of particularly important.Citric acid also can be used for granular recipe, particularly is used in combination with zeolite and/or layered silicate washing assistant.Oxygen di-succinate also is useful especially in such composition and combination.
Also be applicable to be to be disclosed in 3 among the US 4566984 (Bush, on January 28th, 1986 authorized), 3-dicarboxyl-4-oxa--1,6-adipate (hexansdioates) and relevant compound in the detergent composition of the present invention.Useful succsinic acid washing assistant comprises C
5-C
20Alkyl and alkenyl succinic and its salt.Particularly preferred this compounds is the dodecenyl succinic amber.The object lesson of succinic acids washing assistant comprises: lauryl succinic acids, myristyl succinic acids, palmityl succinic acids, 2-dodecenyl succinic succinic acids (preferably), 2-ten pentaene base succinic acidses etc.The lauryl succinic acids is that this class washing assistant is preferred, and in the disclosed european patent application 86200690.5/0200263 description is arranged on November 5th, 1986.
Other suitable many carboxylates are disclosed among US 4144226 (people such as Crutchfield, on March 13rd, 1979 authorized) and the US 3308067 (Diehl, mandate on March 7th, 1967).And referring to the US 3723322 of Diehl.
Also can be with lipid acid, C for example
12-C
18Monocarboxylic acid is sneaked in the composition, individually or with above-mentioned washing assistant, especially lemon acids and/or the combination of succinic acids washing assistant so that additional washing assistant activity to be provided.Use lipid acid that foam is reduced like this, this is that formulator should be considered.
Under the situation that can use phosphorus base washing assistant and particularly, can use various alkali metal phosphates, for example tripoly phosphate sodium STPP, trisodium phosphate and the sodium orthophosphate known of people at the soap bar prescription that is used for hand-washing operation.Also can use the phosphonate washing assistant, ethane-1-hydroxyl-1 for example, 1-diphosphonate and other known phosphonate (see that for example, US 3159581; US3213030; US 3422021; US 3400148 and US 3422137).
Sequestrant
Detergent composition herein also can be chosen wantonly and contain one or more iron and/or manganese sequestrant.Such sequestrant can be selected from: as the aminocarboxylate that is hereinafter limited, and amino phosphonates do, the fragrant chelating agent that polyfunctional group replaces and its mixture.Without being limited by theory, the advantage that it is believed that these materials partly is owing to by forming the inner complex of solubility, remove the special ability of de-iron and mn ion from washing soln.
The aminocarboxylate that uses as optional sequestrant comprises: edetate, N-hydroxyethyl-ethylenediamine triacetate, triglycollamic acid salt, ethylenediamine tetrapropionic acid(EDTP) salt.Triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate, DTPMP and ethanol Diglycocol, the salt of basic metal, ammonium and replacement ammonium and its mixture.Be suitable as the methylglycine oxalic acid (MGDA) in addition of sequestrant.
When allowing to contain carbamate additives for low phosphorus at least in detergent composition, amino phosphonates do also is suitable as sequestrant in the composition of the present invention, and it comprises the ethylenediamine tetraacetic (methylene phosphonic acid salt) that is called DEQUEST.Preferred these amino phosphonates do do not contain alkyl or the alkenyl more than about 6 carbon atoms.
The fragrant chelating agent that polyfunctional group replaces also is useful in this article.See the US 3812044 that people such as Connor authorized on May 21st, 1974.The preferred compound of this class of acid form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.
Be used for this paper preferred biodegradable chelated dose is ethylenediamine disuccinate (" EDDS "), especially [S, the S] isomer described in US 4704233 (Hartman and Perkins, on November 3rd, 1987 authorized).
If you are using, these sequestrants account for about 0.1-10% of composition weight herein usually, and more preferably this sequestrant accounts for about 0.1-3.0% of composition weight.
Clay soil removal/anti is deposition agent again
Composition of the present invention also can be chosen wantonly and contain the water-soluble ethoxylated amine with clay soil removal and antiredeposition character.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of the 0.01-10.0% that has an appointment (weight); Liquid detergent composition generally contains the 0.01-5% that has an appointment (weight).
Most preferred decontamination dirt and anti redeposition agent are the tetrens of ethoxylation.Representational ethoxylated amine has further description in US 4597898 (VanderMeer, on July 1st, 1986 authorized).Another kind of preferred clay soil removal-anti redeposition agent is the amine polymer that is disclosed in the ethoxylation in the european patent application 111965 (Oh and Gosselink, on June 27th, 1984 is open); Be disclosed in the amphoteric ion polymer in the european patent application 112592 (Gosselikn, on July 4th, 1984 is open); With the amine oxide that is disclosed in US4548744 (Connor, on October 22nd, 1985 authorized).Other clay soil removal known in the art and/or anti redeposition agent also can be used for the composition of this paper.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are known in this area.
Polymeric dispersant
It is very useful that the polymeric dispersion agent can be used for this paper composition with the content of about 0.1-7% (weight), when especially having zeolite and/or layered silicate washing assistant.Suitable polymeric dispersant comprises many carboxylates of polymerization and polyoxyethylene glycol, although also can use other dispersion agent known in the art.Although do not plan bound by theory, but it is believed that: when with other washing assistant (comprising the many carboxylates of lower molecular weight) when being used in combination, free peptization and antiredeposition by inhibition crystalline growth, particulate fouling, polymeric dispersant has strengthened the overall performance of detergent builders.
By with suitable unsaturated monomer, preferably, can prepare the many carboxylates of polymerization with its sour form polymerization or copolymerization.The unsaturated monomer acid that can polymerization forms the suitable many carboxylates of polymerization comprises: vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, aconic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In many carboxylates of polymerization herein or the monomer fragment, exist not carboxylic composition for example vinyl methyl ether, vinylbenzene, ethene etc. be suitable, condition is that such fragment is no more than about 40% (weight).
The many carboxylates of specially suitable polymerization can be derived from vinylformic acid.Useful herein described vinylformic acid is that polymer based is the water-soluble salt of polymeric acrylic acid.The molecular-weight average of this polymkeric substance of acid form is preferably in the scope of about 2000-10000, more preferably from about 4000-7000, most preferably from about 4000-5000.The water-soluble salt of this acrylate copolymer can comprise: the salt of basic metal, ammonium and replacement ammonium for example.This class soluble polymer is known material.The purposes of this class polyacrylate in detergent composition has been disclosed in, for example among the US 3308067 (Diehl, on March 7th, 1967 authorized).
Vinylformic acid/toxilic acid is that based copolymers also can be as the preferred ingredient of dispersion agent/anti redeposition agent.Such material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of such multipolymer of acid form is preferably in the scope of about 2000-100000, more preferably from about 5000-75000, most preferably from about 7000-65000.The ratio of the vinylformic acid in this multipolymer and toxilic acid fragment is usually about 30: 1-1: 1 scope, more preferably from about 10: 1-2: 1.The water-soluble salt of such vinylformic acid/maleic acid can comprise: for example, and the salt of basic metal, ammonium and replacement ammonium.This class solubility acrylate/maleate copolymer is known material, it is described in european patent application 66915 (December 15 nineteen eighty-two is open) and EP 193360 (on September 3rd, 1986 is open), and back one piece of patent has also been described this polymkeric substance that contains the hydroxypropyl acrylate.Other useful dispersion agent also comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.Such material also is disclosed among the EP 193360, comprises for example 45/45/10 terpolymer of toxilic acid/vinylformic acid/vinyl alcohol.
