CN1284122A - Stabilised fabric softening compsns - Google Patents
Stabilised fabric softening compsns Download PDFInfo
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- CN1284122A CN1284122A CN98813264A CN98813264A CN1284122A CN 1284122 A CN1284122 A CN 1284122A CN 98813264 A CN98813264 A CN 98813264A CN 98813264 A CN98813264 A CN 98813264A CN 1284122 A CN1284122 A CN 1284122A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
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Abstract
The present invention is a composition comprising a polyamino functional polymer, whereby said composition is stabilised by means of a crystal growth inhibitor.
Description
Invention field
The present invention relates to contain the Fabrid care composition of poly-amino-functional polymkeric substance, thereby obtain the effectively stable of composition.
Background of invention
Colored fabric, for example clothes, bedclothes, home textile, for example the outward appearance of tablecloth is one of aspect of being concerned about of human consumer.In fact, according to the use of the typical consumer of fabric, for example wearing and tearing of fabric, washing, rinsing and/or drum dried, it is impaired appearance of fabrics to take place, this to small part be because the loss of color fidelity and color sharpness.This colour loss problem is especially serious after wash(ing)cycle repeatedly.
Therefore, the purpose of this invention is to provide a kind of composition, it provides the color nursing of improvement to the fabric that is washed, especially after wash(ing)cycle repeatedly.
Recently, a kind of novel substance that is called the amino-functional polymkeric substance is found in the purposes that the fabric treating aspect increases, so that the nursing of fabric color to be provided.
Yet, find that now the composition that contains these amino-functional polymkeric substance has the trend that causes storage stability.This problem is characterised in that the composition jaundice, and produces stench on the fabric of handling.This problem is especially serious when product is formulated as stand-alone product.In fact, when full preparation, for example in soft compound, wherein the spices of Cun Zaiing provides some stench to cover, thereby makes the stench that produces more can accept.In contrast, for stand-alone product, spices is not enough to cover stench, unless exist with very high content.Yet high-load spices has increased the cost of prescription.In addition, covering malodorous high-load spices still can not provide permanent stench to cover.In fact, spices will provide instant stench to cover, but the spices that contains volatility head perfume (or spice) along with storage will evaporate, so reduce the stench coverage effect.
Therefore, the makers-up of Fabrid care composition does not damage the dual problem of the stability of composition in the face of preparation provides fabric nursing.
Now the applicant is surprised to find and adds crystal growth inhibitor overcome this problem in the composition of the amino-functional polymkeric substance that contains modification.
The detailed description amino-functional polymkeric substance of invention
A main ingredient of the present invention is the amino-functional polymkeric substance.The amino-functional polymkeric substance has advantageously provided the nursing of fabric color.
Amino-functional polymkeric substance of the present invention is water-soluble or the dispersible polyamine of water.The amino-functional polymkeric substance that is generally used for this paper has 200-10
6Molecular weight, preferred 600-20000, most preferably 1000-10000.It can be straight chain or cyclic skeleton that these polyamine contain.Polyamine backbone can also contain the polyamine side chain of bigger or less degree.Polyamine backbone described herein is modification as follows preferably, makes at least one of polyamine chain, preferably each nitrogen be described to replace, quaternized, oxidation or their bonded unit.
Being used for hydrogen atom (replacement), quaternized skeleton nitrogen (quaternized) or oxidation skeleton nitrogen that the term " modification " that relates to the chemical structure of polyamine of the present invention is defined as replacing with R ' unit skeleton-NH is N-oxide compound (oxidation).Replace when being connected in the hydrogen atom of skeleton nitrogen when relating to R ' unit, term " modification " and " replacement " are used interchangeably.Quaternized or oxidation can be carried out under some occasion that does not have to replace, but replaces the oxidation that preferably is accompanied by at least one skeleton nitrogen or quaternized.
The straight chain or the non-annularity polyamine backbone that constitute the amino-functional polymkeric substance have following general formula:
The cyclic polyamines skeleton that constitutes the amino-functional polymkeric substance has following general formula:
Optionally, but before preferred subsequently the modification, above-mentioned skeleton contain by the connection of R " connections " unit primary, the second month in a season and tertiary amine nitrogen.
In a single day the primary amine nitrogen that is used for formation skeleton of the present invention or side chain be modified and just be defined as V or Z " end " unit.For example, when the primary amine part with following structure that is positioned at a main polyamine backbone or a link ends is carried out modification according to the present invention: H
2N-[R]-it is defined as V " end " unit subsequently, or abbreviate the V unit as.Yet, in the present invention, being subjected to the following restriction that further describes, some or all primary amine parts can keep unmodified.Consider its position in skeletal chain, these unmodified primary amine parts still are " end " unit.Equally, when the primary amine part with following structure that is positioned at main polyamine backbone end is carried out modification according to the present invention:
-NH
2It is defined as Z " end " unit subsequently, or abbreviates the Z unit as.Be subjected to the following restriction that further describes of this paper, it is unmodified that this unit can keep.
In a similar fashion, in a single day the secondary amine nitrogen of formation skeleton or side chain be modified and just be defined as W " skeleton " unit.For example, when secondary amine part, when the major portion of skeleton of the present invention and side chain is carried out modification according to the present invention with following structure:
It is defined as W " skeleton " unit subsequently, or abbreviates the W unit as.Yet in the present invention, some or all secondary amine parts can keep unmodified.Consider its position in skeletal chain, these unmodified secondary amine parts still are " skeleton " unit.
In further similar mode, in a single day the tertiary amine nitrogen that constitutes skeleton or side chain is modified and also is called Y " side chain " unit.For example, when having following structure, be the tertiary amine part of the chain branching point of polyamine backbone or other side chain or ring when carrying out modification according to the present invention:
It is defined as Y " side chain " unit subsequently, or abbreviates the Y unit as.Yet in the present invention, some or all tertiary amine parts can keep unmodified.Consider its position in skeletal chain, these unmodified tertiary amine parts still are " side chain " unit.The R unit that following description and the V that is used to be connected polyamine nitrogen, W are connected with the Y unit.
The final modified structure of polyamine of the present invention can be represented with following general formula for straight chain amino-functional polymkeric substance:
V
(n+1)W
mY
nZ can represent with following general formula for the cyclic amino functional polymer:
V
(n-k+1)W
mY
nY '
kZ is containing under the polyamine situation of ring the Y ' unit of following formula:
Branch point as a skeleton or a chain link.For each Y ' unit, there is the Y unit of following formula:
It will form the tie point of ring and host polymer chain or side chain.Skeleton is that polyamine backbone has following formula under the single situation of encircling completely therein:
Thereby do not contain the Z terminal units, and have following formula:
V
N-kW
mY
nY '
kWherein k is the quantity that forms the unitary ring of side chain.Polyamine backbone of the present invention does not preferably contain ring.
Under the situation of acyclic polyamine, subscript n is called relative degree of branching with the ratio of subscript m.Complete non-branching straight chain modified polyamine of the present invention has following formula:
VW
mZ is that n equals 0.N value big more (ratio of m and n is more little), degree of branching is big more in the molecule.The scope of m value is usually from minimum value 2-700, preferred 4-400, yet bigger m value also is preferably, especially in the value of coefficient n very little or near 0 in.
Each polyamine nitrogen, no matter it be primary, the second month in a season or uncle's nitrogen, in case carry out modification, also be defined as a kind of in three kinds of common kinds: simply replace, quaternized or oxidation according to the present invention.Those unmodified polyamine nitrogen unit according to its be primary, the second month in a season or uncle's nitrogen, be categorized as V, W, Y, Y ' or Z unit.Be that unmodified primary amine nitrogen among the present invention is V or Z unit, unmodified secondary amine nitrogen is that W or Y ' unit and unmodified tertiary amine nitrogen are the Y unit.
The modification primary amine partly is defined as V " end " unit with one of following three kinds of forms: the simple replacement unit that a) has following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; And c) have the oxidation unit of following structure:
Modification secondary amine partly is defined as W " skeleton " unit with one of following three kinds of forms: the simple replacement unit that a) has following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; And c) have the oxidation unit of following structure:
Other modification secondary amine partly is defined as the Y ' unit with one of following three kinds of forms: the simple replacement unit that a) has following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; And c) have the oxidation unit of following structure:
Enhanced tertiary amine partly is defined as Y " branching " unit with one of following three kinds of forms: the unmodified unit that a) has following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; And c) have the oxidation unit of following structure:
Some modification primary amine partly is defined as Z " end " unit with one of following three kinds of forms: the simple replacement unit that a) has following structure:
B) have the quaternized unit of following structure:
Wherein X provides the suitable counter ion of charge balance; And c) have the oxidation unit of following structure:
When the position on any nitrogen is not replace or when unmodified, be appreciated that hydrogen will replace R '.The primary amine unit that for example contains a unitary hydroxyethyl portion-form of R ' is to have formula (HOCH
2CH
2) the V terminal units of HN-.
There is two types chain end unit in the present invention, V and Z unit.Z " end " unit is by structure-NH
2The amino part of terminal primary obtain.Non-annularity polyamine backbone of the present invention only comprises a Z unit, thereby cyclic polyamines can not comprise the Z unit.Except when outside the Z unit was modified when forming the N-oxide compound, Z " end " unit can replace with any R ' as described below unit.Z unit nitrogen is oxidized under the situation of N-oxide compound therein, and nitrogen must be modified, thereby R ' can not be a hydrogen.
Polyamine of the present invention comprises skeleton R " connection " unit, and it is used to connect the nitrogen-atoms of skeleton.The unitary unit of the R of containing of the present invention is called " alkyl R " unit and " oxygen base R " unit." alkyl " R unit is C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, wherein except the carbon atom that is directly connected in polyamine backbone nitrogen, any position that hydroxylic moiety can be on the R cellular chain; C
4-C
12Alkyl sub-dihydroxy, wherein except the carbon atom that is directly connected in polyamine backbone nitrogen, hydroxylic moiety can connect any two carbon atoms on the R cellular chain; C
8-C
12The dialkyl group arylidene is the arylidene part that contains as two alkyl substituents of connection chain part in the present invention.For example, the dialkyl group arylidene that has following formula:
Though the unit needs not to be 1,4-replaces, and also can be 1,2 or 1,3 C that replaces
2-C
12Alkylidene group, preferred ethylidene, propylene and their mixture, most preferably ethylidene." oxygen base " R unit comprises-(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-,-CH
2CH (OR
2) CH
2-,-(R
1O)
xR
1-and their group of mixture.Preferred R unit is selected from C
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(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-; The R unit is more preferably C
2-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy ,-(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 their mixture; The R unit is C preferably also
2-C
12Alkylidene group, C
3Hydroxy alkylidene and their mixture; Most preferably be C
2-C
6Alkylidene group.Most preferred skeleton of the present invention contain at least 50% be the R unit of ethylidene.
R
1The unit is C
2-C
6Alkylidene group and their mixture, 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 their mixture, preferred C
1-C
12Alkyl, C
7-C
12Aryl alkylene, more preferably C
1-C
12Alkyl, most preferable.R
3The unit is as the unitary part of R ' described below.
R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, preferred C
1-C
10Alkylidene group and 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
5Preferably ethylidene ,-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-, be more preferably-CH
2CH (OH) CH
2-.
R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene.
Preferably " oxygen base " R unit is at R
1, R
2And R
5Further definition in the unit.Preferably " oxygen base " R unit comprises preferred R
1, R
2And R
5The unit.Preferred cotton stain remover of the present invention contains at least 50% and is the R of ethylidene
1The unit.Preferred R
1, R
2And R
5The unit combines with " oxygen base " R unit and obtains following preferred " oxygen base " R unit.ⅰ) at-(CH
2CH
2O)
xR
5(OCH
2CH
2)
xPreferred R is gone in-middle replacement
5Obtain-(CH
2CH
2O)
xCH
2CHOHCH
2(OCH
2CH
2)
x-.ⅱ) at-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1O (CH
2CH (OR
2) CH
2)
wPreferred R is gone in-middle replacement
1And R
2Obtain-(CH
2CH (OH) CH
2O)
z-(CH
2CH
2O)
yCH
2CH
2O (CH
2CH (OH) CH
2)
w-.ⅲ) at-CH
2CH (OR
2) CH
2Preferred R is gone in-middle replacement
2Mention-CH
2CH (OH) CH
2-.
R ' unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Thiazolinyl, C
7-C
22Arylalkyl, 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, most preferably C
1-C
22Alkylidene group ,-(R
1O)
xB and-C (O) R
3When not carrying out modification or replace on nitrogen, then hydrogen atom keeps the part as expression R '.Most preferred R ' unit is-(R
1O)
xB.
Oxidized when V, W or Z unit, when promptly nitrogen was the N-oxide compound, R ' unit did not contain hydrogen atom.For example skeletal chain or side chain do not comprise the unit of following structure:
In addition, oxidized when V, W or Z unit, when promptly nitrogen was the N-oxide compound, R ' unit did not comprise the carbonyl moiety that is directly connected in nitrogen-atoms.According to the present invention, R ' unit-C (O) R
3Part is not attached to the nitrogen of N-oxide modifying, does not promptly have the N-oxide compound acid amides with following structure:
Or their combination.