Another polymeric material that can comprise is polyoxyethylene glycol (PEG).PEG can demonstrate the performance of dispersion agent and play clay soil removal-anti redeposition agent.Be used for the scope of the general molecular weight ranges of this purpose, preferably about 1000-50000, more preferably from about 1500-10000 at about 500-100000.
Also can use polyaspartic acid salts and polyglutamic acid dipersant, especially use with zeolite builders.Dispersion agent such as polyaspartic acid salts preferably have about 10000 molecular weight (on average).
Whitening agent
Generally any white dyes known in the art or other can be increased gorgeous or whitening agent joins in the detergent composition of this paper with the amount of about 0.05-1.2% (weight).Commercially available white dyes useful among the present invention can be classified into subclass, include (but are not necessarily limited to): stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene-5,5-dioxide, pyrroles, 5-and 6-unit's heterocyclic derivative and other all ingredients.The example of such whitening agent is disclosed in " production of white dyes and application " (" The Production and Application, ofFluorescent Brightening Agent ", M.Zahradnik, Published by JoneWiley ﹠amp; Sons, New York (1982)) in the book.
The specific examples of useful white dyes is those that determine in US 4790856 (Wixon, on December 13rd, 1988 authorized) in the present composition.These whitening agent comprise the PHORWHITE series whitening agent of Verona.Other whitening agent that is disclosed in this reference comprises: can be from the Tinopal UNPA of Ciba-Geigy purchase, Tinopal CBS and Tinopal 5BM; Artic White CC and Artic White CWD; 2-(4-styryl-phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The specific examples of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1,3-phenylbenzene-pyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.Also can be referring to US 3646015 (licensing to Hamilton on February 29th, 1972).This paper preferred anionic whitening agent.
Suds suppressor
The compound that reduces or the inhibition foam forms can be joined in the composition of the present invention.Foam inhibition as in so-called " the high density cleaning process " described in United States Patent (USP) 4489455 and 4489574 and in preceding year Europe class washing machine, be particularly important.
Can use various materials as suds suppressor, and suds suppressor is known for those skilled in the art.For example, see " encyclopedia of chemical technology " (Encyclopediaof Chemical Technology) the 3rd edition of Kirk Othmer, the 7th volume, 430-447 page or leaf (Jone Wiley﹠amp; Sons, Inc.1979).The suds suppressor of one class particularly important comprises mono carboxylic lipid acid and its water-soluble salt.See US 2954347 (Wayne St.John, authorize September 27 nineteen sixty).Mono carboxylic lipid acid and its salt as suds suppressor generally have 10-24 carbon atom, the alkyl of preferred 12-18 carbon atom.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.
Detergent composition herein also can contain the nonsurfactant suds suppressor.They comprise, for example: high-molecular-weight hydrocarbons such as paraffin, fatty acid ester (for example, glycerine fatty acid three esters), the fatty acid ester of monovalent alcohol, aliphatic C
18-C
40Ketone (as stearone) or the like.Other suds suppressor comprises: the alkylating aminotriazine of N-, for example three-to six-alkyl melamine or two-to four-alkyl diamine chlorotriazine (forming) as the product of the uncle of containing 1-24 carbon atom of cyanogen muriate and 2 or 3 moles or secondary amine, propylene oxide and single stearyl phosphoric acid ester, for example stearic alcohol ester of mono phosphoric acid ester and single stearyl di(2-ethylhexyl)phosphate an alkali metal salt (for example K, Na and Li) and phosphoric acid ester.Can use hydrocarbon with liquid form, for example paraffinic hydrocarbons and halogenated paraffin.Liquid hydrocarbon is a liquid under room temperature and normal atmosphere, and pour point is-40 ℃ to about 50 ℃ approximately, and minimum boiling point is not less than about 110 ℃ (under normal atmosphere).It also is known using wax shape hydrocarbon, and preferably its fusing point is lower than about 100 ℃.Hydrocarbon has constituted the suds suppressor that a class preferably is used for detergent composition.The hydrocarbon suds suppressor for example has description in US4265779 (people such as Gandolfo, on May 5th, 1981 authorized).Therefore, hydrocarbon comprises saturated and undersaturated aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon and heterocyclic hydrocarbon with about 12-70 carbon atom.The real paraffinic hydrocarbons and the mixture of cyclic hydrocarbon desired to comprise in the term " paraffinic hydrocarbons " that uses in this suds suppressor is discussed.
Another kind of preferred nonsurfactant suds suppressor comprises silicone suds suppressor.Such comprises use poly organic silicon oil (for example polydimethylsiloxane), the binding substances of the dispersion liquid of poly organic silicon oil or resin or emulsion and organopolysiloxane and silica dioxide granule (wherein organopolysiloxane chemisorption or fusion are on silicon-dioxide).Silicone suds suppressor in this area be know and for example be disclosed in US 4265779 people such as (, on May 5th, 1981 authorized) Gandolfo and the european patent application 89307851.9 (disclose February 7 nineteen ninety for Starch, M.S.).
Other silicone suds suppressor is disclosed among the US 3455839, and it relates to by adding a spot of polydimethylsiloxane liquid and is used for the composition and the method for aqueous solution froth breaking.
The mixture of siloxanes and silanized silica is for example having introduction among the German patent application DOS2124526.Silicone antifoam agent in granular detergent composition and Foam Control are disclosed among US 3933672 people such as () Bartolotta and the US 4652392 people such as (, on March 24th, 1987 authorized) Baginski.
The Foam Control that to be used for representative siloxanes suds suppressor herein be foam inhibition significant quantity, it is made up of following material substantially:
(ⅰ) viscosity is the polydimethylsiloxane fluid of about 20-1500cs (25 ℃);
(ⅱ) (ⅰ) of per 100 weight parts, the silicone resin of about 5-50 weight part, this resin is by (CH
3)
3SiO
1/2Unit and SiO
2The unit is formed, (CH
3)
3SiO
1/2Unit and SiO
2Unitary ratio is about 0.6: 1-1.2: 1; With
(ⅲ) (ⅰ) of per 100 weight parts, the solid silicone of about 1-20 weight part.
Be used for preferred silicone suds suppressor herein, the solvent that forms external phase is by some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably), and perhaps polypropylene glycol constitutes.Basic silicone suds suppressor is side chain/crosslinked and preferably is non-straight chain.
In order to further specify this point, the general liquid laundry detergent compositions with control foam can be chosen wantonly and comprise about 0.001-1% (weight), preferred about 0.01-0.7% (weight), the described silicone suds suppressor of 0.05-0.5% (weight) more preferably from about, this silicone suds suppressor comprises: the nonaqueous emulsion of (1) basic foam reducing composition, it is the mixture of following substances: (a) organopolysiloxane, (b) silicone compounds of arborescens siloxanes or generation silicone resin, (c) finely divided packing material, (d) promote component of mixture (a), (b) with the catalyzer that (c) reacts formation siliconization thing; (2) at least a nonionic siloxane tensio-active agent; (3) polyoxyethylene glycol, or the solubleness in water and does not have the polyethylene glycol-propylene glycol copolymers of polypropylene glycol greater than about 2% (weight) under the room temperature.In particulate composition, gel etc., can use similar amount.Referring to US 4978471 (Starch, authorize December 18 nineteen ninety), with US 4983316 (Starch, authorized on January 8th, 1991), US 5288431 (people such as Huber, authorized on February 22nd, 1994) and US 4639489 and US 4749740 people such as (, 46 row-Di, 4 hurdles 35, the 1st hurdle are capable) Aizawa.
Silicone suds suppressor herein preferably includes the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, its molecular-weight average all be lower than about 1000, preferably between about 100-800.The polyoxyethylene glycol herein and the multipolymer of polyethylene/polypropylene glycol, the solubleness under the room temperature in water are greater than about 2%, are preferably greater than about 5% (weight).