B is 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 the water-soluble cationic that is enough to satisfy charge balance.For example, sodium cation just in time satisfies-(CH
2)
pCO
2M and-(CH
2)
qSO
3M, thus obtain-(CH
2)
pCO
2Na and-(CH
2)
qSO
3The Na part.Can be in conjunction with to satisfy required chemical charge balance more than a kind of univalent cation (sodium, potassium etc.).Yet, surpass an anionic group and can use the divalent cation balancing charge, or need be more than one univalent cation to satisfy the electric charge needs of polyanionic group.For example with sodium atom replace-(CH
2)
qPO
3M partly has formula-(CH
2)
qPO
3Na
3Divalent cation, for example calcium (Ca
2+) or magnesium (Mg
2+) be used to replace or combine with other suitable unit price water-soluble cationic.Preferred cation is sodium and potassium, more preferably sodium.
X is a water soluble anion, for example chlorine (Cl
-), bromine (Br
-) and iodine (I
-) or X can be the group that has negative charge, sulfate radical (SO for example
4 2-) and methylsulfate (CH
3SO
3 -).
It is 1-6 that the general formula subscript has following value: p, and q is 0-6; R is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1; M is 2-700, preferred 4-400; N is 0-350, preferred 0-200; M+n is at least 5.
Preferred x is 1-20, preferred 1-10.
Preferred amino-functional polymkeric substance of the present invention contains and wherein is less than 50% R group and comprises the unitary polyamine backbone of " oxygen base " R, preferably is less than 20%, and more preferably less than 5%, most preferably the R unit does not comprise " oxygen base " R unit.
Not comprising the unitary most preferably amino-functional of " oxygen base " R polymkeric substance contains and wherein is less than 50% R group and comprises the polyamine backbone that surpasses 3 carbon atoms.For example comprise 3 or carbon atom still less, for example ethylidene, propylene and trimethylene are preferred " alkyl " R unit.Promptly working as skeleton R unit is C
2-C
12During alkylidene group, preferred C
2-C
3Alkylidene group, most preferably ethylidene.
Amino-functional polymkeric substance of the present invention contains all even non-homogeneous polyamine backbone of modification, wherein 100% or less-NH unit be modified.Be used for term of the present invention " evenly polyamine backbone " and be defined as the polyamine backbone that contains identical R unit (for example whole ethylidene).Yet this identity definition is not got rid of and is contained other external unitary polyamine that contains polymer backbone, and described polymer backbone is owing to the method for selected chemosynthesis exists.For example, those skilled in the art is known, thanomin can be used as " initiator " in polymine synthetic, therefore, the polymine sample that contains a hydroxyethyl part that is produced by polymerization " initiator " will be considered to contain even polyamine backbone in the present invention.Comprising and wherein not having the unitary polyamine backbone of unitary all the ethylidene R of branching Y is even skeleton.Comprising the unitary polyamine backbone of all ethylidene R is and existing degree of branching or the irrelevant even skeleton of ring-type side chain number.
Be used for term of the present invention " non-homogeneous polymer backbone " and be meant polyamine backbone into the mixture of various R element lengths and R cell type.For example, non-homogeneous skeleton contains the R unit, and it is the unitary mixture of ethylidene and propylene." alkyl " and the unitary mixture of " oxygen base " R needn't provide non-homogeneous skeleton in the present invention.
Preferred amino-functional polymkeric substance of the present invention contains even polyamine backbone, it all or part of by polyethyleneoxy partly replace, all or part of quaternised amine; The all or part of nitrogen of N-oxide compound and their mixture of being oxidized to.Yet, not all skeleton amine nitrogen modification in an identical manner, makers-up's special requirement is depended in the selection of modification.Degree of ethoxylation also determines according to makers-up's special requirement.
Constitute the preferred polyamine polyalkyleneimine (PAI) normally of the skeleton of The compounds of this invention, preferably polyethylene imines (PEI), or by having the PEI that connects than parent PAI or the longer unitary part of R of PEI.
Preferred amine polymer skeleton is included as C
2The unitary R of alkylidene group (ethylidene) unit also is called polymine (PEI).Preferred PEI contains medium at least side chain, and promptly the ratio of m and n is less than 4: 1, yet the ratio that most preferably has m and n is 2: 1 PEI.Preferred skeleton has following general formula before modification:
Wherein the definition of R ', m and n as mentioned above.Preferred PEI has the 200 daltonian molecular weight of surpassing.
In polyamine backbone, especially under the situation of PEI, primary, the second month in a season and the unitary relative proportion of tertiary amine will change according to the preparation method.Each hydrogen atom that is connected in each nitrogen-atoms of polyamine backbone chain represents to be used for to replace subsequently, the potential site of quaternized or oxidation.
These polyamine can be for example by at catalyzer, carbonic acid gas for example, polymerising ethylene imines preparation under the existence of sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.The concrete grammar for preparing these polyamine backbone is all classified this paper reference as at the US2553696 of the Wilson of the US2806839 of the Crowther of the US2208095 of US3033746, the Esselmann of promulgation on July 16th, 1940 etc. of US2182306, the Mayle of promulgation on May 8th, 1962 etc. of the Ulrich of promulgation on December 5 nineteen thirty-nine etc., promulgation on September 17 nineteen fifty-seven and promulgation on May 21 nineteen fifty-one.
The example that contains the amino-functional polymkeric substance of PEI illustrates with formula I-IV:
The formula I has been narrated the amino-functional polymkeric substance that contains the PEI skeleton, and wherein all commutable nitrogen are by using polyoxyalkylene oxygen base unit ,-(CH
2CH
2O) H replaces the hydrogen modification, and it has following formula:
This is all with the example of one type group modified amino-functional polymkeric substance for the formula I.
The formula II has been described the amino-functional polymkeric substance that contains the PEI skeleton, and wherein all commutable primary amine nitrogen are by using polyoxyalkylene oxygen base unit ,-(CH
2CH
2O)
7H replaces the hydrogen modification, and by all oxidable primary and secondary nitrogen are oxidized to the N-oxide modifying, described polymkeric substance has following formula to molecule subsequently:
The formula II
The formula III has been described the amino-functional polymkeric substance that contains the PEI skeleton, and wherein all skeleton hydrogen atoms are substituted, and some skeleton amine unit is by quaternized.Substituting group is polyoxyalkylene oxygen base unit ,-(CH
2CH
2O)
7H or methyl.The PEI of modification has following formula:
The formula III
The formula IV has been described the amino-functional polymkeric substance that contains the PEI skeleton, wherein skeleton nitrogen by replace (promptly-(CH
2CH
2O)
3H or methyl), quaternized, be oxidized to N-oxide compound or their combination modification.The polymkeric substance that obtains has following formula:
The formula IV
In as above example, the nitrogen of not all unit kind has identical modification.The present invention allows the makers-up to contain the secondary amine nitrogen of some ethoxylation, contains other secondary amine nitrogen that is oxidized to the N-oxide compound simultaneously.Can also adopt primary amine nitrogen because, the makers-up can be chosen in oxidation or quaternized before with one or more substituting group modifications all or a part of primary amine nitrogen.Any possible combination of R ' group can replace primary and secondary amine nitrogen, except above-mentioned restriction.
It is commercial that available to be used for amino-functional polymkeric substance of the present invention be poly-(ethyleneimine), MW1200, and hydroxyethylization is gathered (ethyleneimine), is obtained by Polysciences, and MW2000 and 80% hydroxyethylization are gathered (ethyleneimine), are obtained by Aldrich.
The typical content that is used for the amino-functional polymkeric substance of composition of the present invention is by weight at the most 90%, preferred 0.01%-50% active substance by weight, and more preferably 0.1%-20% by weight most preferably presses composition weight meter 0.5%-15%.Crystal growth inhibitor
Crystal growth inhibitor (CGI) is a main ingredient of the present invention." crystal growth inhibitor " is meant and reduces the speed that the inorganic crystallites body forms, thereby reduce the size of this microcrystal on the fabric face and/or the compound of quantity.
The suitable CGI that is used for this paper can be by following test method, and so-called crystal growth inhibition test is measured definition.The crystal growth inhibition test is measured
Compound suppresses the ability of crystal growth and can estimate by estimating in the influence of external growth velocity to the inorganic crystallites body.For this reason, can use G.H.Nancollas 1964 the exploitation at Nancollas, G.H and Koutsoukos, P.G. the system of describing among " Calcium PhosphateNucleation and Growth in solution " Prog.Crystal Growth Charact.3,77-102 (1980).This system is included in CaCl
2And NaH
2PO
4Exist down and measure with hydroxylapatite ([Ca
5(PO
4)
3OH] or the HAP) growth velocity of the calcium phosphate crystal of seeding.The calcium phosphate growth discharges proton, its available highly basic titration.The effect that can directly measure crystal growth and measure potential crystal growth rate inhibitor according to the quantity those skilled in the art who in crystal growing process, keeps the constant required alkali of pH.The common plotting of this experiment is as follows:
Viewed t-lagged value has defined compound and has suppressed the efficient that calcium phosphate crystal is grown; Wherein the t-hysteresis is high more, and CGI is good more.
Following method can be used for obtaining the plotting that above-mentioned experiment provides:
In reaction vessel, add 350ml distilled water (distilling twice), 35mlKCl 2.1M, 50mlCaCl
20.0175M and 50mlKH
2PO
40.01M.Insertion is connected in the glass pH electrode and the standard calomel reference electrode of autotitrator.Bubbling is gone into nitrogen, the temperature to 37 of stopping reaction mixture ℃.When temperature and pH stablize, with the concentration of test (for example 1.10
-6M) add the CGI material standed for.Be titrated to pH7.4 with KOH 0.05M.Use 5ml hydroxylapatite soup compound [Ca subsequently
5(PO
4) OH] the seeding reaction mixture.
The hydroxylapatite soup compound is prepared as follows:
100gBio-Gel HTP hydroxyapatite powder is dispersed in the 1L distilled water.Reduce the pH to 2.5 of the soup compound that obtains by dripping hydrochloric acid 6N.Postheating is to boiling, and backflow, stirs 7 days in being connected in the 2L round-bottomed flask of condenser simultaneously.After being cooled to room temperature, regulate pH to 12.0 by Dropwise 5 0% sodium hydroxide, soup compound as above refluxed 7 days again.Make soup compound leave standstill the sucking-off supernatant liquor 2 days.In flask, add 1.5L distilled water again, vigorous stirring, and then left standstill 2 days.Carry out 7 rinsings as mentioned above altogether.Under vigorous stirring, regulate pH to 7.0 by dripping hydrochloric acid.The soup compound that obtains was stored 11 months down at 37 ℃.
Above-mentioned plotting is by being recorded as the quantity acquisition that the pH that keeps reaction medium passes the alkali of adding in time.T-for the particular crystal growth inhibitor lags behind described in above-mentioned figure to scheme to show mensuration.
Be used for crystal growth inhibitor of the present invention 1.10
-6Had at least 10 minutes under the concentration of M, preferably at least 20 minutes, most preferably at least 50 minutes t-lagged behind.
With the comparable appropriate method that other is used to measure the crystal growth inhibition activity of selected component of T-hysteretic method be the range estimation classification.This method is as follows:
Washing of (for example 10 times) multiple and drum dried cycle are carried out multicycle laundry test through several times.Employed condition is representational for required geographic area (fabric articles of the end-use that for example used domestic washing machine, used washing composition, rinsing add, the water hardness, washing etc.).Carry out at least two parallel test branches (leg), comprise composition of the present invention and independent reference branch.Carrying out desired number after wash(ing)cycle, test clothes (clothes article) is compared under controllable illumination condition by expert classification person.By comparison test branch and with reference to branch, the range estimation grading is better/relatively poor contrast of visible crystals resistates on the test garment surface.The knitting cotton products of black are suitable for this comparison most.
In addition, it is their low copper binding affinities that crystal growth inhibitor itself is different from sequestrant, and by its Log K definition, promptly at 25 ℃, the ML/M.L Log K of CGI is less than 15, preferably less than 12 under 0.1 ionic strength.
Be used for CGI of the present invention and be preferably selected from carboxylic acid cpd, organic mono phosphonic acid, organic diphosphonic acid and their mixture.Carboxylic acid cpd
The typical carboxylic acid cpd that is used for this paper is a carboxylic acid cpd, and it is selected from glycolic acid, phytinic acid, monomer poly carboxylic acid, homopolymerization or copolymerization poly carboxylic acid or their salt, and wherein poly carboxylic acid contains at least two quilts and is no more than the carboxyl that 2 carbon atoms separate each other.
When using with salt form, preferred as alkali, for example sodium, potassium and lithium or alkanol ammonium salts.
Be applicable to that organic detergent CGI of the present invention comprises, but be not restricted to various multi-carboxylate's compounds." multi-carboxylate " who is used for this paper is meant contains many carboxylate groups, the compound of preferred at least 3 carboxylate groups.Multi-carboxylate CGI usually can acid form, but form that also can neutralized salt adds in the composition.When using with salt form, preferred as alkali, for example sodium, potassium and lithium or alkanol ammonium salts.
Wherein multi-carboxylate CGI is various useful materials.A kind of important multi-carboxylate CGI comprises the ether multi-carboxylate, comprises oxygen di-succinate, described in US3128287 and US3635830.Also referring to " TMS/TDS " CGI of US4663071.Suitable ether multi-carboxylate also comprises ring compound, especially alicyclic compound, for example material of describing in US3932679,3835163,4158635,4120874 and 4102903.
Other useful CGI comprises ether hydroxypolycarboxylic acid salt, polyacrylate polymkeric substance, maleic anhydride and ethene or vinyl methyl ether or acrylic acid multipolymer, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxyl methoxyl group succsinic acid, polyacetic acid, the ammonium salt of various basic metal, ammonium and the replacement of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) for example, and multi-carboxylate, for example mellic acid, succsinic acid, oxygen di-succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxyl methoxyl group succsinic acid and its soluble salt.
The molecular weight of these polymkeric substance and multipolymer preferably is lower than 100000, most preferably between 500-50000.
The available polymkeric substance of the sedimentary commerce of salt of avoiding buffer components in water when composition dilutes that is applicable to this paper is the polyacrylate polymkeric substance of selling with following trade(brand)name: the Good-Rite of BFGoodrich, Rohm ﹠amp; The Sokalan of Acrysol , the BASF of Haas and the Norasol of Norso Haas.Preferred commercial available polymkeric substance is the polyacrylate polymkeric substance, especially Norasol polyacrylate polymkeric substance, most preferably be polyacrylate polymkeric substance Norasol 410N (MW 10000) and, obtain by Norso Haas with polyacrylate polymkeric substance Norasol 440N (MW 4000) and its corresponding sour form Norasol QR784 (MW 4000) of aminophosphonic acid groups modification.
Citrate trianion, for example citric acid and its soluble salt (especially sodium salt) are to be applicable to multi-carboxylate CGI of the present invention.
What be suitable for the present composition equally is 3,3-dicarboxyl-4-oxa--1,6-adipate and disclosed related compound in US4566984.Useful succsinic acid CGI comprises C
5-C
20Alkyl and alkenyl succinic acid and their salt.The especially preferred compound of this class is the dodecenyl succinic succsinic acid.The specific examples of succinate CGI comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is preferred CGI in this group, describes in EP0200263.
Other suitable multi-carboxylate is disclosed among US 4 144226 and the US 3 308 067.Also referring to US 3723322.Organic mono phosphonic acid
Organic mono phosphonic acid or its salt or title complex one of also be suitable for the CGI make this paper.
Organic mono phosphonic acid is meant organic mono phosphonic acid, and it does not contain the part of nitrogen as its chemical structure.Therefore organic amino phosphonates do has been got rid of in this definition, yet it can be included in the composition of the present invention as heavy metal ion chelating agent.
Organic mono phosphonic acid component can its sour form or the salt of it and suitable counter cation or title complex one of form exist.Preferred any salt/title complex is water miscible, and basic metal and alkaline earth salt/title complex are especially preferred.
Preferred organic mono phosphonic acid is a 2-phosphinylidyne butane-1,2, and the 4-tricarboxylic acid is commercially obtained with trade(brand)name Bayhibit by Bayer.Organic diphosphonic acid
Organic diphosphonic acid or its salt or title complex one of also be suitable for the CGI make this paper.
Organic diphosphonic acid is meant organic diphosphonic acid, and it does not contain the part of nitrogen as its chemical structure.Therefore organic amino phosphonates do has been got rid of in this definition, yet it can be included in the composition of the present invention as heavy metal ion chelating agent.
The organic diphosphonic acid component can its sour form or the salt of it and suitable counter cation or title complex one of form exist.Preferred any salt/title complex is water miscible, and basic metal and alkaline earth salt/title complex are especially preferred.
Organic diphosphonic acid is C preferably
1-C
4Di 2 ethylhexyl phosphonic acid, more preferably C
2Di 2 ethylhexyl phosphonic acid is selected from ethylidene diphosphonic acid, alpha-hydroxy-2 phenylethyl di 2 ethylhexyl phosphonic acid, methylenediphosphonate (MDP), vinylidene 1,1 di 2 ethylhexyl phosphonic acid, 1,2-dihydroxyl ethane 1,1 di 2 ethylhexyl phosphonic acid and hydroxyl-ethane 1,1 di 2 ethylhexyl phosphonic acid and its any salt and mixture.
Most preferred organic diphosphonic acid is hydroxyl-ethane 1,1 di 2 ethylhexyl phosphonic acid (HEDP).
In the CGI of mentioned kind, the kind that is preferred for this paper be organic mono phosphonic acid and/organic diphosphonic acid.
In the present invention, when CGI was selected from carboxylic acid, organic diphosphonic acid and their mixture, CGI to be being lower than 1% by composition weight meter, preferred 0.005%-0.5%, and more preferably 0.05%-0.50%, most preferably the content of 0.1%-0.2% exists.
CGI component except that carboxylic acid, organic diphosphonic acid and their mixture is to be lower than 10% by composition weight meter as the typical content of organic mono phosphonic acid, more preferably 0.005%-0.50%, most preferably 0.1%-0.2%.
For the present invention, preferably, the weight ratio that is stabilized in described CGI and described polymkeric substance that contains the composition of poly-amino-functional polymkeric substance is 0.005: 1-0.5: 1, preferred 0.01: 1-0.1: 1 when existing by best stabilized.
Composition of the present invention can be used as independent product and uses, and comprises pre-wash or after scouring additive.It also can be used in the full compositions formulated, comprise laundry composition and softness is provided and/or the fabric softener composition that adds during the rinsing of aesthetic and moisture eliminator in the composition that adds of the composition (for example sheet) that adds and rinsing.
Composition can contain component selectively, for example dye-fixing agent, fabric softener compound and other component optionally.Dye-fixing agent
Composition of the present invention optionally contains dye-fixing agent, and dye-fixing agent or " fixing agent " are known, commercial available materials, and it improves the outward appearance of DYED FABRICS by the loss that reduces the dye for fabrics that causes owing to washing.Not included within this definition is fabric softener or the component as the amino-functional polymkeric substance described below.
Many dye-fixing agents are cationic, and based on various quaternized or other the band cationic charge organic nitrogen compound.Cationic fixative is obtained by different sources with different trade names.Representative example comprises: CROSCOLOR PMF that is obtained by Crosfield (in July, 1981, numbering № 7894) and CROSCOLOR NOFF (number № 8544 in January, 1988); The INDOSOL E-50 (on February 27th, 1984, the reference number 6008.35.84 that obtain by Sandoz; The polyethylene amido); SANDOFIX TPS, it can be obtained by Sandoz, and this is to be used for preferred polycation fixing agent of the present invention, SANDOFIX SWE (resin cation (R.C.) compound), REWIN SRF, the REWIN SRF-O and the REWINDWR that are obtained by CHT-Beitlich GMBH; Tinofix ECO, the Tinofix FRD and the Solfin that obtain by Ciba-Geigy.
Other cationic dyestuff fixing agent is being described in " improving the aftertreatment of dyestuff fastness on the fabric fibre " among the Christopher C.Cook (REV.PROG.COLORATION, the 12nd volume, 1982).Be applicable to that dye-fixing agent of the present invention is an ammonium compound, lipid acid-diamines condenses for example, for example oxidation products of the hydrochloride of oil base diethylamino buserelin, acetate, Methylsulfate and benzyl hydrochloride, oil base methyl-diethylenediamine Methylsulfate, the amino trimethyl ammonium Methylsulfate of single stearyl-ethylene and tertiary amine; The derivative of polymerization alkyl diamine, polyamine-cyanuryl chloride condenses and amination α-Er Lvganyou.
The dye-fixing agent typical amounts of using in composition of the present invention is preferably by weight at the most 90%, and preferably by weight at the most 50%, more preferably 0.001%-10% by weight most preferably presses composition weight meter 0.5%-5% active substance.
Composition of the present invention also can be mixed with fabric sofetening composition.Therefore when being formulated as soft compound, it will contain fabric soft compound.Fabric soft compound
The common add-on of softening compound thing is for press composition weight meter 1%-80% in soft compound, preferred 5%-75%, more preferably 15%-70%, even more preferably 19%-65%.
The fabric-softening immunomodulator compounds is preferably selected from positively charged ion, nonionic, both sexes or negatively charged ion fabric sofetening component.The soft component of positively charged ion is quaternary ammonium compound or the amine precursor as giving a definition normally.A)-the soft active compound of the preferred quaternary ammonium fabric of the soft active compound of quaternary ammonium fabric (1) has following formula:
Or formula:
Wherein Q is the carbonyl unit of following formula:
Each R unit is respectively hydrogen, C
1-C
6Alkyl, C
1-C
6Hydroxyalkyl and their mixture, preferable methyl or hydroxyalkyl; Each R
1The unit is respectively straight or branched C
11-C
22Alkyl, straight or branched C
11-C
22Thiazolinyl and their mixture, R
2Be hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl and their mixture; X is the negatively charged ion compatible with auxiliary component with fabric softener active matter matter; Subscript m is 1-4, preferred 2; Subscript n is 1-4, preferred 2.
The example of preferred fabric softener active matter matter is the mixture of the quaternary ammonium of following formula:
R methyl preferably wherein; R
1Be to contain at least 11 atoms, the straight or branched alkyl or alkenyl chain of preferred at least 15 atoms.In above-mentioned fabrics softening agent example, unit-O
2CR
1The fatty acyl group unit that expression is obtained by the triglyceride level source usually.The triglyceride level source is preferably by butter, partially hydrogenated butter, lard, partially hydrogenated lard, vegetables oil and/or partially hydrogenated vegetables oil, and for example Tower rape oil, Thistle oil, peanut oil, sunflower oil, Semen Maydis oil, soybean oil, Yatall MA, rice bran wet goods and these oily mixtures obtain.
The soft active substance of preferred fabric of the present invention is diester and/or diamide quaternary ammonium (DEQA) compound, and diester and diamide have following formula:
Wherein R, R
1, X and n have as the identical definition in following formula (1) and (2), Q has following formula:
These preferred fabric sofetening active substances by amine and fatty acyl group unit process to form the amine intermediate of following formula:
R methyl preferably wherein, Q and R ' they are as defined above; Quaternary ammonium turns to final softening agent active substance subsequently.
The unrestricted example that is used to form the preferred amines of DEQA fabric sofetening active substance of the present invention comprises the methyl two of following formula (2-hydroxyethyl) amine:
The methyl two of following formula (2-hydroxypropyl) amine:
The methyl of following formula (3-aminopropyl) (2-hydroxyethyl) amine:
The methyl diethylenetriamine of following formula:
The trolamine of following formula:
Two (2-amino-ethyl) thanomin of following formula:
Above-mentioned counter ion X
(-)Can be the compatible negatively charged ion of any softening agent, the negatively charged ion of preferred strong acid, for example muriate, bromide, iodide, Methylsulfate, sulfovinate, vitriol, nitrate etc., more preferably muriate or Methylsulfate.Negatively charged ion is all right, but not too preferred, has double charge, wherein X
(-)Represent group half.
Butter and Tower rape oil are to be suitable as R of the present invention
1Unitary convenience of unitary fatty acyl group and cheap source.Following is the example that is applicable to the quaternary ammonium compound of composition of the present invention.Term " tallow base " is used for this paper and is meant R
1The unit is obtained by butter triglyceride level source, is the unitary mixture of fatty acyl group.Equally, term canolyl is meant the unitary mixture of the fatty acyl group that is obtained by Tower rape oil.Table II fabric softener active matter matter N, N-two (tallow base-oxygen base-ethyl)-N, N-alkyl dimethyl ammonium chloride; N, N-two (canolyl-oxygen base-ethyl)-N, N-alkyl dimethyl ammonium chloride; N, N-two (tallow base-oxygen base-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride; N, N-two (canolyl-oxygen base-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride; N, N-two (2-tallow base oxygen base-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride; N, N-two (2-canolyl oxygen base-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride; N, N-two (2-tallow base oxygen base ethyl ketonic oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride; N, N-two (2-canolyl oxygen base ethyl ketonic oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride; N-(2-tallow base oxygen base-2-ethyl)-N-(2-tallow base oxygen base-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride; N-(2-canolyl oxygen base-2-ethyl)-N-(2-canolyl oxygen base-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride; N, N, N-three (tallow base-oxygen base-ethyl)-N-ammonio methacrylate; N, N, N-three (canolyl-oxygen base-ethyl)-N-ammonio methacrylate; N-(2-tallow base oxygen base-2-oxoethyl)-N-(tallow base)-N, the N-alkyl dimethyl ammonium chloride; N-(2-tallow base oxygen base-2-oxoethyl)-N-(canoly)-N, the N-alkyl dimethyl ammonium chloride; 1,2-two tallow base oxygen base-3-N, N, N-trimethyl ammonium propane chloride; With 1,2-two canolyl oxygen base-3-N, N, N-trimethyl ammonium propane chloride; Mixture with above-mentioned active substance.
Other example of quaternary ammonium softening compound thing is methyl two (tallow base amido ethyl) (2-hydroxyethyl) ammonium methyl sulphate and methyl two (hydrogenated-tallow group amido ethyl) (2-hydroxyethyl) ammonium methyl sulphate; These materials are obtained with trade(brand)name Varisoft 222 and Varisoft 111 by Witco Chemical Company respectively.
Especially preferred N, N-two (tallow base-oxygen base-ethyl)-N, the N-alkyl dimethyl ammonium chloride, wherein the tallow chain is undersaturated to small part.
The unsaturated content of tallow, Tower rape oil or other fatty acyl group cellular chain is measured by the iodine number (IV) of corresponding lipid acid, under situation of the present invention, should be preferably 5-100, and two kinds of famous compounds have and are below or above 25 IV.
In fact, for the compound of the following formula that obtains by tallow fatty acids:
When IV is 5-25, during preferred 15-20, can find cis/trans isomer weight ratio greater than about 30/70, be preferably greater than approximately 50/50, provide best concentrating capacity more preferably greater than about 70/30.