Preferred solvent herein is a molecular-weight average less than about 1000, more preferably from about between the 100-800, and the multipolymer of polyoxyethylene glycol between the 200-400 and polyethylene/polypropylene glycol most preferably from about, preferred PPG 200/PEG 300.Preferred polyoxyethylene glycol: the weight ratio of the multipolymer of polyethylene glycol-propylene glycol is 1: 1-1: between 10, most preferably 1: 3-1: between 6.
The preferred silicone suds suppressor that is used for does not herein contain polypropylene glycol, and especially molecular weight is 4000 polypropylene glycol.They preferably do not contain the segmented copolymer of oxyethane and propylene oxide yet, as PLURONICL 101.
Other useful herein suds suppressor comprises the mixture (for example being disclosed in the siloxanes among US 4798679,4075118 and the EP 150872) of secondary alcohol (for example 2-alkyl chain triacontanol) and described alcohol and silicone oil.This secondary alcohol comprises having C
1-C
16The C of chain
6-C
16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and it can obtain with trade(brand)name ISOFOL 12 from Condea.The mixture of secondary alcohol can be bought with trade(brand)name ISALCHEM 123 from Enichem.It is 1 that the mixing suds suppressor generally comprises weight ratio: 5-5: the mixture of alcohol+siloxanes of 1.
For the detergent composition that is used for automatic washing machine, should not form and make it overflow the foam of washing machine degree.When it used, suds suppressor preferably existed with " foam inhibition amount "." foam inhibition amount " is meant that the formulator of composition can select the amount of Foam Control to make and be enough to control foam, to obtain being used for the low foam detergent for washing clothes of automatic washing machine.
Composition herein generally includes the suds suppressor of 0-5%.When mono carboxylic lipid acid and salt thereof use as suds suppressor, 5% (weight) of the general as many as detergent composition of its amount.The preferred fatty monocarboxylate suds suppressor that uses about 0.5-3%.2.0% (weight) of the generally as many as detergent composition of the usage quantity of silicone suds suppressor is although also can use higher amount.This upper limit is a practicality, the main low amount of considering to keep least cost and effective control whipability.The preferably about 0.01-1% of amount of the silicone suds suppressor that uses, more preferably from about 0.25-0.5%.As employed in this article, these weight percent numerical value comprise any silicon-dioxide that can be used in combination with organopolysiloxane, and operable any additional materials.The amount of normally used single stearyl phosphoric acid ester suds suppressor accounts for the scope of about 0.1-2% (weight) of composition.The amount of the hydrocarbon suds suppressor that uses generally is about 0.01-5.0%, although can use higher amount.The amount of the pure suds suppressor that uses generally is about 0.2-3% (weight) of the finished product composition.
Fabric softener
In composition of the present invention, can choose wantonly and use the various fabric softeners that work by washing, especially US 4062647 (Storm and Nirschl, mandate on December 13rd, 1977) the particulate montmorillonitic clay in, and other softening agent clay known in the art, its amount generally is about 0.5-10% (weight), so that provide the fabric-softening effect simultaneously with fabric washing.The clay softening agent can be used in combination with amine and cationic softener, and for example US 4375416 (people such as Crisp, authorize March 1 nineteen eighty-three) and US 4291071 people such as (, mandate on September 22nd, 1981) Harris are disclosed.
Dye transfer inhibitor
Composition of the present invention can comprise that also one or more transfer to another fabric effective substance to suppressing dyestuff from a fabric in washing process.Usually, such dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase and its mixture of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If you are using, the amount of these reagent generally is about 0.01-10% of composition weight, preferably about 0.01-5% and 0.05-2% more preferably from about.
More particularly, be preferred for the unit that herein polyamine N-oxide pllymers contains following structural formula: R-A
x-P; Wherein P is a polymerizable unit, and the N-O group can be connected on this polymerizable unit, and perhaps the N-O group can form the part of this polymerizable unit, and perhaps the N-O group can be connected on these two unit; A is one of following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is aliphatic series, aromatic series, heterocycle or alicyclic group or its mixture of aliphatic series, ethoxylation, and the nitrogen of N-O group can connect on it, and perhaps the N-O group is the part of these groups.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example those polyamine N-oxide of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and its derivative.
The N-O group can be represented by following general formula:
R wherein
1, R
2, R
3Be aliphatic series, aromatic series, heterocycle or alicyclic group or its mixture, x, y and z are 0 or 1; The nitrogen of N-O group can be connected or form the part of arbitrary above-mentioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
Can use any polymer backbone,, and have the dye transfer inhibition activity just as long as the amine oxide polymers that forms is water miscible.The example of suitable polymeric skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.These polymkeric substance comprise that wherein a kind of monomer type is that amine n-oxide and other monomer type are the random or segmented copolymers of N-oxide compound.The amine of amine n-oxide polymkeric substance generally is 10 with the ratio of amine n-oxide: 1-1: 1000000.Yet the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-oxidisability.Can obtain polyoxygenated amine with almost any polymerization degree.General its molecular-weight average is in the scope of 500-1000000; More preferably 1000-500000; 5000-100000 most preferably.Preferred this class material can be referred to as " PVNO ".
Useful most preferred polyamine N-oxide is poly-(4 vinyl pyridines-N-oxide compound) in this paper detergent composition, and its molecular-weight average is about 50000, and about 1: 4 of the ratio of amine and amine n-oxide.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being referred to as " PVPVI " class) also is preferred for herein.The preferred 5000-1000000 of the average molecular weight range of PVPVI, more preferably 5000-200000 and most preferably 10000-20000.(average molecular weight range is with people such as Barth, and at Chemical Analvsis.Vol 113, the scattering of light described in " modernism of polymer characterization " (" Modern Methods of PolymerCharacterization ") literary composition is determined.The disclosed content of the document is incorporated herein by reference.) the N-vinyl imidazole of PVPVI multipolymer and the mol ratio of N-vinyl pyrrolidone generally be 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1.These multipolymers can be straight chain also can be side chain.
The present composition also can use molecular-weight average about 400000 for about 5000-, and preferably about 5000-is about 200000, more preferably from about the Polyvinylpyrolidone (PVP) of 5000-about 50000 (" PVP ").PVP is known for the technician of detergent applications; For example see EP-A-262897 and EP-A-256696, they are incorporated herein by reference.It is about 100000 for about 500-that the composition that contains PVP also can contain molecular-weight average, the polyoxyethylene glycol of preferably about 1000-about 10000 (" PEG ").The ratio of PEG and PVP (to be released in the ppm in the washings) preferably about 2: about 50: 1 of 1-, more preferably from about 3: about 10: 1 of 1-.
Detergent composition herein also can be chosen the particular type that contains the 0.005-5% that has an appointment (weight) wantonly also provides dye transfer inhibiting hydrophilic white dyes simultaneously.If you are using, composition herein preferably includes the above-mentioned white dyes of about 0.01-1% (weight).
Useful hydrophilic white dyes is the compound with following structural formula among the present invention:
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, chloro and amino; And M be shape salifiable positively charged ion, for example sodium or potassium.
R in following formula
1Be anilino, R
2Be N-2-two-hydroxyethyl and M are positively charged ions, for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.This specific whitening agent is sold by Ciba-GeigyCorporation with trade(brand)name Tinopal-UNPA-GX.Tinopal UNPA-GX is preferred hydrophilic white dyes useful in this paper detergent composition.