Surpassed the compound of 25 tallow fatty acids preparation by IV for this class, the ratio of cis and trans-isomer(ide) is found to be not too crucial, unless the very high concentration of needs.
Other suitable example of fabric softener active matter matter is obtained by fatty acyl group; wherein the term in the foregoing description " tallow base " and " canolyl " are replaced by term " coconut, palm, lauryl, oil base, castor oil-base, stearyl, palmityl ", and it is corresponding to obtaining the unitary triglyceride level of fatty acyl group source.These other fatty acyl group sources can be contained fully saturated or preferably to the undersaturated chain of small part.
As mentioned above, the R unit is methyl preferably, yet suitable fabric softener active matter matter is by describing with the term " methyl " in the above-mentioned example in the above-mentioned table II of unit " ethyl, oxyethyl group, propyl group, propoxy-, sec.-propyl, butyl, isobutyl-and the tertiary butyl " displacement.
In the example of table II, counter ion X can be replaced by bromide, Methylsulfate, formate, vitriol, nitrate and composition thereof suitably.In fact, negatively charged ion, X only exist as the counter ion of positive charge quaternary ammonium compound.Scope of the present invention is not restricted to any concrete negatively charged ion.
For above-mentioned ester fabric softener, the pH of the composition of this paper is an important parameter of the present invention.In fact, it influences the stability of quaternary ammonium or amine precursor compound under long storage requirement.
Ding Yi pH uses pure composition measuring down at 20 ℃ in the present invention.For the optimum hydrolysis stability of these compositions, in the time of can operating under these compositions are being lower than about 6.0 pH, the pure pH of Ce Dinging is must be preferably about 5 at about 2.0-under these conditions, preferred 2.5-4.5, preferably about 2.5-about 3.5.The pH of these compositions can regulate by adding Bronsted acid.
The example of suitable acid comprises inorganic mineral acid, carboxylic acid, especially lower molecular weight (C
1-C
5) carboxylic acid and alkylsulphonic acid.Suitable mineral acid comprises hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.Appropriate organic comprises formic acid, acetate, methylsulfonic acid and ethyl sulfonic acid.Preferred acid is citric acid, hydrochloric acid, phosphoric acid, formic acid, methylsulfonic acid and phenylformic acid.
When the explanation diester, it will comprise the monoesters that exists usually in preparation in this article.For softness, the percentage ratio of carrying monoesters under the laundry situation at nothing/low washing composition secretly should be low as much as possible, preferably is no more than about 2.5%.Yet, to carry secretly under the laundry situation at high washing composition, some monoesters is preferred.The overall ratio of diester and monoesters is about 2: 1 of about l00: 1-, preferred about 50: about 5: 1 of 1-, more preferably from about 13: about 8: 1 of 1-.Carry secretly under the condition at high washing composition, two/monoesters ratio is preferably about 11: 1.Existing monoester content can be controlled in the softener compound preparation process.
But the mixture of the active substance of preparation formula (1) and (2) also.2)-other suitable quaternary ammonium fabric softening compound thing of being used for this paper is to contain two or more long-chains not have cyclic aliphatic C
8-C
22The positively charged ion of alkyl or described group and a described group and an aralkyl contains nitrogen salt, and it can use separately or as the part of mixture, and it is selected from: (ⅰ) acyclic quaternary ammonium salt of following formula:
R wherein
4Be no cyclic aliphatic C
8-C
22Alkyl, R
5Be C
1-C
4Saturated alkyl or hydroxyalkyl, R
8Be selected from R
4And R
5Group, A-are negatively charged ion as defined above; (ⅱ) the diamino alkoxy quaternary ammonium salt of following formula:
Wherein to equal 1-about 5 for n, R
1, R
2, R
5And A
-Be as defined above; (ⅲ) their mixture.
The example that the positively charged ion of mentioned kind contains nitrogen salt is known dialkyl dimethyl ammonium salt, Varisoft DHT for example, two tallow base dimethyl methyl ammonium sulfate, two (example that hydrogenated tallow is used for commercial available dialkyl dimethyl ammonium salt of the present invention is two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride (commodity is called Adogen 442), (commodity are called Adogen 470 to Varisoft DHT, Praepagen 3445), VARISOFT TA100 (commodity are called Arosurf TA-100) obtains by Witco Chemical Company.Two docosyl alkyl dimethyl ammonium chlorides are sold with trade(brand)name Kemamine Q-2802C by Humko Chemical Division of WitcoChemical Corporation.
Dimethyl stearyl benzyl ammonium chloride is sold with Ammonyx 490 with Varisoft SDC with by Onyx Chemical Company by Witco Chemical Company.B)-amine fabric sofetening active compound
The suitable amine fabric soft compound that is used for this paper that can be amine form or cationic form is selected from as follows: (ⅰ)-and the reaction product of higher fatty acid and the polyamine that is selected from hydroxyalkyl Alkylenediamine and two alkylene triamine and their mixture.In view of the polyfunctional group structure of polyamine, these reaction product are mixtures of some compounds.
Preferred ingredients (ⅰ) is a nitrogenous compound, and it is selected from the component of some selection of mixture of reaction products or mixture.
A kind of preferred ingredients (ⅰ) is the compound of imidazolinium compounds that is selected from the replacement of following formula:
R wherein
7Be no cyclic aliphatic C
15-C
21Alkyl and R
8Be divalence C
1-C
3Alkylidene group.
Component (ⅰ) material is commercial to can be used as following material and obtains: the Mazamide 6 that is sold by Mazer Chemicals or by Sandoz Colors ﹠amp; The Ceranine HC that Chemicals sells; By Alkaril Chemicals, the stearyl hydroxyethyl tetrahydroglyoxaline that Inc. sells with trade(brand)name Alkazine ST or by Scher Chemicals, Inc., the Schercozoline S of sale; N, N "-two tallow base alkyloyl diethylenetriamine; 1-tallow amido ethyl-2-tallow imidazoles (R in said structure wherein
1Be aliphatic C
15-C
17Alkyl and R
8Be the divalence ethylidene).
Some component (ⅰ) can also at first be dispersed in the pKa value and be no more than in about 4 the Bronsted acid dispersing auxiliary; Its prerequisite is that the pH of final composition is no more than about 6.Some preferred dispersing auxiliary is hydrochloric acid, phosphoric acid or methylsulphonic acid.
N; N "-two tallow base alkyloyl diethylenetriamine and 1-tallow base (amido ethyl)-2-tallow tetrahydroglyoxaline all are reaction product of tallow fatty acids and diethylenetriamine; the precursor that is cationic fabric softener methyl isophthalic acid-tallow amido ethyl-2-tallow tetrahydroglyoxaline Methylsulfate is (referring to " as the cats product of fabric softener "; R.R.Egan; Journalof the American Oil Chemicals ' Society; in January, 1978, the 118-121 page or leaf).N, N "-two tallow base alkyloyl diethylenetriamine and 1-tallow base (amido ethyl)-2-tallow tetrahydroglyoxaline all can obtain as the experimental chemistry product by Witco Chemical Company.Methyl isophthalic acid-tallow amido ethyl-2-tallow tetrahydroglyoxaline Methylsulfate is sold with trade(brand)name Varisoft 475 by WitcoChemical Company.(ⅱ) softening agent of following formula:
Each R wherein
2Be C
1-6Alkylidene group, preferred ethylidene; With G be Sauerstoffatom or-the NR-group; Each R, R
1, R
2And R
5Have as above definition and A
-Has as above X
-Definition.
The example of compound (ⅱ) is 1-oil base amido ethyl-2-oil-based imidazoline muriate, wherein R
1Be no cyclic aliphatic C
15-C
17Alkyl, R
2Be ethylidene, G is the NH group, R
5Be that methyl and A-are chlorions.(ⅲ)-softening agent of following formula:
Wherein R, R
1, R
2And A
-Be as defined above.The example of compound (ⅲ) is the compound of following formula:
R wherein
1Be by the oleic acid deutero-.
Other fabric softener that is used for this paper is at promulgation on April 28th, 1987 Toan Trinh, Errol H.Wahl, the US4661269 of Donald M.Swartley and Ronald L.Hemingway; The US4439335 of the Burns of promulgation on March 27th, 1984; And US3861870, Edwards and Diehl; 4308151, Cambre; 3886075, Bernardino; 4233164, Davis; 4401578, Verbruggen; 3974076, Wiersema and Rieke; 4237016, Rudkin, Clint and Young; And EP472178, Yamamura etc., all above-mentioned documents are classified this paper reference as.
Certainly, term " soft active substance " also can comprise the soft promoting agent of mixing.
The preferred kind of above-mentioned disclosed softener compound is the soft active compound (DEQA) of diester or diamido quaternary ammonium fabric.
Except said components, prepare soft compound entirely and can contain one or more following components.Optional ingredient (A) liquid vehicle
Another kind optionally, but preferred ingredients is a liquid vehicle.The liquid vehicle that is used for the present composition preferably at least mainly is a water, and this is because its low cost, relative available, safety and Environmental compatibility.The content of water is counted at least about 50% by vehicle weight in liquid vehicle, more preferably at least about 60%.Water and lower molecular weight, organic solvent for example＜about 200, low-molecular-weight alcohol for example, for example the mixture of ethanol, propyl alcohol, Virahol or butanols is as carrier liq.Low-molecular-weight alcohol comprises monohydroxy, dihydroxyl (ethylene glycol etc.), trihydroxy-alcohol (glycerine etc.) and senior poly-hydroxy (polyvalent alcohol) alcohol.(B) added solvent
Composition of the present invention can contain one or more solvents, and it provides the preparation easiness of increase.Easily the preparation solvent is open in WO97/03169 for these.Situation especially like this for obtaining liq, transparent fabric soft compound.When using, it is preferably about 40% to be less than by composition weight meter easily to prepare solvent system, and preferably about 10%-is about 35%, and more preferably from about 12%-is about 25%, the most preferably from about content of 14%-about 20% use.Select easily the preparation solvent so that in the composition influence of the smell of solvent minimum and so that the low viscosity of final composition to be provided.For example Virahol is not very effective, and has the intensive smell.N-propyl alcohol is more effective but also has significant smell.Some butanols also have smell, but can be effective to transparency/stability, especially as easy preparation solvent system part the time so that their smell minimum.For the low-temperature stability of the best is also selected alcohol, be that they can form composition, said composition has acceptable low viscosity and is translucent when dropping to about 40 °F (about 4.4 ℃), preferably transparent and can restore after about 20 ° (approximately-6.7 ℃) store down dropping to.
For preparation liquid of the present invention, concentrated, and the suitability of any easy preparation solvent with required stability of the fabric softener composition of preferably transparent is unexpectedly selectable.Suitable solvent can be selected according to the octanol/water partition ratio (P) that they are described in WO97/03169.
It is about 0.15-about 0.64 that easy preparation solvent of the present invention is selected from ClogP, preferred about 0.25-about 0.62, the solvent of 0.40-about 0.60 more preferably from about, described easy preparation solvent are preferably asymmetric at least somewhat, preferably have fusing point or solidification point make it or be liquid during near room temperature.For some purposes, it also is desirable having lower molecular weight and biodegradable solvent.The solvent of absolutely wrong title obviously is very desirable, thereby, height symmetry solvent with symmetry centre, for example 1,7-heptanediol or 1, two (hydroxymethyl) hexanaphthenes of 4-obviously can not provide the composition of substantially transparent when using separately, even their ClogP value falls in the preferable range.
As observing by the cryotronics microscopy that is diluted to the composition that is used for rinsing concentration, most preferred easy preparation solvent can be identical with the outward appearance of softening agent bubble.These diluted compositions show to have the dispersion of fabric softener, and its shows than fabrics in general softener composition individual layer shape outward appearance more.Outward appearance is more near the individual layer shape, and composition work must be good more.With provide unexpected good fabric sofetening with identical fabric softener active matter matter with the analogous composition of ordinary method preparation these compositions of comparing.
Following open and list enforceable easy preparation solvent, they have the ClogP numerical value that falls into required scope.They comprise monohydroxy-alcohol, C6 glycol, C7 glycol, ethohexadiol isomer, butyleneglycol derivative, neopentyl glycol isomer, ethyl-methyl pentanediol isomer, propyl group pentanediol isomer, dimethylhexane glycol isomer, ethyl hexane glycol isomer, methylheptane glycol isomer, octane glycol isomer, nonane glycol isomer, alkyl glycerol base ether, two (hydroxyalkyl) ethers and aryl glyceryl ether, fragrant glyceryl ether, alicyclic diol and derivative, C
3-C
7Glycol alkoxy derivative, aromatic diol and unsaturated diol.Especially preferred easy preparation solvent comprises hexane diol, for example 1, and 2-hexane diol and 2-ethyl-1,3-hexane diol and pentanediol, as 2,2,4-trimethylammonium-1,3-pentane diol.(C) dispersing auxiliary
Contain saturated can stably the preparation simultaneously and need not to add concentrated assistant with the relative spissated composition of unsaturated diester quat.Yet composition of the present invention can need organic and/or inorganic concentrated assistant to obtain even greater concn and/or satisfy higher stability criterion according to other component.These may be usually the concentrated assistant of viscosity modifier will be need or preferably to guarantee when specific softening agent activity substance content uses stability under extreme conditions.The tensio-active agent concentrated assistant is selected from (1) single-long-chain alkyl cats product usually; (2) nonionogenic tenside; (3) amine oxide; (4) lipid acid and (5) their mixture.These auxiliary agents especially walk to for the 14th page 12 in 20 page of 12 row and describe at WO94/20597, and it classifies this paper reference as.
When having dispersing auxiliary, total content is for pressing composition weight meter 2%-25%, preferred 3%-17%, more preferably 4%-15%, most preferably 5%-13%.The part that these materials can be used as REACTIVE SOFTNER raw material (I) adds, for example aforesaid single-long-chain alkyl cats product and/or the lipid acid that is used to form the reactant of biodegradable fabric softener, or as independent component adding.The dispersing auxiliary total content comprises any amount that can be used as the existence of component (I) part.
Inorganic viscosity/dispersive ability the control agent that also can be used as or increase tensio-active agent concentrated assistant effect equally comprises water-soluble ionizable salt, and they also optionally add in the composition of the present invention.Can use various ionizable salt.The example of suitable salt is the halogenide of periodic table of elements I A and II A family metal, for example calcium chloride, magnesium chloride, sodium-chlor, Potassium Bromide and lithium chloride.Ionizable salt, is particularly useful in the required viscosity process obtaining preparing composition of the present invention at blending ingredients.The usage quantity of ionizable salt can be regulated according to prescription teacher's needs according to the quantitative changeization of the activeconstituents that uses in composition.The common content of salt that is used for control combination thing viscosity is for by composition weight meter about 20 to 20,000 1,000,000/(ppm), be preferably about 20 to about 11000ppm.
Replace or except above-mentioned water-soluble ionogenic salt, can in composition, add alkylidene group and gather ammonium salt.In addition, these reagent can be used as scavenging agent, and bring by main washing process, in rinse cycle and the anionic detergent on the fabric form ion pair, can improve softness.Compare with inorganic electrolyte, these reagent can be in wide temperature range, especially at low temperatures stable viscosity.
The specific examples of the poly-ammonium salt of alkylidene group comprises 1-Methionin mono-hydrochloric salts and 1,5-two ammonium 2-methylpentane dihydrochlorides.(D)-stablizer
In composition of the present invention, can there be stablizer.The term " stablizer " that the present invention uses comprises antioxidant and reductive agent.The amount of these reagent is for to press composition weight meter 0% to about 2%, for antioxidant, be preferably by composition weight meter about 0.01% to about 0.2% more preferably from about 0.035% to about 0.1%, for reductive agent, more preferably press composition weight meter about 0.01% to 0.2%.For composition and the compound stored with the fusion form, this has guaranteed good odor stable under long storage requirement.For low perfumed product (low levels spices), it is especially crucial using antioxidant and reductive agent stablizer.
The example that can add the antioxidant of the present composition comprises the mixture of xitix, Quicifal, Propylgallate, and by Eastman Chemical Products, Inc. obtains with trade name Tenox PG and Tenox S-1; The mixture of BHT (Yoshinox BHT), BHA (butylated hydroxyanisol), Turkey-galls propionic ester and citric acid, by Eastman Chemical Products, Inc. obtains with trade name Tenox-6 ; Yoshinox BHT is obtained with trade name Sustane BHT by UOP Process Division; Tertiary butylated hydroquinone, by Eastman Chemical Products, Inc. obtains with trade name Tenox TBHQ; Natural tocopherol, by Eastman Chemical Products, Inc. obtains with trade name Tenox GT-1/GT-2; And butylated hydroxyanisol, by EastmanChemical Products, Inc. obtains with trade name BHA ; Long-chain ester (the C of gallic acid
8-C
22), gallic acid dodecyl ester for example; Irganox 1010; Irganox 1035; Irganox B1171; Irganox 1425; Irganox 3114; Irganox 3125; With their mixture, preferred Irganox 3125; Irganox 1425; Irganox 3114 and their mixture, more preferably independent Irganox 3125.Chemical name and CAS numbering for some aforementioned stable agent are listed in the following table II.Chemical name Irganox 1010 6683-19-8 four that use in the table II antioxidant CAS No. federal regulations code (methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogen
Change laurate)) and methane Irganox 1035 41484-35-9 sulfo-di ethylene bis (3,5-di-t-butyl-4-
The hydroxyl hydrogenated cinnamate) Irganox 1098 23128-74-7 N, N '-hexa-methylene two (3,5-di-t-butyl-4-
The hydroxyl hydrocinnamamide) Irganox B1171 31570-04-4 Irganox 1098 is with Irgafos 's 168
1: 1 mixture Irganox of 23128-74-7 , 1425 65140-91-2 pairs (single ethyl (3,5-di-t-butyl-4-hydroxyl benzyl
Phosphonic acids base)) calcium Irganox 3114 65140-91-2 pairs (single ethyl (3,5-di-t-butyl-4-hydroxyl benzyl
Base) calcium Irganox 3125 34137-09-2 3 phosphonic acids), 5-di-t-butyl-4-hydroxyl phenylpropionic acid three
Ester and 1,3,5-three (2-hydroxyethyl)-s-three
Piperazine-2,4,6-(1H, 3H, 5H) triketone Irgafos 168 31570-04-4 three (2, the 4-di-tert-butyl-phenyl) phosphite
The example of reductive agent comprises sodium borohydride, Hypophosporous Acid, 50, Irgafos 16 and its mixture.(E)-stain remover
Stain remover desirably is used for fabric sofetening composition of the present invention.The known any polymerization stain remover of those skilled in the art optionally is used for composition of the present invention.The polymerization stain remover is characterised in that to contain simultaneously to be useful on and makes hydrophobic fiber, the hydrophilic segment of polyester and nylon surface hydrophilic and being deposited on the hydrophobic fiber for example, after finishing, whole washing and rinse cycle keep adhering on the fiber, thereby as the hydrophobic fragment of the fixing agent of hydrophilic segment.This can guarantee with in the washing process afterwards of the spot after the detergent-treatment more easy cleaning fall.
If use, it is about 10.0% that stain remover accounts for about 0.01%-of detergent composition weight of the present invention usually, and it is about 5% typically to be about 0.1%-, preferably about 0.2%-about 3.0%.
Following this paper reference has been described and has been applicable to soil release polymer of the present invention.The US3959230 of the Hays of promulgation on May 25th, 1976; The US3893929 of the Basadur of promulgation on July 8th, 1975; The US4000093 of the Nicol of promulgation on December 28th, 1976 etc.; The US4702857 of the Gosselink of day in October, 1,987 27 promulgations; The US4968451 of the Scheibel of promulgation on November 6 etc.; The US4702857 of the Gosselink of day in October, 1,987 27 promulgations; The US4711730 of the Gosselink of promulgation on December 8th, 1987 etc.; The US4721580 of the Gosselink of promulgation on January 26th, 1988; The US4877896 of the Maldonado of promulgation on October 31st, 1989 etc.; The US4956447 of the Gosselink of promulgation on September 11 nineteen ninety etc.; The US5415807 of the Gosselink of promulgation on May 16 nineteen ninety-five etc.; April in 1987 disclosed Kud on the 22nd etc. EP0219048.
Other suitable stain remover is described in following this paper reference: the US4201824 of Violland etc.; The US4240918 of Lagasse etc.; The US4525524 of Tung etc.; The US4579681 of Ruppert etc.; US4240918; US4787989; US4525524; The EP279134A of Rhone-PoulencChemie, 1988; The EP457205A of BASF (1991); With the DE2335044 of UnileverN.V., 1974.
Commercially available stain remover comprises the METOLOSE SM100 that is produced by Shin-etsu Kagaku Kogyo K.K., METOLOSE SM200, SOKALAN class material, for example SOKALANHP-22, obtain ZELCON 5126 (Dupont) and MILEASE T (ICI) by BASF (Germany).(F)-sterilant
Comprise by at Philadelphia in the example that is used for the sterilant of the present composition by reagent weight 1 to 1000ppm, glutaraldehyde, formaldehyde, 2-bromo-2-nitro-the third-1 that the Inolex Chemicals of Pennsylvania sells with trade name Bronopol , 3-glycol and the 5-chloro-2-methyl-4-isothiazoline-3-ketone sold with trade name Kathon by Rohm and Haas Company and the mixture of 2-methyl-4-isothiazoline-3-ketone.(G)-spices
The present invention can contain spices.Suitable spices is open in US5500138, and described patent is classified this paper reference as.
The spices that is used for this paper comprises the mixture of fragrance material or material, comprises that natural (promptly obtaining by extracting flowering plant, vanilla, leaf, root, bark, timber, flower or plant), artificial (being the mixture of different natural oils or oil ingredient) and synthetic (promptly synthetic obtaining) have the material of smell.This material is by being accompanied by auxiliary substance, for example fixative, supplement, stability and solvent.These auxiliary substances are also included within the implication of " spices " that is used for this paper.Usually spices is the complex mixture of many kinds of organic compound.
Various natural matters not only can comprise volatile, also comprise medium evaporable and slight evaporable component, the synthetic material can comprise the representative of the fragrance material of all kinds, to become clear by following illustrative compilation: natural product, for example tree moss absolute, basil oil, citrus fruit oil (for example Oils, bergamot peel, orange wet goods), olibanum oil, myrtol, rusa oil, patchouli oil, Paraguay's petitgrain oil, wormwood oil; Alcohol, for example farnesol, Geraniol, linalool, vernol, phenylethyl alcohol, rhodinol, styryl carbinol; Aldehyde, for example citral, Helional
TM, jasmonal H, laurine, Lilial
TM(to the tertiary butyl-Alpha-Methyl dihydro cinnamon aldehyde), methyl nonyl acetaldehyde; Ketone, for example allyl ionone, α-Zi Luolantong, alpha, beta-lonone, isoraldein (different methyl-α-Zi Luolantong), methylionone; Ester; phenylium allyl ester for example; benzyl salicylate; propionic acid cinnamyl ester; citronellyl acetate; citronellyl ethoxolate; the acetate decyl ester; acetate dimethylbenzylcarbinol ester; butyric acid dimethylbenzylcarbinol ester; methyl aceto acetate; the ethanoyl ethyl acetate; isopropylformic acid hexenyl ester; acetate linalyl ester; methyl dihydrojasmonate; styroyl acetate; acetate vetiveryl ester etc.; lactone; peach aldehyde for example; the various components that are generally used for spices, for example musk ketone; indoles; p-menthane-8-mercaptan-3-ketone and methyleugenol.Equally, any conventional spices acetal known in the prior art or the ketal optional ingredient that can be used as conventional preparation spices adds in the composition of the present invention.This routine spices acetal and ketal comprise known methyl and ethyl acetals and ketal, and based on the acetal or the ketal of phenyl aldehyde, contain those of phenylethyl group, or the specialty products of developing recently, for example be called the material of describing in the United States Patent (USP) of " Acetals andKetals of Oxo-Tetralins and Oxo-Indanes ", referring to the US5084440 that transfers Giveudan Corp. of promulgation on January 28th, 1992 in name.Certainly, other nearest synthetic specialty products can be included in the fabric sofetening composition that is used for full preparation in the flavor compositions.They comprise oxo 1,2,3,4-tetralin and the oxo 1 that alkyl replaces, and the enol ether of 2-indane is as the US5332725 that transfers Givaudan of promulgation on July 26th, 1994; Or Schiff alkali, as the US5264615 that transfers Givaudan of promulgation on December 9th, 1991.
The spices that is used for the present composition does not have halogenated materials and nitro musk basically.
Spices can be by final composition weight 0%-10%, preferred 0.1%-5%, and more preferably the content of 0.2%-3% exists.Fabric sofetening composition of the present invention provides the fabric spices deposition of improvement.(H)-enzyme
The compositions and methods of the invention optionally adopt one or more enzymes, for example lipase, proteolytic enzyme, cellulase, amylase and peroxidase.Being used for preferred enzyme of the present invention is cellulase.In fact, this fermentoid also provides the color nursing efficacy to the processing fabric.Be used for cellulase of the present invention and comprise bacterium and fungal cellulase, they preferably have the pH optimum value between the 5-9.5.US4435307 has disclosed by Humicola insolens or humicola lanuginosa strain DSM 1800 or has belonged to the suitable fungal cellulase that the fungi of the generation cellulase 212 of Aeromonas obtains, and gives birth to the cellulase that the hepatopancreas of soft material Dolabella Auricula Solander extracts from the sea.GB-A-2075028, GB-A-2095275 and DE-OS-2247832 have also disclosed suitable cellulase.CAREZYME and CELLUZYME (Novo) are useful especially.Other suitable cellulase is open in WO91/17243, WO96/34092, WO96/34945 and the EP-A-0739982 of Novo.In commercial formulation now, typical content is every gram detergent composition 5mg (wt) at the most, and more common is the 0.01mg-3mg organized enzyme.In other words, composition of the present invention will contain 0.001%-5% by weight usually, preferred 0.01%-1% commercial enzyme preparation.The activity of zymin can define in particular cases in another way therein, for example for cellulase, and preferred corresponding activity unit (for example CEVU or cellulase viscosity unit of equal value).Composition for example of the present invention can be equivalent to the active content of about 0.5-1000CEVU/ gram composition and contain cellulase.The cellulase preparation that is used to prepare composition of the present invention has the activity of 1000-10000CEVU/ gram usually when liquid form, about 1000CEVU/ restrains when solid form.Other optional ingredient
The present invention can comprise that routine is used for the optional ingredient of fabric treatment composition, for example whitening agent, tinting material, tensio-active agent, antishrinking agent, fabric stiffener, spotting agent, sterilant, mycocide, antioxidant, for example Yoshinox BHT, sanitas, defoamer etc.