R in following formula
1Be anilino, R
2Be that N-2-hydroxyethyl-N-2-methylamino and M are positively charged ions for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-guanamine-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade(brand)name Tinopal-5BM-GX.
R in following formula
1Be anilino, R
2Be that morpholino and M are positively charged ions, for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino] 2,2 '-the stilbene disulfonic acid sodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade(brand)name Tinopal-AMS-GX.
Specific for selecting to be used for white dyes of the present invention, when being used in combination, provide especially effectively dye transfer rejection advantage with previously described polymeric dye transfer inhibitor through selecting.Compare with these two kinds of detergent composition components of independent use, by the polymeric material of above-mentioned selection (for example, PVNO and/or PVPVI) in aqueous detergent, provide obviously better dye transfer restraining effect with the mixture of the white dyes (for example, TinopalUNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) of above-mentioned selection.Bound by theory not, we believe that it is because they have high affinity to fabric in washings, so they are deposited on these fabrics relatively soon that above-mentioned whitening agent works.The degree that whitening agent is deposited on the fabric in washing soln can be with the parameter-definition that is referred to as " consumption coefficient ".In general consumption coefficient is whitening agent material and the b that a) is deposited on the fabric) ratio of initial whitening agent concentration in the washings.Whitening agent with high relatively consumption coefficient is suitable for suppressing dye transfer in the context of the present invention most.
Certainly, be appreciated that and other conventional fluorescent brightening formulation compound randomly can be used for composition of the present invention, so that provide conventional fabric " to brighten " usefulness, rather than real dye transfer restraining effect.Such use is conventional to the detergent formulation teacher and is known.
The present invention is fit to following method preparation as the modified polyamine of scavenging agent.
The embodiment I
PEI 1800 E
7Preparation
Ethoxylation carries out in the stainless steel autoclave of 2 gallons of stirrings, and this autoclave is equipped with the device of temperature survey and control, pressure survey, vacuum and inert gas purge, sampling and introducing liquid epoxy ethane.The oxyethane (ARC) of net weight～20 pound jar is placed on the scale pan so that can monitor its changes in weight, liquid epoxy ethane is sent in this autoclave with pump.
The polymine of 750g portion (PEI) (Nippon Shokubai, Epomin SP-018 indicate molecular-weight average 1800, are equivalent to about 0.417 moles of polymer and 17.4 mole of nitrogen functional groups) is added in this autoclave.(" Hg then is pressurized to 250 pounds/inch with nitrogen to be evacuated down to-28 then this autoclave to be sealed and removes air
2, be disposed to normal atmosphere then).The thing of autoclave the inside is heated to 130 ℃ to vacuumize simultaneously.After about one hour, charge into autoclave to about 250 pounds/inch with nitrogen
2, simultaneously autoclave is cooled to about 105 ℃.Then oxyethane is joined in this autoclave with incremental manner in time, pay close attention to the flow velocity of pressure, temperature and the oxyethane of autoclave simultaneously.The oxyethane pump is turned off also refrigeration to limit owing to the caused temperature of any exothermic reaction raises.In reaction process, temperature remains between 100 and 110 ℃, and total pressure allows progressively to improve.(be about as much as 1 moles of ethylene oxide/every PEI nitrogen functional group) after 750g oxyethane is all injected this autoclave, temperature rises to 110 ℃, allows this autoclave restir 1 hour.At this moment, vacuumize to remove remaining unreacted oxyethane.
Next step is to vacuumize continuously to make this autoclave be cooled to about 50 ℃ simultaneously, adds the methanol solution (1.74 moles is that benchmark loads 10% catalyzer to reach with PEI ammonia functional group) of the sodium methylate of 376g 25% more simultaneously.Methylate solution is drawn in this autoclave, makes the temperature control set(ting)value of this autoclave be elevated to 130 ℃ then.Monitor the power that agitator consumes with a kind of device.From autoclave, remove methyl alcohol thereupon mixture viscosity increase and within about 1 hour, settle out, illustrate that when most methyl alcohol had been removed, agitator power and temperature value can raise gradually.Further heated mixt and stirring 30 minutes under vacuum again.
Stop to vacuumize and make autoclave be cooled to 105 ℃, fill nitrogen to 250 pound/inch 2 simultaneously, be vented to environmental stress then.Autoclave is charged to 200 pounds/inch 2 with nitrogen.Increase progressively like before again and add oxyethane in autoclave, pay close attention to autoclave pressure, temperature and ethylene oxide flow rate simultaneously, and maintain the temperature between 100 and 110 ℃, restriction is because the temperature rising that exothermic reaction causes.Within several hrs, reach addition 4500g oxyethane (reaching every mole of PEI nitrogen functional group 7 moles of ethylene oxide altogether) afterwards, be warmed up to 110 ℃ and restir mixture 1 hour.
Then reaction mixture is collected in the container that nitrogen purge crosses, and finally transferred in the 22 liter of three neck round-bottomed flask that is equipped with heating and whipping appts, in the adding 167g methylsulfonic acid (1.74 moles) and strong alkali catalyst.Make about 100 cubic feet rare gas element (argon gas or nitrogen) by disperseing the sintered glass filter of gas then, and by reaction mixture, stir simultaneously and heated mixt to 130 ℃, thereby make reaction mixture slough stink.
Embodiment I A
PEI 1800 E7's is quaternized
Adding molecular-weight average in 500 milliliters of Erlenmeyer flasks that are equipped with magnetic stirring bar is 1800, and further uses the modification of ethoxylation method, reaches each nitrogen and has an appointment that (PEI 1800, E for the polymine of 7 ethyleneoxy group group degree
7) (207.3g, 0.590 mole of nitrogen are pressed the preparation of embodiment I) and acetonitrile (120g).Methyl-sulfate (28.3g, 0.224 mole) portion is joined in this solution of quick stirring, cover flask and stirring all night at room temperature then.Remove acetonitrile with the rotary distillation method down at 60 ℃, then use Kugelrohr equipment further extraction solvent under about 80 ℃, can provide the needed part of 220g quaternized material, it is the viscous liquid of burgundy.Resulting to the reaction product sample
13C-NMR (D
2O) spectrum is pointed out: do not have corresponding with the dimethyl sulfate carbon resonance peak at～58ppm place.
1H-NMR (D
2O) stave is bright: should partly be displaced to about 3.0ppm place at the resonance peak at about 2.5ppm place with the methylene radical of on-quaternised nitrogen adjacency.This is consistent with desirable about 38% nitrogen quaternization degree.
The embodiment II
PEI 1800 E
7The formation of amine oxide
Adding molecular-weight average in 500 milliliters of Erlenmeyer flasks that are equipped with magnetic stirring bar is 1800, and ethoxylation reaches polymine (PEI-1800, the E of about 7 the ethoxy group degree of each nitrogen
7) (209g, 0.595 mole of nitrogen are pressed the preparation of embodiment I), and hydrogen peroxide (the 30wt% aqueous solution of 120g, 1.06 moles).Cover flask, and after the heat release in the early stage, at room temperature stirred solution all night.Resulting to the reaction mixture sample
1H-NMR (D
2O) spectrum can show whether conversion is complete.Moved on to～the 3.5ppm place from starting position～2.5ppm with the resonance peak of the adjacent methene proton of unoxidized nitrogen.Add about 5g to reaction soln and carry the little pill of aluminum oxide of 5%Pd, and allow this solution at room temperature keep about three days.With the test paper test soln and find that this solution is negative to superoxide.Resulting material is suitable for storing with 51.1% active water solution.
The embodiment III
Quaternized PEI 1800 E
7Form amine oxide again
Adding molecular-weight average in 500 milliliters of Erlenmeyer flasks that are equipped with magnetic stirring bar is 1800, and further ethoxylation makes it to reach about 7 (the PEI1800 E of ethyleneoxy group group of each nitrogen
7), and then quaternized to about 38% and modified polyethylene imines (130g ,～0.20 mole of oxidable nitrogen press the embodiment II and prepared), hydrogen peroxide (the 30wt% concentration of aqueous solution of 48g) with methyl-sulfate, and water (～50g).Cover flask, in the early stage after the heat release, stirred solution all night under room temperature.Resulting to the sample of taking from reaction mixture
1H-NMR (D
2O) spectrum shows that resonance peak is changed fully because the methylene peak at previous observed 2.5-3.0ppm place has become chemical shift has been the material of about 3.7ppm methylene radical.Add about 5g to reaction soln and carry the little pill of aluminum oxide of 0.5%Pd, and allow solution at room temperature shelve about three days.With the test paper test soln and find that it is negative to hydrogen peroxide.Obtained desirable material (nitrogen wherein～38% is oxidized to amine oxide by the nitrogen of quaternized and 62%), and be suitable for storing in 44.9% actives aqueous solution mode.
The embodiment IV
PEI 1200 E
7Preparation
Ethoxylation stirs in the stainless steel autoclave at 2 gallons and carries out, and this autoclave is equipped with temperature survey and control, pressure survey, vacuum and indifferent gas purify, take a sample and the device of introducing liquid epoxy ethane.The oxyethane jar (ARC) of net weight～20 pound is placed on the scale pan, so that can monitor the variation of this jar weight, and with pump liquid epoxy ethane is sent in this autoclave.
The polymine of 750g portion (PEI) (indicate that molecular-weight average is 1200, be equivalent to about 0.625 moles of polymer and 17.4 mole of nitrogen functional groups) is joined in this autoclave.Seal this autoclave then and remove air that (" Hg then is pressurized to 250 pounds/inch with nitrogen to be evacuated down to-28
2, be disposed to normal atmosphere then).Autoclave contents is heated to 130 ℃ to vacuumize simultaneously.After about 1 hour, charge into this autoclave with nitrogen and reach about 250 pounds/inch
2, make autoclave be cooled to about 105 ℃ simultaneously.Then oxyethane is joined in the autoclave with incremental manner in time, pay close attention to autoclave pressure, temperature simultaneously, and ethylene oxide flow rate.Closing ring oxidative ethane pump, and cooling is to limit owing to the caused temperature of exothermic reaction raises.In reaction process, temperature remains between 100 and 110 ℃, and total pressure can allow to raise gradually.After 750g oxyethane all injects autoclave, (be about as much as each PEI nitrogen functional group 1 moles of ethylene oxide), raise the temperature to 110 ℃ and allow autoclave restir 1 hour.Vacuumize to remove all remaining unreacted oxyethane this moment.
Next step is to continue to vacuumize, and makes autoclave be cooled to about 50 ℃ simultaneously, and injects the methanol solution (1.74 moles is that benchmark loads 10% catalyzer to reach with the PEI nitrogen functional group) of the sodium methylate of 376g25%.Methylate solution is drawn in the autoclave, then autoclave temp controller set(ting)value is elevated to 130 ℃.Monitor the power that agitator consumes with a kind of device.Agitator power and temperature and pressure are monitored together.The mixture viscosity increases when remove methyl alcohol from autoclave, and when settling out in about 1 hour, illustrates that most methyl alcohol has been removed, and agitator power and temperature can progressively raise.Further heated mixt and under vacuum restir 30 minutes.
Stop to vacuumize and make autoclave be cooled to 105 ℃, fill nitrogen to 250 pound/inch simultaneously
2, and then be disposed to environmental stress.Charge into autoclave to 200 pound/inch with nitrogen
2Like before oxyethane is joined in the autoclave with incremental manner again, pay close attention to autoclave pressure, temperature and ethylene oxide flow rate simultaneously, and maintain the temperature between 100 and 110 ℃, raise to limit the temperature that causes owing to thermopositive reaction.In several hrs,, temperature is raised to 110 ℃, restir mixture 1 hour with after 4500g oxyethane (be equivalent to every mole of PEI nitrogen functional group and the have 7 moles of ethylene oxide) adding.
Then reaction mixture is collected in the container that nitrogen purge crosses, and finally transfers in the 22 liter of three neck round-bottomed flask that is equipped with heating and whipping appts.Add in the 167g methylsulfonic acid (1.74 moles) and strong alkali catalyst.Allow about 100 cubic feet rare gas element (argon gas or nitrogen) by disperseing the sintered glass filter of gas then, and by reaction mixture, stir simultaneously and heated mixt to 130 ℃, make reaction mixture slough stink.
Final reaction product is cooled down slightly and be collected in the Glass Containers of crossing with nitrogen purge.
In other preparation method, neutralization and deodorizing are to finish in the reactor before discharging.
Adopt aforesaid method, adjust the oxyethane relative quantity of using in reaction times and the reaction, can prepare other preferred sample such as PEI 1200 E15 and PEI 1200 E20.
The embodiment V
PEI 1200 E
79.7% quaternized
Add poly-(ethyleneimine) (its molecular weight is 1200, and ethoxylation degree reaches 7) (248.4g, 0.707 mole of nitrogen are pressed embodiment 5 preparations) and acetonitrile (Baker, 200 milliliters) to 500 milliliters of Erlenmeyer flasks that are equipped with magnetic stirring bar.Dimethyl sulfate (Aldrich, 8.48g, 0.067 mole) once all join in the solution of quick stirring, cover flask then and stirring all night under room temperature, under～60 ℃, make the acetonitrile evaporation, then provide～the needed burgundy mucus of 220g shape material with Kugelrohr equipment (Aldrich) down at～80 ℃ with rotatory evaporator.
13C-NMR (D
2O) spectrum shows; There is not peak corresponding to being positioned at of methyl-sulfate～58ppm.
1H-NMR (D
2O) spectrum shows: peak (being connected the methylene radical on the non-quaternary nitrogen) part that is positioned at 2.5ppm is displaced to～3.0ppm.
Laundry composition
Embodiment VI-IX
High-density (more than 600g/l) granular detergent composition contains following ingredients.
Weight %
Composition VI VII VIII IX
1.LIPOLASE
Enzyme is available from Novo Industri A/S, Denmark.2. according to the polyamine scavenger agents of embodiment I preparation.3. by the soil release polymer of U.S. Pat 4,968,451 (people such as Scheibel, authorize November 6 nineteen ninety) preparation.4. for example can comprise white dyes, spices, suds suppressor, dirt dispersant, proteolytic enzyme, cellulase, sequestrant, dye transfer inhibitor, additional water, and weighting agent (comprises CaCO
3, talcum, silicate) etc. auxiliary material, the introducing of these compositions makes total amount reach 100%.