The present invention also can comprise the component that other is compatible, is included in disclosed material among WO96/02625, WO96/21714 and the WO96/21715, and dispersible polyolefin, for example disclosed Velustrol etc. in the PCT/US97/01644 that does not examine.The present invention also contains sequestrant selectively.
Adopting effect provided by the invention is that the composition that contains poly-amino-functional polymkeric substance is stablized by CGI.Therefore, on the other hand, it provides crystal growth inhibitor the stable purposes that contains the composition of amino-functional polymkeric substance.
Therefore, compare with the composition that does not adopt these stabilising method, composition of the present invention provides fabric nursing preferably.Therefore, in another aspect of this invention, it provides the method for nursing colored fabric, and it comprises the step that fabric is contacted with composition of the present invention.
The color nursing efficacy can be by range estimation or by measuring the evaluation of so-called Δ E value.
When adopting visual assessment, one group of expert grading person relatively uses according to scoring unit (PSU) of the panel standard of having set up and fabric that need not compositions-treated of the present invention.PSU value representation preferable performance (the PSU standard: the 0=indifference, I think 1=and there are differences, I know 2=and there are differences, I know and have many differences that I know complete difference 4=3=).
The other method of estimating the fabric color nursing efficacy is to measure so-called Δ E value.Δ E value is for example defining among the ASTMD2244.Δ E value is the calculating color distortion as defining among the ASTM D2244, i.e. two size and Orientations by the difference between the psychophysics colour stimulus of tristimulus values definition, or the calculating color distortion by the definition of tristimulus coordinates and luminance factor, calculate as color difference equation by one group of regulation in CIE 1976 CIELAB opponent-colors color spaces, Hunter opponent-colors color space, the Friele-MacAdam-Chickering color space or any suitable color space, defining.Use
Composition of the present invention is applicable to any family expenses treatment step, promptly as pretreatment compositions, the composition that adds as detergent additive, as the rinse cycle that is applicable to wash cycle or the composition that is used for the moisture eliminator sheet.Obviously, for the purpose of the present invention, can adopt repeatedly and use, for example handle fabric, use subsequently to be applicable to rinse cycle and/or to be suitable for the composition of the present invention of making the moisture eliminator sheet with pretreatment compositions of the present invention.Composition of the present invention can also be spraying, foam or aerosol form, and they for example can use or be applied in the rotary drum drier surface when flatiron.
The present invention illustrates that with following unrestricted embodiment wherein all percentage ratios are actives weight basis, except as otherwise noted.
In an embodiment, the components description of abbreviation has following implication: DEQA: two-(tallow base-oxygen base-ethyl) alkyl dimethyl ammonium chloride DOEQA: two-(oil base oxygen base ethyl) dimethyl methyl ammonium sulfate DTDMAC: Varisoft DHT DHEQA: two-(soft-tallow base-oxygen base-ethyl) hydroxyethyl methyls
Ammonium sulfate lipid acid: tallow fatty acids, IV=18 ionogen: calcium chloride DTDMAMS: two tallow base dimethyl methyl ammonium sulfate SDASA: the stearyl dimethyl amine of 1: 2 ratio: triple pressed stearic acid Glycosperse: polyethoxylated sorbitan monostearate, obtain clay by LonzaS-20: calcium bentonite, wilkinite L, by Southern Clay Products
Obtain TAE25: every mol of alcohol is with the tallow alcohol PEG of 25 moles of ethylene oxide ethoxylations: Macrogol 4000 PEI 1800 E1: as synthetic embodiment 1 synthetic ethoxylation polymine
(MW1800,50% activity) PEI 1800 E3: as synthetic embodiment 1 synthetic ethoxylation polymine
(MW1800,50% activity) PEI 1800 E7 A: as synthetic embodiment 4 synthetic ethoxylation polymines
Amine oxide (MW1800,50% activity) PEI 1200 E1: as synthetic embodiment 5 synthetic ethoxylation polymines
(MW1200,50% activity) PEI 1200 E2: as synthetic embodiment 5 synthetic ethoxylation polymines
(MW1200,50% activity) PEI 1200 E4: as synthetic embodiment 5 synthetic ethoxylation polymines
(MW1200,50% activity) PEI 1200 E7: as synthetic embodiment 5 synthetic ethoxylation polymines
(MW1200,50% activity) PEI 1200 E7 A: as synthetic embodiment 5 and 4 synthetic ethoxylation polyethyleneimine :s
The amine oxide of amine (MW1200,50% activity) dye-fixing agent 1: cationic dyestuff fixing agent (50% activity), by Ciba-Geigy
Obtain dye-fixing agent 2 with trade(brand)name Tinofix Eco: emulsive cationic dyestuff fixing agent (30% activity), by CHT-
Beitlich obtains NH4Cl with trade(brand)name Rewin SRF-O: ammonium chloride LAS: straight chain C
12Sodium alkyl benzene sulfonate TAS: tallow alcohol sodium sulfate C
25AS: C
12-C
15Straight-chain alkyl sulfate CxyEzS: with the C of z moles of ethylene oxide condensation
1x-C
1yBranched-chain alkyl sulfuric acid
Sodium C45E7: with the main C of average 7 moles of ethylene oxide condensations
14-C
15Straight chain
Primary alconol C25E3: with the C of average 3 moles of ethylene oxide condensations
12-C
15Branched-chain primary alcohol cationic ester: C
12/ C
14The mixture soap of cholinesterase: the straight chained alkyl that obtains by tallow and Oleum Cocois 80/20 mixture
Carboxylic acid sodium TFAA: C
16-C
18Alkyl N-methyl glucose amide TPKFA: C
12-C
14The full cut lipid acid of topping zeolite A: formula Na
12(AlO
2SiO
2)
12The hydrated sodium aluminosilicate of 27HxO, just
Grade particles is of a size of 0.1-10 micron citric acid: Citric Acid, usp, Anhydrous Powder carbonate: anhydrous sodium carbonate, particle size are 200-900 micron silicate: amorphous sodium silicate (SiO
2: Na
2O ratio=2.0) vitriol: anhydrous slufuric acid na citrate: citrate trisodium dihydrate, activity 86.4%, particle size
Distribution 425-850 micron MA/AA: 1: 4 toxilic acid/acrylic copolymer, the about 70000CMC of molecular-weight average: Xylo-Mucine Savinase: the proteolytic enzyme Carezyme of active 4KNPU/g: the cellulase Termamyl of active 1000CEVU/g: the amylase Lipolase of active 60KNU/g: the lipolytic enzyme of active 100KLU/g
By above-mentioned active sale of Novo Industries A/S, unless have in addition
Bright PB4: sodium perborate tetrahydrate, nominal formula: NaBO
23H
2OH
2O
2PB1: anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, nominal formula: NaBO
2H
2O
2TAED: tetra acetyl ethylene diamine DTPMP: diethylenetriamine five (methylene phosphonic acid salt), by Meng Shan all with
Trade(brand)name Dequest 2060 sells the photoactivation SYNTHETIC OPTICAL WHITNER: the capsular sulfonation zinc phthalocyanine phthalocyanine whitening agent of bag in the dextrin dissolved polymers: 4,4 '-two (4-anilinos-6-morpholino-1,3,5-triazines-2-
Base) stilbene-2:2 '-disulfonic acid disodium polysiloxane froth breaking amino): with polydimethyl agent silicone foam control agent, described Foam Control and the described branch of siloxanes-oxyalkylene copolymers as dispersion agent
The ratio of powder is 10: 1-100: 1.HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid PBT: 2-phosphinylidyne butane-1,2,4-tricarboxylic acid poly carboxylic acid: by the poly carboxylic acid of BASF with trade(brand)name Sokalan CP 10 sale
The compound oxyacetic acid: oxyacetic acid synthesizes embodiment 1-PEI1800E
1Preparation
Steps A)-ethoxylation is equipped with temperature survey and control, pressure survey, vacuum and inert gas purge at 2 gallons, take a sample and be used to import the stirring stainless steel autoclave of the device of oxyethane liquid.The clean steel cylinder of the oxyethane of placement～201b (ARC) provides oxyethane with liquid by pump in autoclave, steel cylinder is placed on the scale to monitor the changes in weight of steel cylinder.
The polymine (PEI) of 750g part (Nippon Shokubai, Epomin SP-018 have 1800 listed molecular-weight average, are equivalent to 0.417mol polymkeric substance and 17.4mol nitrogen functional group) adds autoclave.Sealing autoclave subsequently, with air purge (apply vacuum to-28 " Hg, then with nitrogen pressure to 250psia, empty to normal atmosphere subsequently).Under applying vacuum, the material in the autoclave is heated to 130 ℃.After about 1 hour, in autoclave, charge into nitrogen to about 250psia, cool off autoclave simultaneously to about 105 ℃.Incrementally in autoclave, add oxyethane then as time passes, monitor autoclave pressure, temperature and oxyethane flow simultaneously closely.Closing ring oxidative ethane pump, cooling off with restriction is increased by the temperature that any exothermic heat of reaction causes.In reaction process, when stagnation pressure is increased gradually, maintain the temperature at 100-110 ℃.After all 750g oxyethane added autoclave (roughly being equivalent to every PEI nitrogen functional group 1 moles of ethylene oxide), temperature rose to 110 ℃, makes the autoclave restir 1 hour.At this moment, apply vacuum to remove the unreacted ethylene oxide of any remnants.
Step B)-stir and heated mixt to 130 ℃ in, import about 100 feet by gas dispersion frit and reaction mixture
3Rare gas element (argon gas or nitrogen) makes the reaction mixture deodorizing.
Final reaction product is collected in the Glass Containers of sweeping with nitrogen slightly through cooling.
In other preparation process, neutralization and deodorization are carried out in reactor before discharging product.
PEI 1800 E if desired
7, between steps A and B, will comprise following catalysis addition step.
Be continuously applied vacuum, simultaneously autoclave be cooled to about 50 ℃, and the methanol solution of sodium methylate of input 376g 25% (1.74mol is to obtain the catalyst loading based on PEI nitrogen functional group 10%).Under vacuum methylate solution is sucked autoclave, autoclave temp controller setting point increases to 130 ℃ then.Power with the consumption of device monitoring agitator.Along with temperature and pressure monitoring agitator power.Along with remove methyl alcohol from autoclave, agitator power and temperature value increase gradually, and the viscosity of mixture increases and is stable in about 1 hour, illustrates that most of methyl alcohol are removed.Under vacuum, further heat and stirred the mixture other 30 minutes.
Remove vacuum, autoclave is cooled to 105 ℃, charge into nitrogen simultaneously, empty to normal pressure then to 250psia.In autoclave, charge into nitrogen to 200psia.Increase to add oxyethane as mentioned like that once more gradually, monitoring autoclave pressure, temperature and oxyethane flow closely maintains the temperature at 100-110 ℃ simultaneously simultaneously, with restriction is any because the temperature increase that exothermic heat of reaction causes.Added 4500g oxyethane (every mole of PEI nitrogen functional group produces 7 moles of ethylene oxide altogether) in several hours, temperature increases to 110 ℃, mixture restir 1 hour.
In the container of nitrogen purging, collect reaction mixture, transfer at last in the 22L three neck round-bottomed flasks that have heating and whipping appts.Add in the 167g methylsulfonic acid (1.74mol) and strong alkali catalyst.
Relative populations by the oxyethane of use in adjusting reaction time and the reaction adopts aforesaid method can prepare other preferred embodiment, for example PEI 1800 E2, PEI 1800 E3, PEI1800 E15 and PEI 1800 E20.Synthetic embodiment 2-PEI1800E
74.7% quaternized
500ml be equipped with add in the Erlenmeyer flask of magnetic stirring bar polymine (224g, 0.637mol nitrogen is as preparation among the synthetic embodiment 1) that degree of ethoxylation is 7 MW1800 and acetonitrile (Baker, 150g, 3.65mol).(0.030mol), stopper at room temperature stirs and spends the night then for Aldrich, 3.8g once to add methyl-sulfate in the solution that stirs rapidly.On rotatory evaporator,, by obtaining about 220g desired substance at about 80 ℃ of stripping solvents, be the dark-brown thick liquid then with Kugelrohr device (Aldrich) at about 60 ℃ of evaporation acetonitriles.
13C-NMR (D
2O) spectrum shows the peak at～58ppm do not exist corresponding to methyl-sulfate.
1H-NMR (D
2O) spectrum is presented at the peak partial dislocation of 2.5ppm (being connected in the not methylene radical of quaternized nitrogen) to about 3.0ppm.The synthetic quaternized PEI1800E of embodiment 3-4.7%
7Oxidation
Be equipped with at 500ml and add molecular weight 1800 in the Erlenmeyer flask of magnetic stirring bar, degree of ethoxylation is 7 and with methyl-sulfate about 4.7% quaternised polymine (121.7g, the oxidable nitrogen of about 0.32mol, as preparation among the synthetic embodiment 2), hydrogen peroxide (Aldrich, the 40g 50wt% aqueous solution, 0.588mol) and water (109.4g).Filled in flask then, at room temperature stirred solution spends the night after initial heat release.