| C 11-C 13Sodium alkyl benzene sulfonate | ?13.3 | ??13.7 | ??10.4 | ??11.1 |
| C 14-C 15Alcohol sodium sulfate | ?3.9 | ??4.0 | ??4.5 | ??11.2 |
| Ethoxylation (0.5) C 14-C 15Alcohol sodium sulfate | ?2.0 | ??2.0 | ??0.0 | ??0.0 |
| Ethoxylation (6.5) C 14-C 15Sodium alkoxide | ?0.5 | ??0.5 | ??0.5 | ??1.0 |
| Tallow fatty acids | ?0.0 | ??0.0 | ??0.0 | ??1.1 |
| Tripoly phosphate sodium STPP | ?0.0 | ??41.0 | ??0.0 | ??0.0 |
| Zeolite A hydrate (0.1-10 micron) | ?26.3 | ??0.0 | ??21.3 | ??28.0 |
| Yellow soda ash | ?23.9 | ??12.4 | ??25.2 | ??16.1 |
| Sodium polyacrylate (45%) | ?3.4 | ??0.0 | ??2.7 | ??3.4 |
| Water glass (NaO/SiO 2Ratio be 1: 6) (46%) | ?2.4 | ??6.4 | ??2.1 | ??2.6 |
| Sodium sulfate | ?10.5 | ??10.9 | ??8.2 | ??15.0 |
| Poly-(ethylene glycol), MW～4000 (50%) | ?1.7 | ??0.4 | ??1.0 | ??1.1 |
| Citric acid | ?0.0 | ??0.0 | ??3.0 | ??0.0 |
| P-hydroxy benzenyl sulfonate sodium nonyl ester | ?0.0 | ??0.0 | ??5.9 | ??0.0 |
| Lipase 1(100LU/mg) | ?0.3 | ??0.5 | ??0.3 | ??0.5 |
| Scavenging agent 2(obtaining) from the embodiment I | ?1.5 | ??1.5 | ??2.0 | ??1.0 |
| Soil release polymer 3 | ?1.5 | ??0.0 | ??0.0 | ??0.0 |
| Moisture and auxiliary material 4 | Surplus | Surplus | Surplus | Surplus |
When test contains the detergent composition degrease of lipase and scavenging agent and removes the human body fouling performance, adopt following testing method:
The embodiment X
Be fit to the extrusion process preparation of the laundry bar shaped agent of hand washing dirt fabric, contain following compositions with standard:
Composition weight %C
12Linear alkylbenzene sulfonate 30 phosphoric acid salt (as tripoly phosphate sodium STPP) 7 yellow soda ash 25 trisodium phosphate 7 coconut single ethanol amides, 2 zeolite A (0.1-10 micron) 5 carboxymethyl celluloses, 0.5 polyacrylates (molecular weight 1400) 0.2 polyamine scavenger agents (routine I) 1.0 lipase 1 (100LU/mg) 0.1 whitening agent, spices 0.2CaSO
41MgSO
41 moisture 4 comprises a small amount of auxiliary material of filler etc.
2Add to 100%1.LIPOLASE
Enzyme is available from Novo Industri A/S, Denmark.2. can be selected from common used material such as CaCO
3, talcum, clay, silicate etc.
US 3,178, and detergent for washing clothes bar and preparation method thereof has been introduced in 370 (Okenfuss, nineteen sixty-five mandates in April 13).Philippine patents 13,778 (Anderson, on September 23rd, 1980 authorized) has been introduced the synthetic detergent laundry bars.Method with various extrusion process manufacturing laundry detergent bars is well known in the art.
Embodiment XI and XII
The laundry soap bar that is suitable for hand-washing the dirt fabric is with the preparation of standard extrusion process and contain following ingredients.
Weight %
1. soil release polymer is according to US 4,968,451 people such as (, authorize November 6 nineteen ninety) Scheibel.2.LIPOLASE
Enzyme is available from Novo Industri A/S, Denmark.3. can be selected from common used material such as lime carbonate, talcum, clay, silicate etc.
| Composition | ????Ⅺ | ????Ⅻ |
| LAS | ????12 | ????6 |
| Soap | ????44 | ????29 |
| Tripoly phosphate sodium STPP | ????5 | ????5 |
| Yellow soda ash | ????4 | ????6 |
| White dyes | ????0.03 | ????0 |
| Talcum | ????0 | ????35.5 |
| Spices | ????0.45 | ????0 |
| Sodium sulfate | ????0.29 | ????0 |
| Wilkinite | ????12.81 | ????0 |
| Sodium-chlor | ????2 | ????2 |
| Soil release polymer 1 | ????0.5 | ????0.5 |
| Polyamine scavenger agents (embodiment I) | ????0.5 | ????1.0 |
| Lipase 2(100?LU/mg) | ????0.05 | ????0.1 |
| Water and a small amount of auxiliary material 3 | Surplus | Surplus |
Embodiment X III-X IV
Liquid detergent composition of the present invention is described below:
Weight %
1. auxiliary material-comprise white dyes.2. soil release polymer is according to US 4,968,451 people such as () Scheibel preparation.3.LIPOLASE
Enzyme is available from Novo Industri A/S, Denmark.4. polyamine scavenger agents PEI 1200 E20 prepare according to the embodiment IV.
| Composition | ????ⅩⅢ | ????ⅩⅣ |
| Poly-hydroxyl coconut fatty amide | ????3.65 | ????3.50 |
| E 9Ethoxylation C 12-C 15Alcohol | ????3.65 | ????0.80 |
| C 12-C 15Alcohol sodium sulfate | ????6.03 | ????2.50 |
| E 2.5Ethoxylation C 12-C 15Alcohol sodium sulfate | ????9.29 | ????15.10 |
| C 10The amido propylamine | ????0 | ????1.30 |
| Citric acid | ????2.44 | ????3.0 |
| Lipid acid (C 12-C 14) | ????4.23 | ????2.00 |
| Ethanol | ????3.00 | ????2.81 |
| Monoethanolamine | ????1.50 | ????0.75 |
| Propylene glycol | ????8.00 | ????7.50 |
| Boric acid | ????3.50 | ????3.50 |
| Tetren | ????0 | ????1.18 |
| Toluenesulfonic acid sodium salt | ????2.50 | ????2.25 |
| NaOH | ????2.08 | ????2.43 |
| Auxiliary material 1 | ????1.60 | ????1.30 |
| Soil release polymer 2 | ????0.33 | ????0.22 |
| Lipase 3(100LU/mg) | ????0.3 | ????0.5 |
| Polyamine scavenger agents 4 | ????0.50 | ????0.50 |
| Water | Surplus | Surplus |
The dishwashing composition
Another aspect of the present invention relates to the dishwashing composition, specifically is the composition of automatic bowl dish and manual dishwashing, especially hand dishwashing liquid composition.
Liquid dishwashing composition according to the present invention preferably contains at least about 0.1%, and more preferably from about 0.5% to about 30%, most preferably from about 1% to about 15% dispersion agent and about 1% to about 99.99% detergent surfactant.
Liquid dishwashing composition according to the present invention can contain this paper any composition listed above.In addition, the dishwashing composition can also contain other composition, as sterilant, sequestrant, suds booster, opalizer and calcium and magnesium ion.
Embodiment X V
Following liquid composition of the present invention can mix by specified rate with following compositions:
Composition (wt%)
Composition A B C D E F water 28.0 34.0 30.0 41.0 41.0 36.0 ethanol 13.0 8.0 8.0 8.0 8.0 8.0 straight chain DBSAs 9.0 9.0 9.0 9.0 9.0 9.0 coco group sodium sulphate 1.0-1.0---1 mole of C13-C
151 mole of C of the condenses of oxo ethanol and 7.0---7.0-7 moles of ethylene oxide
13-C
15The condenses C of oxo ethanol and-7.0 7.0 7.0-7.05 moles of ethylene oxide
12-C
14(2 hydroxyethyl) dimethyl-0.5 0.5-0.5 0.5 ammonium chloride laurylene base succsinic acid 12.5--10.0--laurylene base-tetradecene base succsinic acid----10.0-TMS/TDS
1-12.5---sodium phosphate trimer--15.0---zeolite-----15.0 citric acids, 1.0 3.0 2.8 2.8 3.0 2.8 oleic acid 3.0-----diethylenetriamine pentamethylenophosphonic acid 0.7 0.7---hexamethylene diamine four (methylene--0.6--0.7 phosphonic acids) scavenger (Ex.I) 0.5 1.5 2.0 0.5 1.0 1.0 lipase2(80: 20) mixture of 100LU/mg 0.3 0.3 0.5 0.5 0.3 0.3 proteinase 8 KNPU/g 0.5-----protease 16 KNPU/g-0.3 0.3 0.3 0.3 0.3 amylase 0.2----0.2 sodium formate 1.0-1.5 1.0--sodium acetate-2.5 2.5---magnesium acetate 4 hydrate 1.7-1.7 0.1--magnesium chloride hexahydrate-1.7--0.1 0.7 NaOH 5.0 5.0 5.0 5.0 5.0 5.0 spices and a small amount of other auxiliary material surplus to 100%1. tartaric acid monosuccinic acid salt/tartaric acid disuccinate. 2.LIPOLASEEnzyme is available from Novo Industri A/S, Denmark.
Embodiment X VI automatic bowl dish composition is as follows:
Composition % (Wt.) trisodium citrate 15 yellow soda ash 20 silicate
19 nonionogenic tensides
23 sodium polyacrylates (m.w.4000)
35 lipase
4(100LU/mg) 0.5Termamvl enzyme (60T) 1.1Savinase enzyme (12T) 3.0 scavenging agents (embodiment I) 1.0 a small amount of other auxiliary materials add to 100%1.BRITESIL, PQ Corporation.2. polyethylene/polypropylene oxides is hanged down infusion.3.ACCUSOL, Rohm and Haas.4.LIPOLASE
Enzyme is available from Novo Industri A/S, Denmark.
In above-mentioned composition, tensio-active agent can replace with any low bubble, the nonionogenic tenside of equivalent amount.Example comprises the Plurafac of low bubble or still ethoxylation straight chain ethanol such as Eurane Co. supply
RA series, the Lutensol of BASF Co. supply
LF series, Rohm﹠amp; The Triton of Haas Co. supply
The Synperonic of DF series and ICI Co. supply
LF series.
Automatic bowl dish composition can be particulate state, sheet, strip or rinse aid shape.The method of making particle, sheet, bar or drifting the auxiliary agent shape is well known in the art.Referring to, for example, United States Patent (USP) series number 08/106,022,08/147,222,08/147,224,08/147,219,08/052,860,07/867,941.
Claims (10)
1. laundry detergent composition, it contains:
A. detergent surfactant;
B. lipase, its amount has an appointment 0.004 to about 6 steatolysis units (LU/mg) for containing in every milligram of composition;
C. about 0.01% to about 15% scavenging agent, and this scavenging agent contains the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n+1)W
mY
nZ or contain the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n-k+1)W
mY
nY '
kZ, wherein k is less than or equal to n, and the molecular weight of described polyamine main chain before modification is greater than about 200 dalton, in the formula
ⅰ) the V unit is the end group unit of following formula:
ⅱ) the W unit is the backbone units of following formula:
ⅲ) the Y unit is a chain unit of following formula:
ⅳ) the Z unit is the end group unit of following formula:
The R unit that wherein is connected on the main chain is selected from following radicals: C
2-C
12Alkylidene group ,-(R
1O)
xR
3(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-CH
2CH (OR
2) CH
2-and mixed base; If when R contains C
1-C
12Alkylidene group, R also contain at least one-(R
1O)
xR
3(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1-(OCH
2CH (OR
2) CH
2)
w-, or-CH
2CH (OR
2) CH
2-unit; R
1Be C
2-C
6Alkylidene group and mixed base thereof; R
2Be hydrogen ,-(R
1O)
xB, and mixed base; R
3Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Dihydroxyl-alkylidene group, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
5NHC (O)-, C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-, and mixed base; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkylene group, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and mixed base thereof; R
5Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from following groups :-(CH
2)
p-CO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
qPO
3M ,-(R
1O)
xB, and mixed base; B is a hydrogen ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
qCH (SO
3M) CH
2SO
3M ,-(CH
2)
qCH (SO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, and mixed base; M is hydrogen or water-soluble cationic, and its quantity is enough to satisfy charge balance; X is a water soluble anion; The k value is 0 to about 20; The m value is 4 to about 400; The n value is 0 to about 200; The p value is 1 to 6; The q value is 0 to 6; The r value is 0 or 1; The w value is 0 or 1; The x value is 1 to 100; The y value is 0 to 100; The z value is 0 or 1; And
D. all the other are adjunct ingredient.
2. composition according to claim 1, wherein lipase is to plant bacterium by thin cotton wool shape corruption to derive, its enzymic activity is every milligram of composition about 1 to about 50LU.
3. composition according to claim 1 contains at least about 0.01% and is selected from following detergent surfactant: negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics and composition thereof.
4. composition according to claim 3, wherein R is C
2-C
6Alkylidene group; R
1It is at least 50% ethylidene; R
2Be hydrogen; The E unit is selected from following groups: hydrogen, C
1-C
22Alkyl ,-(R
1O)
xB ,-C (O) R
3With its mixture; B be hydrogen ,-(CH
2)
qSO
3M and its mixture; And the q value is 0 to 3.
5. composition according to claim 4, wherein R
1It is ethylidene; The E unit is-(R
1O)
xB; And B is a hydrogen.
6. composition according to claim 5 contains and has an appointment 0.05% to about 8% scavenging agent.
7. laundry detergent composition, contain:
A. be selected from following detergent surfactant at least about 0.1% (weight): negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and composition thereof;
B. lipase, its amount has an appointment 0.007 to about 3 steatolysis units (LU/mg) for containing in every milligram of composition;
C. about 0.05% to about 8% scavenging agent, and this scavenging agent contains the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n+1)W
mY
nZ or contain the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n-k+1)W
mY
nY '
kZ, wherein k is less than or equal to n, and the molecular weight of described polyamine main chain before modification is greater than about 200 dalton, in the formula
ⅰ) the V unit is the end group unit of following formula:
ⅱ) the W unit is the backbone units of following formula:
ⅲ) the Y unit is a chain unit of following formula:
ⅳ) the Z unit is the end group unit of following formula:
The R unit that wherein is connected on the main chain is selected from following groups: C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Dihydroxyl-alkylidene group, C
8-C
12Two alkyl arylenes ,-(R
1O)
xR
1,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-, and mixed base; R wherein
1Be C
2-C
6Alkylidene group and mixed base thereof; R
2Be hydrogen ,-(R
1O)
xB, and mixed base; R
3Be C
1-C
18Alkyl, C
7-C
12Aralkyl, C
7-C
12The aryl that alkyl replaces, C
6-C
12Aryl, and mixed base; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkylene group, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and mixed base thereof; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Dihydroxyl-alkylidene group, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-, and mixed base, R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from following groups: hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3, and mixed base; Oxide compound; B is a hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, and mixed base; M is hydrogen or water-soluble cationic, and its quantity is enough to satisfy charge balance; X is a water soluble anion; The m value is 4 to about 400; The n value is 0 to about 200; The p value is 1 to 6; The q value is 0 to 6; The r value is 0 or 1; The w value is 0 or 1; The x value is 1 to 100; The y value is 0 to 100; The z value is 0 or 1; And
D. all the other are adjunct ingredient.
8. composition according to claim 7, wherein lipase is to be derived by thin cotton wool shape humic bacterium, its enzymic activity is every milligram of composition about 0.01 to about 1LU.
9. composition according to claim 8 contains and has an appointment 0.1% to about 3% scavenging agent.