1H-NMR (D
2O) compose the methylene peak that is presented at 2.5-3.0ppm and be moved to about 3.5ppm fully.In solution, add the 0.5%Pd of about 5g on alumina globule, solution was at room temperature left standstill about 3 days.Superoxide indication test paper is presented at system and does not have superoxide.Material stores as 46.5% aqueous solution.Synthetic embodiment 4-PEI 1800E
7The formation of amine oxide
Be equipped with at 500ml and add molecular weight 1800 and ethoxylation in the Erlenmeyer flask of magnetic stirring bar (PEI 1800, E to about 7 the oxyethyl group degree of every mole of nitrogen
7) polymine (209g, 0.595mol nitrogen is as preparation among the synthetic embodiment 1) and hydrogen peroxide (120g, the 30wt% aqueous solution, 1.06mol).Filled in flask then, at room temperature stirred solution spends the night after initial heat release.The sample of reaction mixture obtains
1H-NMR (D
2O) spectrum shows conversion fully.The response that produces adjacent to the methene proton of nitrogen oxide not is displaced to about 3.5ppm by the original position of about 2.5ppm.In reaction soln, add the 0.5%Pd of about 5g on alumina globule, solution was at room temperature left standstill about 3 days.Test soln finds that superoxide indication test paper is negative.The material that obtains is suitable for storing as the 51.1% active substance aqueous solution.Synthetic embodiment 5-PEI1200E
1Preparation
Steps A)-ethoxylation is equipped with temperature survey and control, pressure survey, vacuum and inert gas purge at 2 gallons, take a sample and be used to import the stirring stainless steel autoclave of the device of oxyethane liquid.Place the clean steel cylinder of oxyethane (ARC) of one～20lb, in autoclave, provide oxyethane, steel cylinder is placed on the scale to monitor the changes in weight of steel cylinder with liquid by pump.
The polymine (PEI) of 750g part (have 1200 listed molecular-weight average, be equivalent to about 0.625mol polymkeric substance and 17.4mol nitrogen functional group) adding autoclave.Sealing autoclave subsequently, with air purge (apply vacuum to-28 " Hg, then with nitrogen pressure to 250psia, empty to normal atmosphere subsequently).Under applying vacuum, the material in the autoclave is heated to 130 ℃.After about 1 hour, in autoclave, charge into nitrogen to about 250psia, cool off autoclave simultaneously to about 105 ℃.Incrementally in autoclave, add oxyethane then as time passes, monitor autoclave pressure, temperature and oxyethane flow simultaneously closely.Closing ring oxidative ethane pump, cooling off with restriction is increased by the temperature that any exothermic heat of reaction causes.In reaction process, when stagnation pressure is increased gradually, maintain the temperature at 100-110 ℃.After all 750g oxyethane added autoclave (being equivalent to every PEI nitrogen functional group 1 moles of ethylene oxide approximately), temperature rose to 110 ℃, makes the autoclave restir 1 hour.At this moment, apply vacuum to remove the unreacted ethylene oxide of any remnants.
Step B)-stir and heated mixt to 130 ℃ in, import about 100 feet by gas dispersion frit and reaction mixture
3Rare gas element (argon gas or nitrogen) makes the reaction mixture deodorizing.
Final reaction product is collected in the Glass Containers of sweeping with nitrogen slightly through cooling.
In other preparation process, neutralization and deodorization are carried out in reactor before discharging product.
PEI 1200 E if desired
7, between steps A and B, will comprise following catalysis addition step.
Be continuously applied vacuum, simultaneously autoclave be cooled to about 50 ℃, and the methanol solution of sodium methylate of input 376g 25% (1.74mol is to obtain the catalyst loading based on PEI nitrogen functional group 10%).Under vacuum methylate solution is sucked autoclave, autoclave temp controller setting point increases to 130 ℃ then.Power with the consumption of device monitoring agitator.Along with temperature and pressure monitoring agitator power.Along with remove methyl alcohol from autoclave, agitator power and temperature value increase gradually, and the viscosity of mixture increases and is stable in about 1 hour, illustrates that most of methyl alcohol are removed.Under vacuum, further heat and stirred the mixture other 30 minutes.
Remove vacuum, autoclave is cooled to 105 ℃, charge into nitrogen simultaneously, empty to normal pressure then to 250psia.In autoclave, charge into nitrogen to 200psia.Increase to add oxyethane as mentioned like that once more gradually, monitoring autoclave pressure, temperature and oxyethane flow closely maintains the temperature at 100-110 ℃ simultaneously simultaneously, with restriction is any because the temperature increase that exothermic heat of reaction causes.Added 4500g oxyethane (every mole of PEI nitrogen functional group produces 7 moles of ethylene oxide altogether) in several hours, temperature increases to 110 ℃, mixture restir 1 hour.
In the container of nitrogen purging, collect reaction mixture, transfer at last in the 22L three neck round-bottomed flasks that have heating and whipping appts.Add in the 167g methylsulfonic acid (1.74mol) and strong alkali catalyst.
Relative populations by the oxyethane of use in adjusting reaction time and the reaction adopts aforesaid method can prepare other preferred embodiment, for example PEI 1200 E2, PEI 1200 E3, PEI1200 E15 and PEI 1200 E20.
Also available following synthetic example 4 preparations of the corresponding oxidation amine of above-mentioned ethoxy base PEI.Synthetic embodiment 6-PEI1200E7's is 9.7% quaternized
500ml be equipped with the polymine (248.4g, 0.707mol nitrogen is as preparation among the synthetic embodiment 5) that adds MW1200 and degree of ethoxylation 7 in the Erlenmeyer flask of magnetic stirring bar and acetonitrile (Baker, 200ml).(0.067mol), stopper at room temperature stirs and spends the night then for Aldrich, 8.48g once to add whole methyl-sulfates in the solution that stirs rapidly.At about 60 ℃ of evaporation acetonitriles, by obtaining about 220g desired substance at about 80 ℃ of stripping solvents, be the dark-brown thick liquid by rotatory evaporator then with Kugelrohr device (Aldrich).
13C-NMR (D
2O) spectrum show do not exist corresponding to methyl-sulfate～peak of 58ppm.
1H-NMR (D
2O) spectrum is presented at peak (being connected to the not methylene radical of the quaternised nitrogen) partial dislocation of about 2.5ppm to about 3.0ppm.4.7% oxidation of the synthetic quaternized PEI1200E7 of embodiment 7-9.5%
Be equipped with at 500ml and add molecular weight 1200 in the Erlenmeyer flask of magnetic stirring bar, degree of ethoxylation is 7 and with methyl-sulfate about 9.5% quaternised polymine (144g, the oxidable nitrogen of about 0.37mol, as among the embodiment 6 preparation), hydrogen peroxide (Aldrich, 35.4g the 50wt% aqueous solution, 0.52mol) and water (100g).Filled in flask then, at room temperature stirred solution spends the night after initial heat release.
1H-NMR (D
2O) compose the methylene peak that is presented at 2.5-3.0ppm and be moved to about 3.5ppm fully.In solution, add enough sodium bisulfite 40% aqueous solution, make residual peroxide level drop to 1-5ppm.The sodium sulfate that forms makes aqueous phase separation, and it contains salt, contains organism on a small quantity or not but contain.Remove aqueous salt phase, obtain the polyethylenimine derivates of required oxidation, store as 52% aqueous solution.
Embodiment 1
Following is composition of the present invention:
Embodiment 2
| Component | A | B | C | D | E | F | G | H |
| DEQA | 2.6 | 2.9 | 18.0 | 19.0 | 19.0 | - | - | - |
| TAE25 | - | - | 1.0 | - | - | - | - | - |
| Lipid acid | 0.3 | - | 1.0 | - | - | - | - | - |
| Hydrochloric acid | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | - | - | - |
| PEG | - | - | 0.6 | 0.6 | 0.6 | - | - | - |
| Spices | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | ?0.1 | ?0.1 | 0.1 |
| Polysiloxane defoamers | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | - | - | - |
| PEI?1200?E1 | 3 | 3 | 3 | 3 | - | ?15 | - | 10 |
| PEI?1200?E2 | - | - | - | - | 3 | - | 10 | - |
| Dye-fixing agent 1 | - | 1 | 1 | 1 | - | - | 10 | - |
| Dye-fixing agent 2 | - | 2 | 2 | 2 | - | - | - | - |
| HEDP | 0.2 | - | - | 0.2 | - | 0.4 | - | 0.8 |
| Oxyacetic acid | - | 0.2 | - | - | 0.5 | - | 0.4 | - |
| The multi-carboxylate | - | - | 0.5 | - | - | 0.4 | - | - |
| Ionogen (ppm) | - | - | 600 | 600 | 1200 | - | - | - |
| Dyestuff (ppm) | 10 | 10 | 50 | 50 | 50 | - | - | - |
| Water and small number of groups balance-dividing amount to 100 | ||||||||
| Component | I | J | K | L | M |
| DEQA | 2.6 | 19.0 | - | - | - |
| Lipid acid | 0.3 | - | - | - | - |
| Hydrochloric acid | 0.02 | 0.02 | - | - | - |
| PEG | - | 0.6 | - | - | - |
| Spices | - | 1.0 | 0.1 | 0.1 | 0.2 |
| Polysiloxane defoamers | 0.01 | 0.01 | - | - | - |
| PEI?1200?E1 | 3 | 3 | 15 | - | 10 |
| PEI?1200?E4 | - | - | - | 10 | - |
| Dye-fixing agent 1 | - | 1 | - | - | 2.5 |
| Dye-fixing agent 2 | - | 2 | - | - | - |
| PBT | 0.2 | 0.2 | 0.4 | 0.8 | 0.5 |
| The multi-carboxylate | - | - | 0.4 | - | - |
| Ionogen (ppm) | - | 600 | - | - | - |
| Dyestuff (ppm) | 10 | 50 | - | - | - |
| Water and small number of groups balance-dividing amount 100 | |||||
| Component | ????N | O | ????P | ????Q | ????R | ????S |
| DTDMAC | ????- | ????- | ????- | ????15 | ????- | ????- |
| DEQA | ????2.6 | ???19.0 | ????- | ????- | ????2.6 | ????19.0 |
| TAE25 | ????0.3 | ????- | ????- | ????- | ????0.3 | ????- |
| Lipid acid | ????0.3 | ????- | ????- | ????- | ????0.3 | ????- |
| Hydrochloric acid | ???0.02 | ???0.02 | ????- | ????0.02 | ????0.02 | ????0.02 |
| PEG | ????- | ????0.6 | ????- | ????0.6 | ????- | ????0.6 |
| Spices | ????1.0 | ????1.0 | ????0.1 | ????1.0 | ????1.0 | ????1.0 |
| Polysiloxane defoamers | ???0.01 | ???0.01 | ????- | ????0.01 | ????0.01 | ????0.01 |
| PEI?1800?E1 | ????3 | ????3 | ????10 | ????3 | ????3 | ????3 |
| HEDP | ????0.2 | ????0.2 | ????- | ????- | ????- | ????- |
| PBT | ????- | ????- | ????- | ????- | ????0.2 | ????0.2 |
| Oxyacetic acid | ????- | ????- | ????0.2 | ????- | ????- | ????- |
| Poly carboxylic acid | ????- | ????- | ????- | ????0.2 | ????- | ????- |
| Dye-fixing agent 1 | ????1 | ????1 | ????10 | ????1 | ????1 | ????1 |
| Dye-fixing agent 2 | ????2 | ????2 | ????- | ????2 | ????2 | ????2 |
| Ionogen (ppm) | ????- | ???600 | ????- | ???600 | ????- | ???600 |
| Dyestuff (ppm) | ????10 | ????50 | ????- | ????50 | ????10 | ????50 |
| Water and small number of groups balance-dividing amount to 100 | ||||||
Following is the composition that is used as the sheet of moisture eliminator adding of the present invention:
Embodiment 3
| ???T | ???U | ???V | ???W | ???X | ???Y | ???Z | ???AA | ???BB | |
| ?DOEQA | ??40 | ??40 | ??25 | ??- | ??- | ??- | ??- | ??- | ??- |
| ?DHEQA | - | - | - | ??20 | ??20 | ??- | ??- | ??- | ??- |
| ?DTDMAMS | ??- | ??- | ??- | ??- | ??- | ??20 | ??20 | ??12 | ??60 |
| ?SDASA | ??30 | ??3 | ??30 | ??20 | ??20 | ??30 | ??30 | ??20 | ??- |
| ?Glycosperse?S- 20 | ??- | ??- | ??- | ??10 | ??10 | ??- | ??- | ??- | ??- |
| Zerol | ??- | ??- | ??- | ??- | ??- | ??20 | ??20 | ??10 | ??- |
| Clay | ??4 | ??4 | ??4 | ??3 | ??3 | ??4 | ??4 | ??4 | ??- |
| Spices | ??0.7 | ??0.7 | ??- | ??0.7 | ??0.7 | ??1.6 | ??1.6 | ??2.6 | ??1.4 |
| ?PEI?1800?E4 | ??- | ??- | ??5 | ??- | ??- | ??- | ??- | ??- | ??- |
| ?PEI?1200?E1 | ??- | ??- | ??- | ???4 | ??4 | ??2.2 | ??2.2 | ??- | ??- |
| ?PEI?1800?E3 | ??2 | ??2 | - | - | - | - | - | ??5 | ??7.0 |
| Dye-fixing agent 1 | ??2 | ??2 | ??5 | ??4 | ??4 | ??2.2 | ??2.2 | ??5 | ??3 |
| ?HEDP | ??0.2 | ??- | ??- | ??0.5 | ??- | ??- | ??- | ??- | ??0.7 |
| BPT | ??- | ??0.2 | ??- | ??- | ??0.9 | ??- | ??0.2 | ??- | ??- |
| Oxyacetic acid | ??- | ??- | ??0.2 | ??- | ??- | ??0.2 | ??- | ??- | ??- |
| Poly carboxylic acid | ??- | ??- | ??0.2 | ??- | ??- | ??- | ??- | ???0.4 | ??- |
| The stearic acid equal amount | |||||||||
Following is detergent formulation of the present invention:
| ????CC | ????DD | ????EE | |
| Zeolite A | ????24.0 | ????23.0 | ????23.0 |
| Vitriol | ????9.0 | ????- | ????- |
| ????MA/AA | ????4.0 | ????4.0 | ????4.0 |
| ????LAS | ????8.0 | ????8.0 | ????8.0 |
| ????TAS | ????- | ????2.0 | ????2.0 |
| Silicate | ????3.0 | ????3.0 | ????3.0 |
| ????CMC | ????1.0 | ????0.4 | ????0.4 |
| Whitening agent | ????0.2 | ????- | ????- |
| Soap | ????1.0 | ????- | ????- |
| ????DTPMP | ????0.4????? | ????0.4 | ????0.4 |
| ????C45E7 | ????2.5 | ????2.0 | ????2.0 |
| ????C25E3 | ????2.5 | ????2.0 | ????2.0 |
| Polysiloxane defoamers | ????0.3 | ????5.0 | ????5.0 |
| Spices | ????0.3 | ????0.3 | ????0.3 |
| Carbonate | ????13.0 | ????16.0 | ????16.0 |
| Citrate trianion | ????- | ????5.0 | ????5.0 |
| ????PB4 | ????18.0 | ????- | ????- |
| ????PB1 | ????4.0 | ????14.0 | ????14.0 |
| ????TAED | ????3.0 | ????6.0 | ????6.0 |
| The photoactivation SYNTHETIC OPTICAL WHITNER | ???0.02％ | ????- | ????- |
| ????Savinase | ????1.0 | ????1.0 | ????1.0 |
| ????Lipolase | ????0.4 | ????0.4 | ????0.4 |
| ????Termamyl | ????0.30 | ????0.6 | ????0.6 |
| ????Carezyme | ????- | ????0.6 | ????0.6 |
| ?PEI?1800?E7?AO | ????1.0 | ????- | ????- |
| ?PEI?1200?E7?AO | ????- | ????1.0 | ????1.0 |
| ????HEDP | ????0.2 | ????- | ????- |
| ????BPT | ????- | ????- | ????0.2 |
| Oxyacetic acid | - | ????0.2 | ???0.2 |
| Poly carboxylic acid | - | ????0.2 | ????0.2 |
| Equipoise (moisture and minor component) is to 100 | |||
Embodiment 4
Be prepared as follows liquid detergent formula of the present invention:
| ????FF | |
| C25AS | ????13 |
| C25E3S | ????2 |
| TFAA | ????6 |
| C12-14 alkyl dimethyl hydroxyethyl ammonium chloride | ????1 |
| Cationic ester | ????1.5 |
| TPKFA | ????15 |
| Citric acid | ????1 |
| Ethanol | ????2 |
| 1,2 propylene glycol | ????8 |
| The as many as pH of sodium hydroxide | ???7.5???? |
| DTPMP | ???1.2 |
| Savinase | ???0.5 |
| Termamyl(300KNU/g) | ???0.15 |
| Boric acid | ???1.5 |
| The mild clay of wilkinite type | ????4 |
| Suspended clay SD3 | ???0.3???? |
| PEI?1200?E7 | ????1 |
| HEDP | ???0.2 |
| Equipoise (moisture and minor component) | ???100 |
Claims (15)
1. Fabrid care composition that contains polyamine functional polymer and crystal growth inhibitor, wherein when described crystal growth inhibitor is selected from carboxylic acid, organic diphosphonic acid and their mixture, crystal growth inhibitor exists to be lower than 1% amount by composition weight meter.
2. according to the composition of claim 1, wherein said polymkeric substance contains and has formula V
(n+1)W
mY
nThe polyamine backbone corresponding to following formula of the polyamine of Z:
Or has a formula V
(n-k+l)W
mY
nY '
kThe polyamine backbone corresponding to following formula of the polyamine of Z:
Wherein k is less than or equal to n, and described polyamine backbone has greater than 200 daltonian molecular weight, wherein ⅰ) the V unit is the terminal units of following formula:
ⅱ) the W unit is the skeleton unit with following formula:
ⅲ) the Y unit is the branching unit of following formula:
And ⅳ) Y ' unit is a skeleton branch point or a chain link of following formula:
ⅴ) the Z unit is the terminal units of following formula:
Wherein skeleton connection R unit is selected from C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(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 their mixture; R wherein
1Be selected from C
2-C
6Alkylidene group and their mixture; R
2Be selected from hydrogen ,-(R
1O)
xB and their mixture; R
4Be selected from C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and their mixture; R
5Be selected from 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)-,-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 their mixture; R
6Be selected from C
2-C
12Alkylidene group or C
6-C
12Arylidene; R ' unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Thiazolinyl, C
7-C
22Arylalkyl, 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
3And their mixture; B is selected from 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 their mixture; R
3Be selected from C
1-C
18Alkyl, C
7-C
12Arylalkyl, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and their mixture; M is hydrogen or the water-soluble cationic that is enough to satisfy charge balance; X is a water soluble anion; M is the numerical value of 2-700; N is the numerical value of 0-350; P is the numerical value of 1-6; Q is the numerical value of 0-6; R is 0 or 1 numerical value; W is 0 or 1 numerical value; X is the numerical value of 1-100; Y is the numerical value of 0-100; Z is 0 or 1 numerical value.
3. according to the composition of claim 2, wherein R ' the unit of amino-functional polymkeric substance is selected from hydrogen, C
3-C
22Hydroxyalkyl, benzyl, C
1-C
22Alkyl ,-(R
1O)
xB ,-C (O) R
3,-(CH
2)
pCO
2-M
+,-(CH
2)
qSO
3-M
+,-CH (CH
2CO
2M) CO
2M and their mixture, preferred R ' unit is selected from hydrogen, C
1-C
22Alkyl ,-(R
1O)
xB ,-C (O) R
3With their mixture, more preferably R ' unit is-(R
1O)
xB.
4. according to the composition of one of claim 2 or 3, wherein x is 1-20, the numerical value of preferred 1-10.
5. according to one of any composition among the claim 1-4, wherein said polymkeric substance is with by weight at most to 90%, preferred 0.01%-50% actives by weight, more preferably the 0.1%-20% and the amount of most preferably pressing composition weight meter 0.5%-15% exist by weight.
6. according to one of any composition among the claim 1-5, wherein said crystal growth inhibitor is selected from carboxylic acid cpd, organic mono phosphonic acid, organic bisphosphate and their mixture, preferably organic diphosphonic acid.
7. according to the composition of claim 6, wherein said organic mono phosphonic acid is a 2-phosphoryl butane-1,2, the 4-tricarboxylic acid.
8. according to the composition of claim 6, wherein said organic diphosphonic acid compound is hydroxyl-ethane 1,1 di 2 ethylhexyl phosphonic acid.
9. according to one of any composition among the claim 1-7, wherein said crystal growth inhibitor is press composition weight meter 0.005%-0.50%, the amount existence of preferred 0.1%-0.2%.
10. according to one of any composition among the claim 1-9, wherein said composition also contains fabric softener.
11. the composition of claim 10, wherein said softening agent is a cationic fabric softener, is preferably selected from
Or formula:
Wherein Q is the carbonyl unit of following formula:
Each R unit is respectively hydrogen, C
1-C
6Alkyl, C
1-C
6Hydroxyalkyl and their mixture, preferable methyl or hydroxyalkyl; Each R
1The unit is respectively straight or branched C
11-C
22Alkyl, straight or branched C
11-C
22Thiazolinyl and their mixture, R
2Be hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl and their mixture; X is the negatively charged ion compatible with fabric softener; Subscript m is 1-4, preferred 2; Subscript n is 1-4, preferred 2.
12. according to one of any composition among the claim 1-11, wherein said composition also contains dye-fixing agent.
13. one of any composition among the claim 1-12, wherein said composition is a liquid form.
14. crystal growth inhibitor is used for the stable purposes that contains the composition of amino-functional polymkeric substance.
15. one kind provides the method for nursing to colored fabric, it comprises the step that the composition that makes among fabric and the claim 1-13 one of any contacts.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97870187 | 1997-11-24 | ||
| EP98202164.4 | 1998-06-27 | ||
| EP98202164A EP0924293B2 (en) | 1997-11-24 | 1998-06-27 | Use of a crystal growth inhibitor to reduce fabric abrasion |
| EP97870187.8 | 1998-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1284122A true CN1284122A (en) | 2001-02-14 |
Family
ID=26148309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98813264A Pending CN1284122A (en) | 1997-11-24 | 1998-11-20 | Stabilised fabric softening compsns |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP0924293B2 (en) |
| JP (1) | JP2001524618A (en) |
| CN (1) | CN1284122A (en) |
| BR (1) | BR9815004A (en) |
| CA (1) | CA2310434C (en) |
| WO (1) | WO1999027056A1 (en) |
Families Citing this family (5)
| 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 |
| WO2001016262A2 (en) * | 1999-09-02 | 2001-03-08 | Colgate-Palmolive Company | Fabric care composition containing polycarboxylate polymer and compound derived from urea |
| EP1238138A1 (en) * | 1999-10-22 | 2002-09-11 | The Procter & Gamble Company | Non-reactive fabric enhancement treatment |
| GB0229557D0 (en) * | 2002-12-19 | 2003-01-22 | Eastman Kodak Co | Partially oxidized polyalkyleneimine antioxidant for photographic developers |
| US20040261194A1 (en) * | 2003-06-27 | 2004-12-30 | The Procter & Gamble Company | Fabric article treating system |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3577556A (en) † | 1968-01-05 | 1971-05-04 | Dow Chemical Co | Polyamines stabilized with aminocarboxylate chelants |
| EP0112593B1 (en) * | 1982-12-23 | 1989-07-19 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
| US4602108A (en) † | 1984-08-01 | 1986-07-22 | Ethyl Corporation | Alkyl amine color inhibitor |
| GB9013784D0 (en) * | 1990-06-20 | 1990-08-08 | Unilever Plc | Process and composition for treating fabrics |
| EP0692019B1 (en) * | 1993-04-01 | 1998-02-11 | Unilever N.V. | Solid detergent briquettes |
| CN1145093A (en) * | 1994-03-30 | 1997-03-12 | 普罗格特-甘布尔公司 | Laundry detergent bars with improved whitening and dye transfer inhibition |
| PE6995A1 (en) * | 1994-05-25 | 1995-03-20 | Procter & Gamble | COMPOSITION INCLUDING A PROPOXYLATED POLYKYLENE OAMINE POLYKYLENE OAMINE POLYMER AS DIRT SEPARATION AGENT |
| US5726280A (en) * | 1994-08-24 | 1998-03-10 | Bayer Ag | Sulfonic acid group-containing polyaspartic acid derivatives, use thereof and prepartion thereof |
| US5460736A (en) † | 1994-10-07 | 1995-10-24 | The Procter & Gamble Company | Fabric softening composition containing chlorine scavengers |
| IL116638A0 (en) * | 1995-01-12 | 1996-05-14 | Procter & Gamble | Method and compositions for laundering fabrics |
| DE69608546T2 (en) * | 1995-03-03 | 2001-01-18 | The Procter & Gamble Company, Cincinnati | DETERGENT COMPOSITION CONTAINING DYE FIXING AGENTS AND CELLULASE |
| GB2303146A (en) * | 1995-07-08 | 1997-02-12 | Procter & Gamble | Detergent compositions |
| GB9513990D0 (en) * | 1995-07-08 | 1995-09-06 | Procter & Gamble | Detergent compositions |
| US5747440A (en) * | 1996-01-30 | 1998-05-05 | Procter & Gamble Company | Laundry detergents comprising heavy metal ion chelants |
| US5968893A (en) * | 1996-05-03 | 1999-10-19 | The Procter & Gamble Company | Laundry detergent compositions and methods for providing soil release to cotton fabric |
| BR9710663A (en) * | 1996-05-03 | 1999-08-17 | Procter & Gamble | Compositions for treating fabrics comprising modified polyamines |
| CN1237199A (en) † | 1996-09-19 | 1999-12-01 | 普罗格特-甘布尔公司 | Fabric softeners having increased performance |
-
1998
- 1998-06-27 EP EP98202164A patent/EP0924293B2/en not_active Expired - Lifetime
- 1998-11-20 BR BR9815004-9A patent/BR9815004A/en not_active IP Right Cessation
- 1998-11-20 WO PCT/US1998/024838 patent/WO1999027056A1/en not_active Application Discontinuation
- 1998-11-20 CN CN98813264A patent/CN1284122A/en active Pending
- 1998-11-20 JP JP2000522200A patent/JP2001524618A/en active Pending
- 1998-11-20 CA CA002310434A patent/CA2310434C/en not_active Expired - Fee Related
- 1998-11-20 EP EP98958669A patent/EP1034244A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999027056A1 (en) | 1999-06-03 |
| BR9815004A (en) | 2000-10-03 |
| CA2310434C (en) | 2005-11-15 |
| CA2310434A1 (en) | 1999-06-03 |
| EP1034244A1 (en) | 2000-09-13 |
| EP0924293B1 (en) | 2005-10-12 |
| EP0924293A1 (en) | 1999-06-23 |
| JP2001524618A (en) | 2001-12-04 |
| EP0924293B2 (en) | 2009-11-11 |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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