10. laundry detergent composition, contain:
A. be selected from following detergent surfactant at least about 0.1% (weight): negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and composition thereof;
B. lipase, its amount in every milligram of composition about 0.007 to about 3 steatolysis units (LU/mg);
C. about 0.05% to about 8% scavenging agent, this scavenging agent contain the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n+1)W
mY
nZ or contain the polyamine main chain of following formula:
Its modified polyamine molecular formula is V
(n-k+1)W
mY
nY '
kZ, wherein k is less than or equal to n, and the molecular weight before the described polyamine backbone modification is greater than about 200 dalton, in the formula
ⅰ) the V unit is the end group unit of following formula:
ⅱ) the W unit is the backbone units of following formula:
ⅲ) the Y unit is a chain unit of following formula:
ⅳ) the Z unit is the end group unit of following formula:
The R unit that wherein is connected on the main chain is selected from following groups: C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Dihydroxyl-alkylidene group, C
8-C
12Two alkyl arylenes ,-(R
1O)
xR
1,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-, and mixed base; R wherein
1Be C
2-C
6Alkylidene group and mixed base thereof; R
2Be hydrogen ,-(R
1O)
xB, and mixed base; R
3Be C
1-C
18Alkyl, C
7-C
12Aralkyl, C
7-C
12The aryl that alkyl replaces, C
6-C
12Aryl, and mixed base; R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenyl, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and mixed base thereof; R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Dihydroxyl-alkylidene group, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-, and mixed base, R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene; The E unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Aralkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3, and mixed base; Oxide compound; B is a hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, and mixed base; M is hydrogen or water-soluble cationic, and its quantity is enough to satisfy charge balance; X is a water soluble anion; The m value is 4 to about 400; The n value is 0 to about 200; The p value is 1 to 6; The q value is 0 to 6; The r value is 0 or 1; The w value is 0 or 1; The x value is 1 to 100; The y value is 0 to 100; The z value is 0 or 1;
D. amylase, its amount is about 0.00018% to about 0.06% a pure amylase of composition gross weight; And
E. all the other are adjunct ingredient.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9606275 | 1996-05-03 | ||
| USPCT/US96/06275 | 1996-05-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1224446A true CN1224446A (en) | 1999-07-28 |
Family
ID=22255039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96180364A Pending CN1224446A (en) | 1996-05-03 | 1996-06-03 | Detergent compositions comprising polyamine scavenger agents and enzymes |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0900262B1 (en) |
| JP (1) | JP3739408B2 (en) |
| CN (1) | CN1224446A (en) |
| AR (1) | AR006949A1 (en) |
| AT (1) | ATE222285T1 (en) |
| AU (1) | AU6033696A (en) |
| BR (1) | BR9612629A (en) |
| CA (1) | CA2252883A1 (en) |
| CZ (1) | CZ354598A3 (en) |
| DE (1) | DE69623049T2 (en) |
| ES (1) | ES2177788T3 (en) |
| HU (1) | HUP9903729A3 (en) |
| IL (1) | IL120765A0 (en) |
| MA (1) | MA24161A1 (en) |
| WO (1) | WO1997042284A1 (en) |
| ZA (1) | ZA973764B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0945500A1 (en) * | 1998-03-23 | 1999-09-29 | The Procter & Gamble Company | Liquid laundry detergent compositions comprising HEDP and polyamines |
| US6677289B1 (en) | 1999-07-16 | 2004-01-13 | The Procter & Gamble Company | Laundry detergent compositions comprising polyamines and mid-chain branched surfactants |
| US6696401B1 (en) | 1999-11-09 | 2004-02-24 | The Procter & Gamble Company | Laundry detergent compositions comprising zwitterionic polyamines |
| EP1537198B2 (en) | 2002-09-12 | 2011-11-16 | The Procter & Gamble Company | Polymer systems and cleaning compositions comprising same |
| MX2008014924A (en) * | 2006-05-22 | 2008-12-09 | Procter & Gamble | Liquid detergent composition for improved grease cleaning. |
| US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
| JP5882991B2 (en) * | 2010-05-14 | 2016-03-09 | ザ サン プロダクツ コーポレーション | Polymer-containing cleaning compositions and methods for their production and use |
| WO2015030940A1 (en) | 2013-08-26 | 2015-03-05 | The Procter & Gamble Company | Compositions comprising alkoxylated polyalkyleneimines having low melting points |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8627915D0 (en) * | 1986-11-21 | 1986-12-31 | Procter & Gamble | Detergent compositions |
| JPS6490296A (en) * | 1987-09-30 | 1989-04-06 | Kao Corp | Detergent composition |
| EP0553607B1 (en) * | 1992-01-31 | 1998-03-18 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
| PE6995A1 (en) * | 1994-05-25 | 1995-03-20 | Procter & Gamble | COMPOSITION INCLUDING A PROPOXYLATED POLYKYLENE OAMINE POLYKYLENE OAMINE POLYMER AS DIRT SEPARATION AGENT |
-
1996
- 1996-06-03 CN CN96180364A patent/CN1224446A/en active Pending
- 1996-06-03 JP JP53987797A patent/JP3739408B2/en not_active Expired - Fee Related
- 1996-06-03 EP EP96917961A patent/EP0900262B1/en not_active Expired - Lifetime
- 1996-06-03 HU HU9903729A patent/HUP9903729A3/en unknown
- 1996-06-03 AT AT96917961T patent/ATE222285T1/en not_active IP Right Cessation
- 1996-06-03 DE DE69623049T patent/DE69623049T2/en not_active Expired - Lifetime
- 1996-06-03 CA CA002252883A patent/CA2252883A1/en not_active Abandoned
- 1996-06-03 BR BR9612629-9A patent/BR9612629A/en active Search and Examination
- 1996-06-03 WO PCT/US1996/008511 patent/WO1997042284A1/en not_active Application Discontinuation
- 1996-06-03 CZ CZ983545A patent/CZ354598A3/en unknown
- 1996-06-03 ES ES96917961T patent/ES2177788T3/en not_active Expired - Lifetime
- 1996-06-03 AU AU60336/96A patent/AU6033696A/en not_active Abandoned
-
1997
- 1997-04-30 ZA ZA9703764A patent/ZA973764B/en unknown
- 1997-05-02 MA MA24580A patent/MA24161A1/en unknown
- 1997-05-02 AR ARP970101825A patent/AR006949A1/en unknown
- 1997-05-02 IL IL12076597A patent/IL120765A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0900262B1 (en) | 2002-08-14 |
| BR9612629A (en) | 2001-06-19 |
| EP0900262A1 (en) | 1999-03-10 |
| IL120765A0 (en) | 1997-09-30 |
| JP3739408B2 (en) | 2006-01-25 |
| JP2002506464A (en) | 2002-02-26 |
| MX9809205A (en) | 1999-02-01 |
| AU6033696A (en) | 1997-11-26 |
| MA24161A1 (en) | 1997-12-31 |
| CA2252883A1 (en) | 1997-11-13 |
| DE69623049T2 (en) | 2003-04-24 |
| ATE222285T1 (en) | 2002-08-15 |
| DE69623049D1 (en) | 2002-09-19 |
| CZ354598A3 (en) | 1999-02-17 |
| WO1997042284A1 (en) | 1997-11-13 |
| ES2177788T3 (en) | 2002-12-16 |
| HUP9903729A3 (en) | 2001-10-29 |
| AR006949A1 (en) | 1999-09-29 |
| ZA973764B (en) | 1997-12-01 |
| HUP9903729A2 (en) | 2000-03-28 |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |